KR20100116866A - New organic europium(iii) complexes and a composite for latent fingerprint detector containing it as an active ingredient - Google Patents

Abstract

PURPOSE: A novel 1,10-phenanthroline Eu III complex compound and a composition for detecting latent fingerprint containing the same are provided to simplify complex compound synthesis. CONSTITUTION: A phenanthroline Eu III complex compound is denoted by general formula 1. A chemical composition for detecting latent fingerprint contains the complex compound of general formula 1 as an active ingredient. The concentration of the Eu III complex compound is 0.5×10^-6~ 0.5×10^-5M. The composition additionally contains cationic or anionic surfactant. A method for detecting latent fingerprint comprises: a step of spraying the chemical composition for detecting latent fingerprint to a test sample; and a step of irradiating UV ray to the test sample.

Description

New organic europium complexes and a composite for latent fingerprint detector containing it as an active ingredient

The present invention relates to a novel 1,10-phenanthroline europium (Eu (III)) complex compound and a composition for detecting latent fingerprints containing the same as an active ingredient.

Fingerprints are unique to each individual, and identity identification methods using them are considered the most reliable. Conventional representative methods for detecting latent fingerprints from a sample with or having a fingerprint attached to them include a hair brushing method and a color reaction method.

The bristling method rubs metal inorganic dye powders such as aluminum oxide (AlO ₃ ), silicon oxide (SiO ₂ ), silver (Ag) and titanium oxide (TiO ₂ ) onto the surface of the fingerprint sample with a bristle (brush) to rub the latent fingerprint. It is a method of making it present by attaching the powder and then displaying it on gelatin paper. This hair removal method requires the scrubbing of the latent fingerprints and requires skill, and the ridges of the latent fingerprints are frequently erased by an inexperienced person regardless of the wet or dry condition. In addition, when the surface of the sample is large or the number of oil products is large, the amount of work required for rubbing with bristles with careful attention in succession is too large and there are problems that the nanopowder is scattered and impairs health.

The color reaction method uses a color reaction resulting from a chemical reaction between a fingerprint component and a detection agent. Among them, a long-used method is to develop an amino acid in a fingerprint component with a ninhydrin solution (Oden S. and von Hofsten B. (1954) Detection of fingerprints by the ninhydrin, Nature . 173 : 449-450), silver acetate solution Methods for detecting chlorine ions and for detecting unsaturated fatty acids with urethral gas (Haan PVD, (2006) Physics and fingerprints. Contemporary Physics , 47 : 209-230). These methods are inconvenient for fingerprint detection process, and in particular, the detection resolution is low, there is a lot of room for improvement, and there is a risk to the health of the operator due to the volatility of the organic solvent.

Fingerprint identification determines the identity by observing and analyzing fine ridge flow patterns and various feature points (Kalle Karu, Anil K. Jain. (1996) Fingerprint classification.Pattern Recognition , 29 , 389-404 .: Jain, AK; Prabhakar, S .; Lin Hong. (1999) A multichannel approach to fingerprint classification.IEEE transactions on pattern analysis and machine intelligence, 21 , 348-359 .: Salil Prabhakar, Anil K. Jain, Sharath Pankanti. (2003) Learning fingerprint minutiae location and type.Pattern Recognition 36 , 1847-1857.). Therefore, in order to extract the accurate feature points of the latent fingerprints, the resolution of the feature points and the sensitivity of the detection technique must be improved significantly as a prerequisite. In particular, since the detection of the latent fingerprint is greatly influenced by the degree of porosity and the chromaticity of the background depending on the material of the surface on which the fingerprint is present, a detection method that can be applied to a wider area is required.

The present invention causes changes in the fluorescence emitted by reaction with various anionic compounds such as amino acids, chlorine ions, RNA, DNA, fatty acids, chlorine ions, and phospholipids contained in the fingerprint, thereby making it possible to express latent fingerprints quickly and accurately. It is an object to provide new Eu (III) complex compounds.

Still another object of the present invention is to provide a chemical composition for detecting latent fingerprints, which is easy to manufacture, has low manufacturing cost, and is more useful than conventional methods, and has a very high resolution for detecting latent fingerprints.

In addition, the present invention provides a latent fingerprint detection method that can quickly and accurately detect the latent fingerprint with a high resolution on the porous surface as well as non-porous surface in a variety of background chromaticity using the chemical composition for detecting the latent fingerprint. Protecting health by preventing the effects of risk and toxicity on the operator by blocking the risk of volatile by organic solvents and scattering by nanoparticles composed of inorganic metal powders, which are used in the method For that purpose.

