| JP2003227800 | GAS DETECTION MATERIAL |
ENİSOĞLU ATALAY VILDAN (TR)
ÖZKÖK FUNDA (TR)
ŞAHİN YEŞIM MÜGE (TR)
ONUL NIHAL (TR)
ASGAROVA KAMALA (TR)
ISTANBUL UENIVERSITESI CERRAHPASA REKTOERLUEGUE (TR)
T C ISTANBUL AREL UENIVERSITESI (TR)
| WO2015179273A1 | 2015-11-26 | |||
| WO2018130476A1 | 2018-07-19 |
| CLAIMS 1. A method of producing a reagent comprising the steps of: i. mixing 1 -Cloro anthraquinone and ethylene glycol, ii. adding 1-Dodecanethiol to mixed 1-Chloro anthraquinone and ethylene glycol, iii. adding aqueous potassium hydroxide solution to the mixture of (ii) process step and obtaining 1-(Dodecylthio)anthracene-9,10-dione molecule with reflux, iv. purifying of obtained 1-(Dodecylthio)anthracene-9,10-dione molecule, characterized by comprising; v. mixing the purified 1-(Dodecylthio)anthracene-9,10-dione molecule by adding into it an organic solvent, vi. obtaining the solution by diluting hydrogen peroxide with distilled water, vii. preparing iron (II) sulphate distilled water solution, viii. mixing the solution prepared in (v) process step and the solution prepared in (vii) process step, ix. mixing the solution prepared in (viii) process step and the solution prepared in (vi) process step, x. adding stabilizer to the solution obtained in (ix) process step. 2. A method of producing a reagent according to Claim 1 ; characterized by comprising; the process of adding a solution of trisodium citrate dihydrate as said stabilizer. 3. A method of producing a reagent according to Claim 1 or 2; characterized in that; 1- (Dodecylthio)anthracene-9,10-dione synthesis reaction is performed at a temperature of 110ºC to 120ºC. 4. A method of producing a reagent according to Claim 1 or 2; characterized by comprising; extracting the synthesized 1-(Dodecylthio)anthracene-9,10-dione molecule with chloroform. 5. A method of producing a reagent according to Claim 1 , characterized by comprising; said purifying process is made by colon chromatography. 6. A method of producing a reagent according to Claim 1 , characterized by comprising; acetonitrile is used as said organic solvent. 7. A method of producing a reagent according to Claim 1 , characterized by comprising; the process step of measuring the absorbance of the solution obtained in (x) process step at 304 nM. 8. A reagent for using in the determination of iron (II) sulphate, characterized by comprising; 1-(Dodecylthio)anthracene-9,10-dione molecule solved in a solvent. 9. A reagent according to Claim 8, characterized by comprising; said solvent is an organic solvent. 10. A reagent according to Claim 8, characterized by comprising; said solvent is acetonitrile or another solvent. 11. A kit for using in the determination of iron (II) sulphate, characterized by comprising; • the solution obtained by adding organic solvent to 1-(Dodecylthio)anthracene-9,10- dione molecule, • the solution obtained by diluting the hydrogen peroxide with distilled water, • the solution of trisodium citrate dihydrate or a solution having stabilizer feature, iron (II) sulphate in distilled water. |
TECHNICAL FIELD
The invention relates to a novel reagent called Catal’s reagent and kit for use in the determination of iron (II) sulphate in water systems, wastewater, biological materials, food products, soil samples and synthetic mixtures in the chemical, biochemistry, farming, agriculture and biotechnology industries.
STATE OF ART
Anthraquinones are active organic compounds known for reactions in important research areas such as medical, drug delivery systems, analytical applications, textile industry, materials and tissue engineering. Said compounds are the subject of particular interest due to their biological activities, such as anti-cancer, anti-tumor anti-microbial, anti-fungal, anti-inflammatory (S.K. Agarwal, 2000; R.K.Goel, 1991 ; N, Abu 2013; E. M. Perchellet, 2000). Anthraquinone compounds are one of the first G-Quadruplex DNA ligands. DNA interaction can be used as a potential transcription factor since they indicate the binding and recognition of the synthesis of DNA binding sites (Hsin et al., 2008; Lown, 1993).