The present invention for achieving the above object is characterized in that the 1,10-phenanthroline Eu (III) complex compound represented by the following general formula (1) or a hydroisomer thereof.

                             [Formula 1]

Provided that U, V, W, X, Y, and Z may be the same or different as ligands, and each may be H ₂ O (water), NH ₃ (ammonia), Cl (chlorine), or combined form NH ₂ -NH ₂ (hydrazine), (NH ₂ CH ₂ ) ₂ NH (dimethylene triamine), (NH ₂ CH ₂ CH ₂ ) ₂ NH (diethylene triamine) or phenanthroline ligands and are R, S, T May be the same or different as the non-ligand and are halogen (F, Br and Cl), H ₂ O or ClO ₄ .

Here, the ligand refers to a molecule or ion coordinating with Eu (III) ion, and the non-ligand refers to a molecule or ion not coordinating with a metal ion. A halogen or perchloric acid coupled to a non-ligand (ClO ₄ ^-) is actually negative (-) ions and positive ions are present metal ions and the whole complex compounds as would be coupled achieve a neutral, ion for convenience of description The notation of is omitted.

Neutral water molecules and negatively charged halogens It can exist as a ligand and can exist as a non-ligand. Accordingly, among the complex compounds having the same molecular formula, there are compounds in which a water molecule is substituted at the coordination region with a halogen atom and a compound which exists as a ligand and a compound which is present as a non ligand, and these compounds are referred to as 'hydroisomers'. The present invention includes compounds represented by the general formula (1) and their hydration isomers. In general, since the hydroisomers exhibit the same spectroscopic properties, it is not important in the fingerprint detection composition using spectroscopic properties whether water molecules or anions exist as ligands or non-ligands. Although not specifically mentioned hydroisomers, when referring to the compound below includes their hydroisomers. Perchloric acid anion (ClO ₄ ^-) in the present invention because the ion size is large, the dispersion of the negatively charged oxygen atoms binding to the metal ion in the center of the molecule due to the steric hindrance good present in a mainly non-ligand.

The more preferable chemical formula of the phenanthroline Eu (III) complex compound may be represented by the following formula (1-10).

[Formula 1]

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Chemical Formula 8]

[Formula 9]

[Formula 10]

The compounds of the present invention can be used for detection of latent fingerprints because the sensitivity of fluorescence emitted when reacted with anionic compounds such as trace amounts of RNA, DNA, fatty acids, amino acids, phospholipids, chlorine anions or nucleophiles changes in the fingerprint. have.

That is, the present invention provides a chemical composition for detecting latent fingerprints containing the Eu (III) complex compound of Formula 1 and its amine complex compound as an active ingredient.

The reaction between the phenanthroline Eu (III) complex and the anionic component in the fingerprint according to the present invention not only moves the UV absorption to a long wavelength, but also reduces the absorbance and increases the quenching in the excited state. Quantum efficiency is reduced. For this reason, the fluorescence intensity of the portion reacted with the fingerprint component is significantly reduced compared to the fluorescence intensity of the phenanthrroline Eu (III) complex compound itself, and this difference appears as a fingerprint.

The latent fingerprint detection composition (1-10) containing the Eu (III) complex compound of the present invention, as shown in Table 1, exhibited 34 to 81 feature points in fingerprints and was collected using a conventional ninhydrin. Compared with 13 features of latent fingerprint, it showed 2.5 ~ 6 times higher latent fingerprint display ability. In particular, 80 non-porous glass surfaces with a white background color and a black non-porous glass surface exhibited 80 feature points, thus exhibiting latent fingerprints regardless of the background color. In addition, 80 feature points appeared on the porous paper surface, showing high latent fingerprint performance regardless of the surface material.

In the chemical composition for detecting latent fingerprints, the Eu (III) complex compound of the present invention may be dissolved in a polar solvent such as water, and thus may be diluted in water, alcohol, or an aqueous solution thereof. At this time, the concentration of the Eu (III) complex compounds is preferably 0.5 × 10 ^-6 M ~ 5 × 10 ^-5 M. If the concentration of the complex compound is too low, the fluorescence intensity is too weak to reduce the sensitivity of latent fingerprint detection, and even if the concentration is increased, the concentration of components such as amino acids and chlorine anions in the fingerprint reacting with the Eu (III) complex compound is increased. Is very low, so the sensitivity is not increased further.