In the state of art applications, there are various studies for the detection of iron (II) salts. For example, starch substrate 10-phenanthrol can be used for colorimetric detection of iron (II) (Gu and Zhou 1996; Choodum et al., 2019). The computer analytical chemistry techniques can be used for the determination of iron concentration in pharmaceutical products (Solana-Altabella et al., 2018). For the determination of spectrophotometric iron (III) by using Bis thiosemicarbazone ligand, (2Z, 2'Z)-2,2'-((4S, 5R)-4,5,6-trihydroxyhexane-1 ,2-diyldene)bis(N- phenylhydrazinecarbotioamide) chemometric methods are available (Rohani Moghadam et al., 2016). Iron (III) in iron (II) samples can be measured spectrophotometrically by using quercetin and morine (Balcerzak et al., 2008). In human serum (Carter 1971 ), bathophenanthroline and triazine are used for colorimetric measurement of iron (II) in fresh water (Peter et al., 1956; Stookey 1970; Vershoor and Molot, 2013). Iron (II) can be oxidized with ceric ammonium sulphate producing ferric thiocyanide colour complex, which is a useful reaction for the determination spectrophotometric iron (II) (Goswami and Kalita, 1988). A flow injection solid phase spectrophotometry is used for the detection of iron by the principle of interaction between iron (II) and 1-(2-thiazolylazo)-2-naphthol (Teixeira and Rocha, 2007). It has been reported that solid phase spectrophotometry can be used to detect 2,3-dichloro-6- (3-carboxy-2-hydroxy-1- naphthylazo) quinoxaline and iron (II) (Amin and Gouda, 2008). Determining iron in fuels such as bioethanol was performed by using the principle of colorimetric reaction between iron (III) and thiocyanide (Joao et al., 2019).
As a result, existing applications are insufficient in solving problems and negatives. This requires an improvement and innovation in the technical field.
BRIEF DESCRIPTION OF THE INVENTION
The present invention relates to a reagent and kit for use in the determination of iron (II) sulfate, which meets the requirements mentioned above, eliminates all disadvantages and brings some additional advantages.
The main aim of the invention is to obtain a sensitive, having high specificity and a wide range of concentration detection reagents and related kits that can be synthesized without requiring the use of hazardous chemicals in acid character. Further, it is possible to develop the concentration detection range of the reagent of the invention with the method modification.
Another aim of the invention is to develop a novel reagent and kit towards commercial use field for the colorimetric detection and quantitative analysis of dissolved iron (II) sulfate or iron (II) sulfate in solid form in various examples. When the solutions described by the invention are mixed in certain order and at certain concentrations, the iron (II) sulfate changes the color by rapidly reacts quantitatively and the color change can be analyzed in spectrophotometer against the blind. Further, it can be detected by color change in fabrics, surfaces or other materials that are qualitatively saturated with iron (II) or including iron (II) sulphate in undissolved form.
Another aim of the invention; without requiring the use of any method of detection, diluted or concentrated acid treatment, is to develop a novel non-corrosive reagent and related kit in order to easily, rapidly and safely determine iron (II) sulphate in a large concentration.
Another aim of the invention is to provide qualitative and quantitative determination of iron (II) sulfate with a new reagent called Catal’s Reagent, comprising 1 - (Dodecylthio)anthracene-9,10- dione. The structural and characteristic features and all advantages of the invention will become apparent from the following detailed description and drawings. Therefore, the evaluation should be made by taking into consideration the detailed description and figures.
BRIEF DESCRIPTION OF DRAWINGS
Figure 1 gives the chemical structure of 1- (Dodecylthio) anthracene-9,10-dione molecule.
Figure 2 gives maximum absorbance values of thio anthraquinone molecule in acetonitrile solvent in wavelength range of 185 nm - 700 nm in UV-visible spectrophotometer (A), maximum absorbance value of the reaction mixture formed after triple solution in the wavelength range of 185 nm - 700 nm (B).
Figure 3 gives the absorbance of iron (II) sulphate heptahydrate in 1 - 10 mg mL -1 (A) ve 0,2 - 1 mg mL -1 (B) concentrations.
Figure 4 gives iron (II) sulphate - absorbance values of color change relation to Catal reaction at 304 nm depending on time.
Figure 5 gives the synthesis reaction of 1 - (Dodecylthio) anthracene-9,10-dione molecule.
Table 1 gives the chemical parameters calculated by the B3LYP / 6-311 + G (d, p) method in various phases. (ΔE: Energy stability, c: electronegativity, EA: electron affinity, n: hardness, S: softness, ω: electrophilicity index, EHOMO: Highest Full Molecular Orbital Energy, ELUMO: Lowest Full Molecular Orbital energy)
DETAILED DESCRIPTION OF THE INVENTION
In this detailed description, preferred embodiments of the invention are described with respect to a better understanding of the subject matter such that it will not form any limiting effect.