The composition may vary in intensity of fluorescence according to the form of a compound ionized by pH and not ionized, and may measure fluorescence due to the appearance of latent fingerprints in all pH regions, as shown in FIG. 5. Since the fluorescence intensity of the complex compound is significantly increased at 10.0, the pH of the compositions is preferably 6.0 ~ 10.0. The pH of the composition may be adjusted using an acid or base commonly used, such as Na ₂ HPO ₄ , KH ₂ PO ₄ , NaOH, and H ₃ PO ₄ .

It is also preferred to further contain cationic or anionic surfactants in the composition. When the composition further contains a surfactant, the fluorescence intensity increases by more than two times, and the effect of the surfactant's ionicity is not large. In the embodiment, the effects of NaLS (sodium dodecyl-sulfate) and CTAB (cetyltrimethylammonium bromide) were verified only as representative examples of the anionic and cationic surfactants, but the present invention is not limited thereto. chloride, octylpyridinium bromide, anionic surfactant sodium octylsulfonate, sodium dodecylsulfonate, sodium decylsulfate The same effect can be obtained. If the concentration of the surfactant is less than the critical micelle concentration (CMC) is not significantly affected by the concentration, a compound in the range of 1 × 10 ^-5 ~ 9 × 10 ^-3 M is preferred.

The present invention also comprises the steps of (A) spraying the sample chemical composition for detecting latent fingerprints; (B) providing a latent fingerprint detection method comprising the step of irradiating the sprayed sample with ultraviolet light and saturating the latent fingerprints manifested by fluorescence. At this time, it is preferable that the wavelength of the ultraviolet (UV) to be irradiated is 250 ~ 280nm and the saturation of the latent latent fingerprint can be easily taken by taking a picture using a digital camera.

As described above, according to the present invention, it reacts with anionic compounds such as various amino acids, chlorine ions, RNA, DNA, fatty acids, chlorine ions and phospholipids contained in the fingerprint, causing a change in the emitted fluorescence so that the characteristic features of the fingerprint can be identified. Therefore, the detection resolution of the latent fingerprint can be greatly improved as compared with the existing methods. Complex compounds of the present invention can be widely used as an alternative to the conventional methods because of the simple synthesis and the detection of latent fingerprints at low concentrations, the simple detection method, the excellent resolution and low manufacturing cost. Can be. In addition, the composition for detecting latent fingerprints of the present invention exhibits an excellent latent fingerprint display ability on a porous surface as well as a non-porous surface, and can quickly and accurately recognize a latent fingerprint having a high resolution regardless of the background color.

In addition, the composition for detecting latent fingerprints of the present invention can be manufactured and used in an aqueous solution state. Because it does not volatilize or scatter, the risk of volatility and scattering of nanoparticles consisting of metal inorganic dye powders by organic solvents of materials used in conventional methods is blocked, thereby preventing the effects of risk and toxicity on the user. There is no fear of harm.

With the development of this new concept of latent fingerprint detection material, it is expected that various challenges in detecting potential fingerprints at the field of forensic investigation can be smoothly overcome and resolved.

The present invention will be described in detail through the following examples. However, these examples are for illustrative purposes only and the present invention is not limited thereto.

Example

Preparation Example 1 Formula 1 (R = S = T = H) ₂ O) Preparation of Compound

0.37 g (1 mM) of europium (III) chloride hexahydrate (Eu (III) Cl ₃ .6H ₂ O) and 1,10-phenanthroline (hereinafter referred to as phen) in 200 ml of tetrahydrofuran 0.18 g (1 mM, 1 eq.) Was dissolved in the mixture and refluxed at 50 ° C. for 12 hours, followed by filtration to obtain a white solid compound of formula 1 (1,10-phenanthrolinetrichlorotriaquoeuropium (III) trihydrate: (phenEuCl ₃ (H ₂ O) ₃ ] (H ₂ O) ₃ )) 0.415 g (yield; 76%) were obtained.

Anal. Calcd: C ₁₂ H ₂₀ Cl ₃ EuN ₂ O ₆ : C, 26.37; H, 3.69; N, 5.12., Found: C, 25.65; H, 3. 60; N, 5.00.

Preparation Example 2 Preparation of Compound of Chemical Formula 2-5

A) Ammine complex compounds (Formula 2, R = S = H ₂ O, T = Cl)

Dissolve 0.22 g (0.4 mM, 1 eq) of the compound of Formula 1 prepared in Preparation Example 1 in 100 ml of 95% MeOH, and 0.056 ml (0.4 mM, 1) of 25% aqueous ammonia (NH ₄ OH: specific gravity, 0.908) using a micropipette. eq.) was added slowly to room temperature to 60 ℃ and refluxed for 6 hours. Then filtered to give a pale pink solid compound of formula 2 (1,10-phenanthrolinedichlorotriaquoammineeuropium (III) diaquochloride: ([phen (Cl) ₂ NH ₃ (H ₂ O) ₃ Eu] (H ₂ O) ₂ Cl)) 0.212 g (Yield; 97.3%) was obtained.

Anal. Calcd: C ₁₂ H ₂₁ Cl ₃ EuN ₃ O ₅ : C, 26.41; H, 3.88; N, 7.70, Found: C, 25.80; H, 3.97; N, 7.52.

B) Diammine complex compound (Formula 3, R = H ₂ O, S = T = Cl)

Except for using 0.11 ml (0.8 mM, 2 eq.) Of ammonia water, the compound of formula 3 (1,10-phenanchlorochlorotriaquodiammineeuropium (III) aquodichloride: ( 0.21 g (yield; 96%) of [phenClN ₂ H ₆ (H ₂ O) ₃ Eu] (H ₂ O) ₁ Cl ₂ )) was obtained.

Anal. Calcd: C ₁₂ H ₂₂ Cl ₃ EuN ₄ O ₄ : C, 26.46; H, 4.07; N, 10.29, Found: C, 26.00; H, 4.00; N, 9.97

C) Preparation of Triammine Complex Compound (Formula 4, R = S = T = Cl)

Except for using 0.168 ml (1.2 mM, 3 eq.) Of ammonia water, the compound of the formula (1,10-phenanthrothrotriaquotriammineeuropium (III) trichloride: ( 0.202 g (yield; 92.8%) of [phenN ₃ H ₉ (H ₂ O) ₃ Eu] Cl ₃ )) was obtained.

Anal. Calcd: C ₁₂ H ₂₃ EuN ₅ O ₃ Cl ₃ : C, 26.51; H, 4. 26; N, 12.88, Found: C, 25.88; H, 4.02; N, 13.01.

D) Preparation of Tetraammine Complex Compound (Formula 5, R = S = T = Cl)

A compound of formula (1,10-phenanthrothrodiaquotetraammineuropium (III) trichloride: (A) with the same method as the ammonia complex of A), except that 0.168 ml (1.2 mM, 3 eq.) Of ammonia water was used. 0.205 g (yield; 94.4%) of [phenN ₄ H ₁₂ (H ₂ O) ₂ Eu] Cl ₃ )) was obtained.

Anal. Calcd: C ₁₂ H ₂₄ EuN ₆ O ₂ Cl ₃ : C, 26.56; H, 4. 46; N, 15.49, Found: C, 27.00; H, 4. 12; N, 15.03

Preparation Example 3 Preparation of Compound 6-7.

A) Hydrazine complex compound (Formula 6, R = S = T = ClO ₄ Manufacturing

In 200 ml of 95% MeOH, 0.22 g (0.4 mM, 1eq.) Of the compound of formula 1 prepared in Preparation Example 1 and 0.025 ml (0.4 mM, 1eq) of hydrazine hydrate (NH ₂ -NH ₂ · H ₂ O, specific gravity; 1.03) .) Was added and refluxed at 60 DEG C for 12 hours and then filtered. The filtered product ([phenH ₄ N ₂ (H ₂ O) ₄ Eu] Cl ₃ ) was re-dissolved in a small amount of MeOH, and then 2-3 drops of sodium perchlorate (0.01 M) dissolved in water to increase crystallinity were added to room temperature. After stirring for 1 day while stirring in the white solid compound of the formula (1,10-phenan-throlinetetraaquo (hydrazine) europium (III) triperchlorate: ([phenH ₄ N ₂ Eu (H ₂ O) ₄ ] ( ClO ₄ ) ₃ )) 0.205 g (yield; 68%).