The invention relates to a novel reagent and kit for use in the determination of iron (II) sulfate. Said reagent comprises a thioanthraquinone molecule and is referred to as Catal’s reagent.
In the method of synthesizing said thioanthraquinone molecule, the method described in patent application No TR 2016/19610 is used. Accordingly, first, 1 gram of 1-Chloro anthraquinone and preferably 25 mL of ethylene glycol are mixed in a reaction flask. Then, 0.83 grams of 1- Dodecanethiolare preferably added to the reaction flask and a yellowish reaction mixture is obtained. 10 ml of aqueous potassium hydroxide solution is preferably added to this mixture and the reaction temperature is increased to 110ºC to 120ºC. Preferably, after 48 hours of reflux, a yellow thio anthraquinone molecule (1- (Dodecylthio) anthracene-9,10-dione) is obtained. Figure 5 gives the synthesis reaction of 1-(Dodecylthio)anthracene-9,10-dione. The obtained thio anthraquinone (1 -(Dodecylthio) anthracene-9,10-dione) is preferably extracted with 30 mL of chloroform. The organic phase is washed with water and dried with sodium sulfate. The synthesized thio anthraquinone molecule (1-(Dodecylthio)anthracene-9,10-dione) is purified with the column chromatography. The chemical structure of the thio anthraquinone molecule 1- (Dodecylthio)anthracene-9,10-dione is characterized by spectroscopic methods (FT-IR, NMR, MS, UV).
The synthesized 1-(Dodecylthio)anthracene-9,10-dione is mixed by adding an organic solvent (preferably acetonitrile). At this stage, a solution is obtained by diluting hydrogen peroxide with distilled water. The solution of iron (II) sulfate in distilled water is also prepared. In the subsequent process step, the solution formed by adding organic solvent to 1-(Dodecylthio)anthracene-9,10- dione molecule is mixed with the solution of iron (II) sulfate in distilled water.
The solution diluted with hydrogen peroxide distilled water is added to the solution formed by adding organic solvent to 1 -(Dodecylthio)anthracene-9,10-dione molecule and the new solution obtained by mixing the solution of iron (II) sulphate in distilled water. Therefore, three separate solutions are mixed together. Preferably, 30 mM trisodium citrate dihydrate solution is added to said triple solution. Within the scope of the invention, it is also possible to use other stabilizers instead of trisodium citrate dihydrate. The absorbance of the obtained solution is measured at 304 nM.
The solution obtained by adding an organic solvent to 1 -(Dodecylthio) anthracene-9,10-dione molecule can be applied directly to fabrics, solids and surfaces containing iron (II) sulfate and the surface treated with this solution can be indicated as the presence of iron (II) sulphate qualitatively by the addition of the solution obtained by diluting the hydrogen peroxide with distilled water. In quantitative measurement different concentration ranges and different wavelengths can be used for spectrophotometric or other colorimetric analysis.
The kit developed for the determination of iron (II) sulphate comprises: • The solution obtained by adding organic solvent to 1- (Dodecylthio) anthracene-9,10- dione (Catal’s reagent),
• the solution obtained by diluting the hydrogen peroxide with distilled water,
• trisodium citrate dihydrate or a solution of stabilizer feature,
• the solution of iron (II) sulphate in distilled water.
A reagent is obtained by dissolving the 1-(Dodecylthio)anthracene-9,10-dione molecule preferably in organic solvents. The reagent obtained is called Catal’s reagent. Solvents such as ethanol, methanol and acetonitrile can be used as organic solvents in the invention. In the invention, preferably 20 mg of thio anthraquinone derivative (~ 0.816 mM) is dissolved in 60 mL of solvents, respectively and preferably, said Catal reagent is prepared by dissolving 20 mg of 1- (Dodecylthio)anthracene-9,10-dione in 60 mL of absolute acetonitrile (Merck, USA). Three peaks were observed in the wavelength range of 185 - 700 nm (Figure 2A). All mixtures prepared by mixing 1-(Dodecylthio)anthracene-9,10-dione with any solvent are referred as Catal’s reagent. It is important that the anthraquinone molecule (1-(Dodecylthio)anthracene-9,10-dione) to be used in producing said Catal’s Reagent is pure. For this purpose, in the invention, column chromatography is used according to the purification purposes.
In addition to acetonitrile, the reagent of the invention is also soluble in all organic solvents such as chloroform, dichloromethane, ethylacetate, ethanol and methanol and in dimethylsulfoxide (DMSO).