Anal. Calcd: C ₁₂ H ₂₀ Cl ₃ EuN ₄ O ₁₆ : C, 19.62; H, 2. 74; N, 7.63, Found: C, 19.37; H, 2.48; N, 7.66

B) Bishydrazine Complex (Formula 7, R = S = T = ClO ₄ ^- Manufacturing

A compound obtained by the same method as the hydrazine complex compound (6) of A) ([phenH ₈ N ₄ (H ₂ O) ₂ Eu] Cl ₃ ), except that 0.168 ml (1.2 mM, 3 eq.) Of hydrazine hydrate was used. ) Was added 2-3 drops of sodium perchlorate (0.01 M) to the white solid compound of formula (1,10-phenanthrolinediaquo (bis-hydrazine) europium (III) triperchlorate: ([phenH ₈ N ₄ (H ₂ O) ₂ Eu ] (ClO ₄ ) ₃ )) 0.208 g (yield; 71%).

Anal. Calcd: C ₁₂ H ₂₀ Cl ₃ EuN ₆ O ₁₄ : C, 19.73; H, 2.76; N, 11.50, Found: C, 19.57; H, 2.71; N, 11.24.

Preparation Example 4 Preparation of Compound of Formula 8-9

A) Preparation of Dimethylenetriamine Complex Compound (Formula 8, R = S = T = Cl)

First, dimethylene triamine was prepared according to the method of Miyakoshi, K. et al. ( Tetrahedron 57, 3355-3360, 2001). More specifically, a reaction obtained by dissolving 1 g of 2,4-dithiobiuret (sigma) and 20 ml of Ranney-Ni (W-2) (0.5 g / ml) in 20 ml of Tetrahydrofurane (THF) was stirred under an argon gas at room temperature for 5 hours. I was. The reaction mixture was filtered through celite, washed with THF, the filtrates were collected, evaporated under reduced pressure, purified by silica gel column chromatography (developing solvent; Ethylacetate: Ethanol = 2: 1), and the filtrate was evaporated to give dimethylene triamine 0.12 as an oily liquid. g (yield: 22%) was obtained.

To 0.2 ml of MeOH, 0.22 g (0.4 mM, 1eq.) Of the compound of Formula 1 prepared in Preparation Example 1 and 0.03 g (0.4 mM, 1eq.) Of dimethylene triamine prepared above were added thereto, and the mixture was refluxed at 60 ° C. for 12 hours, followed by filtration. (1,10-phenanthroline (N, N ', N''-dimethylenetriammine) triaquoeuropium (III) trichloride: ([phenC ₂ N ₃ H ₉ Eu (H ₂ O) ₃ ] (Cl) ) ₃ )) 0.16 g (yield; about 70%).

Anal. Calcd: C ₁₄ H ₂₃ EuN ₅ O ₃ Cl ₃ : C, 29.62; H, 4.08; N, 12.34, Found: C, 30.06; H, 4. 15; N, 13.00

B) Preparation of Diethylenetriamine Complex Compound (Formula 9, R = S = T = Cl)

To 0.2 ml of MeOH, 0.22 g (0.4 mM, 1 eq.) Of Compound (1) prepared in Preparation Example 1 and 0.043 ml (0.4 mM, 1 eq.) Of diethylenetriamine (specific gravity: 0.95) were added by a micropipette and added at 60 ° C. After refluxing for 12 hours, the mixture was filtered to give a pale pink solid compound of formula 9 (1,10-phenanthroline (N, N'N ''-diethylenetriamine)-triaquoeuropium (III) trichloride: ([phenC ₄ H ₁₃ EuN ₃ (H ₂ O) ₃ ] (Cl) ₃ )) 0.162 g (yield; about 68%).

Anal. Calcd: C ₁₆ H ₂₇ EuN ₅ O ₃ Cl ₃ : C, 32.26; H, 4.57; N, 11.76, Found: C, 32.86; H, 4.83; N, 12.00.

Preparation Example 5 Formula 10 (R = S = Cl, T = H) ₂ O) Preparation of Compound

To 200 ml of ethyl alcohol, 0.37 g (0.1 mM, 1 eq.) Of europium (III) chloride hexahydrate (Eu (III) Cl ₃ · 6H ₂ O) and 0.36 g (0.1 mM, 2 eq.) Of 1,10-phenanthroline were dissolved. After refluxing at 12 ° C. for 12 hours, the precipitate was filtered and washed with ethyl ether to give a white solid compound of formula 10 (chloro (bis-1,10-phenanthroline) triaquo- europium (III) aquodichloride: ([phen ₂ EuCl 0.585 g of ₁ (H ₂ O) ₃ ] Cl ₂ (H ₂ O)) was obtained (yield; 87%) and washed with ether solution.

Anal. Calcd: C ₂₄ H ₂₄ Cl ₃ EuN ₄ O ₄ : C, 41.73; H, 3.50; N, 8.11, Found: C, 41.64; H, 3. 28; N, 8.15.

Example 1 Confirmation of Reaction of Eu (III) Complex with Amino Acids

UV-Vis spectrum and fluorescence spectrum were observed to confirm the reactivity of Eu (III) complex compounds according to the present invention with amino acids in the fingerprint component. The UV spectra of the Eu (III) complex compounds (1-10) prepared in the above preparations were all absorbed at λ _max . = 265 nm (π → π *; forbibben) (ε = 2.5 × 10 ⁴ to 3.0 × 10 ⁴ ), only the Eu (III) complex compound of Formula 10 in which two chromophores of phenanthroline were combined showed a hyperchromic effect (ε = 6.50 × 10 ⁴ ) with increased absorbance compared to other compounds. The fluorescence spectrum showed maximum luminescence at λ ₁ = 361.5 nm and λ ₂ = 720.5 nm. This is because the absorbance and luminescence effect of the phenanthroline europium complex compound of the present invention is due to phenanthroline, only the results for the Eu (III) complex compound of Formula 7 prepared in Preparation Example 3 Although described, the other compounds showed similar results.

More specifically, 1 × 10 ⁻⁵ M each of Eu (III) complex compound of Formula 7 and / or tryptophan of Preparation Example 3 was added to distilled water by reaction using a UV-Vis spectrometer (Scinco S-3100). The change in the UV-Vis spectrum was measured and measured in the Fluorescence spectrometer of LS-45 model of Perkinelmer, as shown in FIG.

1 shows the UV-Vis spectrum and a represents the Eu (III) complex compound represented by Chemical Formula 7; b is tryptophan; c corresponds respectively to the UV spectrum of these mixtures. As a result of comparing the UV peaks, the UV-Vis absorbance peaks of the Eu (III) complex of Formula 7 show a hypsochromic effect in which the 227 nm peak shifts to the left when tryptophan is added, and the hypochromic in which the near peak of 264 nm goes down. It showed an effect phenomenon and changed to another substance by reacting with amino acid tryptophan, one of the fingerprint components.

As a result of confirming the fluorescence spectrum of the right side of Figure 1, the material produced by the reaction showed a peak at 361.5 nm and 720.5 nm, respectively. Among them, it was confirmed that the intensity at 361.5 nm is higher. On the right, the black spectrum is the fluorescence of Eu (III) complex compound (a), and the red spectrum is the fluorescence of Eu (III) complex compound and tryptophan reaction mixture (c).

Example 2 latent fingerprint detectability test on non-porous glass surface

The detection ability of the latent fingerprint was measured by using the Eu (III) complex compound of Formula 7. More specifically, after fingerprinting the glass slide, an aqueous solution of Eu (III) complex compound of Formula 7 (1 × 10 ^-4 M) was applied with a soft brush or sprayed with a spray, followed by UV lamp (model UVGL-58). nm The photo was taken under UV light and is shown in FIG. 2. For comparison, black ink was applied to the fingerprint area, and fingerprints were taken on a glass slide and the fingerprints were exposed with ninhydrin and photographed together. For detection of latent fingerprints using ninhydrin, the BVDA international No. The B-78500.d product was sprayed.

FIG. 2 is a photograph of fingerprints taken with black ink, the center using Eu (III) complex compound of Formula 7, and the right using ninhydrin. The characteristic points of the fingerprints exhibited using the ink and the compound of the present invention were measured using AFIS (Automated fingerprint identification systems), and the number of the characteristic points was calculated. As a result, 69 fingerprints using black ink measured as a control group, Eu (III) In case of fingerprint using complex compound 7, 81 feature points were shown.