Figure 1 gives the chemical structure of the 1-(Dodecylthio)anthracene-9,10-dione molecule. The molecular weight of yellow, solid molecule is 408.6 g/mol and does not have toxic and carcinogenic feature. The chemical features of said molecule is given in Table 1 .
1 -Dodecanethiol molecule used in the synthesis reaction of 1-(Dodecylthio)anthracene-9,10- dione molecule is a compound from the thiol class. Thiols are biologically very active and their radical ion capturing capacity is known from the scientific studies (Devasagayam et al., 1991). 1- (Dodecylthio)anthracene-9,10-dione molecule synthesized with the synergy formed by both the anthraquinone skeleton and the thiol is a highly active compound.
In one embodiment of the invention, 17.5% H2O2 was prepared from a 35% stock solution of H2O2 by using distilled water (Merck KGaA, Kat. No. 1.08600.1000, Billerica, USA). Serial dilutions of iron (II) sulphate heptahydrate (VWR, Leuven, Belgium) were prepared by using 10 mg mL -1 stock solution in distilled water and 1-2-3-4-5-6-7-8-9-10 mg mL -1 concentrations were prepared by using distilled water. The concentration range was also analyzed at 0.2-1 mg mL -1 . 50 μL Η 2 O 2 çözeltisi (17.5%, ν: ν) was added to the mixture by adding 50 μL of Catal’s reagent to preferably 100 μL of iron (II) sulphate solution. Preferably 9 ml. of trisoduim citrat dihydrate 30 mM, VWR, Lot. No. 16D144103, Leuven, Belgium) was added to the reaction mixture. Absorbances were measured in a wavelength of 304 nM by using a UV-visible spectrophotometer (Shimadzu UV-2600, Cat. No. 206-27600-45, Kyoto, Japan). After the reaction, a single peak (Maximum absorbance, 304 nm) was obtained in the screening performed in a wavelength range of 185 - 700 nm. Figure 2B gives the maximum absorbance value of the reaction mixture formed after triple solution in the wavelength range of 185 nm to 700 nm.
This method can be used in all materials, mixtures, solutions containing iron (II) sulphate and Catal’s reagent, hydrogen peroxide, trisodium citrate dihydrate and sample can be used in different mixing ratios based on the concentration range of iron (II) sulfate in the desired samples.
The absorbance values measured depending on the iron (II) sulfate concentration increased linearly and R 2 values were above 0.9. Figure 3 gives the absorbance of iron (II) sulfate at concentrations of 1 - 10 mg mL 1 (A) and 0.2 - 1 mg mL 1 (B).
Depending on the color change, absorbance values can be stable up to 40 hours. Figure 4 gives the absorbance values of the color change based on iron (II) sulfate heptahydrate - Catal’s reagent reaction at 304 nm based on time.
The characteristics and characterization of the synthesized 1 -(Dodecylthio)anthracene-9, 10- dione molecule are given below.
Efficiency: 0,81 g (%48).
Rt (Chloroform) : 0,49.
FT-IR (cm- 1 ): v = 2960, 2915, 2846 (C-Harom), 1567 (C=C), 1666 (C=0).
UV-vis(Acetonitrile): λ max (logε) = 3,91 (436 nm), 4,14 (304 nm), 4,54 (266 nm), 4,66 (253 nm), 4,73 (233 nm).
1 H NMR (499,74 MHz, CDCI 3 ): δ= 0,81-0,83 (m, 3H, CH 3 ), 1,17-1 ,19 (m, 2H, CH 2 ), 1,52-1,55 (m, 2H, SCH 2 CH 2 ), 2,28-2,32 (m, 2H, SCH 2 CH 2 ), 7,18-8,25 (m, 7H, H arom ).
13 C NMR (125,66 MHz, CDCI3): δ= 12,24, 132,20, 132,46, 132,52, 133,08, 133,14, 133,64, 135,70, 136,69 (C arom and CHarom), 182,09 (C=0).
MS [+ESI]: m/z = 409,15 [M+H] + , [M-Dodecanthiol] + 241 C 26 H 32 0 2 S, (M, 408,60 g/mol). The characteristic C = O band was observed in the FT-IR spectrum at 1666 cm -1 . The carbonyl carbon in the anthraquinone skeleton was seen at 182.09 ppm in 13 C NMR. In the mass spectrum of the new anthraquinone analog, the molecular ion peak was confirmed as m/z = 409.15 [M + H] + . The ion fragment was observed at m/z = 241 [M-Dodecanethiol] + .
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