Example 3: Test for latent fingerprint detection on porous paper surface

In the case of latent fingerprint detection, since the detection on the porous surface is generally less effective than the detection on the non-porous surface, the Eu (III) complex compound prepared in Preparation Examples 1 to 5 was used on A4 paper which is a porous surface. Potential fingerprints were revealed and their efficacy was verified. More specifically, as a sample for the appearance of latent fingerprints, the Eu (III) complex compounds prepared in Preparation Examples 1 to 5 were dissolved in water at a concentration of 1 × 10 ^-4 M to 1 × 10 ^-5 M, respectively, and fingerprints were taken. Was sprayed onto A4 paper. The latent fingerprints were exposed to UV at 254 nm wavelength, measured by AFIS system, and the total number of feature points was calculated by classification. The results are summarized in Table 1. For comparison, the results using ninhydrin, the most commonly used latent fingerprint detection material, are also described. A commercially available product (The BVDA international No. B-78500.d) was sprayed onto fingerprinted A4 paper for latent fingerprint detection using ninhydrin (FIG. 2, feature points: 13). The numerical values shown in Table 1 are average values for the number of feature points obtained as a result of detecting five latent fingerprints per Eu (III) complex compound.

According to Table 1, the Eu (III) complex compounds represented by the formulas (6) and (7) showed the best latent fingerprint appearance ability, and the average number of 80 feature points was shown. ) Complex compounds also showed a number of 34 feature points, it was confirmed that the latent fingerprint display ability of 2.5 to 6 times higher than ninhydrin used in the prior art.

FIG. 3 is a photograph showing latent fingerprints on glass slides and white A4 paper using Eu (III) complex compound of Chemical Formula 7. FIG. The two photographs on the left show the latent fingerprints on the glass slide, the non-porous surfaces of the black and white background, respectively. The right photograph shows the latent fingerprints on the A4 paper, the porous surface. The number of feature points of 80 and 81 was not significantly different, and it could be confirmed that the synthetic material showed the ability to display latent fingerprints without being significantly affected by the porosity of the surface.

Example 4 Identification of Optimal pH of Composition for Potential Fingerprint Representation

Eu (III) complex compound of the present invention is a property that the fluorescence intensity is reduced when reacting with the fingerprint component, so that the first fluorescence sensitivity of the compound was identified in order to explore the optimal composition of the composition.

In order to find out the optimal pH condition when using the new latent fingerprint detection reagent, first, the UV absorbance spectra were measured for each pH, and the absorbance for each pH at 264 nm, the maximum absorption wavelength (λ _max ), was shown in FIG. 4. Eu (III) complex compound of Formula 7 was used as an aqueous solution of 1.7 × 10 ^-5 M concentration, pH was adjusted by using NaOH and H ₃ PO ₄ . As can be seen in the right graph of Figure 4, the absorbance at 264 nm showed a maximum value at pH 9.0. As the pH was further increased, it was confirmed in the spectrum on the left that the maximum absorption wavelength shifted to the long wavelength region and the absorbance at 264 nm decreased.

Irradiation of 264 nm of the maximum absorption wavelength to an aqueous solution of the Eu (III) complex compound at a concentration of 1.1 × 10 ⁻⁶ M was performed to measure the fluorescence spectra of each pH in the same manner as the UV spectrum measurement, and to measure pH 361.5 nm. It is shown in Figure 5 together with the luminous intensity at. As can be seen in the fluorescence spectrum on the left of FIG. Fluorescence peaks were observed in the 300-500 nm range (λ ₁ = 361.5 nm) and 600-800 nm range (λ ₂ = 720.5 nm), and stronger fluorescence was observed in the 300-500 nm range. . 5 is a graph showing the intensity for each pH at 361.5 nm showing the strongest emission intensity. As the pH changes from low to high pH, the intensity increases and then decreases again at pH 9.0.

Although not separately shown, the fluorescence intensity at 720.5 nm also increased in intensity from low pH to high pH and then decreased at pH 9.0.

Example 5 Confirmation of the Effect of Surfactant on the Composition for Potential Fingerprint Display

The effects of surfactants were investigated to facilitate chemical bonding of highly polar composites with less polar fingerprints. UV and fluorescence spectra were measured by adding varying concentrations of the surfactant under the same conditions as in Example 5 at pH 9.0 showing the strongest absorbance and emission intensity for the Eu (III) complex compound of Formula 7. As the surfactant, anionic surfactant sodium dodecylsulfate (NaLS) and cationic surfactant hexadodecylammonium bromid (CTAB) were used to change the concentration within the concentration range not exceeding the critical micell concentration (CMC). For reference, the CMC of NaLS is 9.8 × 10 ⁻³ M and the CMC of CTAB is 9.8 × 10 ⁻³ M. 6 and 7 illustrate UV spectra and fluorescence spectra according to NaLS concentrations, and FIGS. 8 and 9 illustrate UV spectra and fluorescence spectra according to CTAB concentrations, respectively.

As can be seen in FIG. 6, NaLS exhibited the largest absorbance of 265 nm at a concentration of 2.0 × 10 ⁻³ M, and the fluorescence intensity at 363.5 nm and 725.5 nm in FIG. 7 was compared with that without NaLS treatment. The intensity increased greatly. Fluorescence intensity also increased most at 2.0 × 10 ⁻³ M, as did UV absorbance.

8 and 9 show results for CTAB, which is a cationic surfactant, showing that the highest absorbance was obtained at 1.3 × 10 ⁻⁴ M in FIG. 8. 9 for fluorescence spectra, the fluorescence intensity at 363.5 nm and 725.5 nm was increased compared to when CTAB was not treated.

NaLS and CTAB increased fluorescence intensity significantly compared to when no surfactant was added, but the effect of surfactant concentration was not significant and the effect of surfactant ionicity was not significant.

1 is a UV spectrum and a fluorescence spectrum showing the reaction of tryptophan with Eu (III) complex compound of one embodiment of the present invention.

Figure 2 is a photograph showing the latent fingerprint detection ability of one embodiment Eu (III) complex compound of the present invention.

3 is a photograph showing the latent fingerprint detection ability of one embodiment Eu (III) complex of the present invention in comparison with the non-porous surface and the porous surface according to the change of the background color.

Figure 4 is a graph showing the change in the UV spectrum and the absorbance of λ ₁ = 265 nm with pH of one embodiment Eu (III) complex compound of the present invention.

Figure 5 is a graph showing the change in fluorescence spectrum with pH of one embodiment Eu (III) complex compound of the present invention.

Figure 6 is a graph showing the change in the UV spectrum according to the concentration of the anionic surfactant NaLS in an aqueous solution of pH 9.0 of one embodiment Eu (III) complex compound of the present invention.

FIG. 7 is a graph showing changes in fluorescence spectra according to the concentration of NaLS, an anionic surfactant, in an aqueous solution of pH 9.0 of an embodiment Eu (III) complex compound.

8 is a graph showing the change in UV spectrum according to the concentration of the cationic surfactant CTAB in an aqueous solution of pH 9.0 of one embodiment Eu (III) complex compound of the present invention.

Figure 9 is a graph showing the change in fluorescence spectrum according to the concentration of the cationic surfactant CTAB in an aqueous solution of pH 9.0 of one embodiment of the present invention Eu (III) complex.

Claims (9)

Penanthroline Eu (III) Complex Compounds Represented by General Formula 1 Or a hydroisomer thereof.

                           [Formula 1] However, U, V, W, X, Y and Z may be the same or different from each other, respectively, H ₂ O, NH ₃ , Cl or in the form of bonding to each other NH ₂ -NH ₂ , (NH ₂ CH ₂ ) ₂ NH, (NH ₂ CH ₂ CH ₂ ) ₂ NH, or phenanthroline ligands, RST is F, Br, Cl, H ₂ O or ClO ₄ . A chemical composition for detecting latent fingerprints comprising the Eu (III) complex of claim 1 as an active ingredient. The method of claim 2, The concentration of the Eu (III) complex compound of claim ¹ is 0.5 × 10 ^-6 ~ 0.5 × 10 ^-5 M, characterized in that the latent fingerprint detection chemical composition. The method of claim 2, PH of the composition is a chemical composition for detecting latent fingerprints, characterized in that 6 to 10. The method according to any one of claims 2 to 4, The composition is a chemical composition for detecting latent fingerprints further containing a cationic or anionic surfactant. The method of claim 5, The surfactant is NaLS (sodium dodecylsulfate) or CTAB (hexado- decylammonium bromid) characterized in that the latent fingerprint detection chemical composition. The method of claim 6, The concentration of the surfactant is Chemical composition for detecting latent fingerprints, characterized in that 1 × 10 ^-5 ~ 9 × 10 ^-3 M. (A) spraying a sample with a chemical composition for detecting latent fingerprints of claim 2; (B) irradiating the sprayed sample with ultraviolet light to extract latent fingerprints exhibited by fluorescence; The latent fingerprint detection method comprising a. The method of claim 8, The wavelength of the ultraviolet rays of step (B) is 250 ~ 280nm and the wavelength of fluorescence is 320 ~ 450nm or 500 ~ 800nm The latent fingerprint detection method characterized in that the.

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