• Journal of the Korean Chemical Society
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• v.47 no.6
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• pp.569-577
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• 2003

Ligands, Br-PEMP, Cl-PEMP and $CH_3O-PEMP$ having Br, Cl and $CH_3O$ substituents at 5-position of the $N_2O$ tridentate ligand, 2-[(2-pyridine-2-ethylamio)-methyl]-phenol (H-PEMP) containing pyridine and phenol were synthesized. Another ligand, Naph-PEMP having pyridine and 2-hydroxy-1-naphthalene was also synthesized. The ligands were characterized using elemental analysis, UV-visible, IR, $^1H\;NMR\;and\;^{13}C$ NMR spectroscopy and mass analysis. The potentiometric titration study in aqueous solution revealed that the proton dissociation of the ligands occurred in three steps and the order of overall proton dissociation constants (log${\beta}$) was $CH_3O-PEMP$ > Naph-PEMP > H-PEMP > Cl-PEMP > Br-PEMP. The order of stability constants (logML and log$ML_2$) of their transition metal complexes was Co(II) < Ni(II) < Cu(II) > Zn(II). The order in their stability constants values of each transition metal complex agreed well with that in overall proton dissociation constant value of the ligands.

• Journal of the Korean Chemical Society
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• v.39 no.9
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• pp.698-704
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• 1995

The ion-selective membrane fabricated with 33 wt% PVC, 66 wt% o-NPOE and 1 wt% 4'-benzothiazolylbenzo-15-crown-5 (TB15C5) as a neutral carrier exhibited an enhanced selectivity to potassium ion over sodium ion compared to those prepared with other 15-crown-5 or 18-crown-6 derivatives. The potentiometric properties (response slope, selectivity, detection limits and lifetime) of TB15C5-based ISE membranes along with those based on valinomycin, benzo-15-crown-5 (B15C5), 4'-aminobenzo-15-crouwn-5 (AB15C5), benzo-18-crown-6 (B18C6), dibenzo-18-crown-6 (DB18C6) and bis[(benzo-15-crown-5)-4'-ylmethyl]pimelate (PI-Ⅱ) ionophores were carefully examined under the same experimental conditions. The enhanced selectivity of TB15C5-based membrane to potassium is explained in terms of the effect of the benzothiazol functional group and the distribution coefficients of metal ions.

• Journal of the Korean Chemical Society
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• v.48 no.6
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• pp.577-582
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• 2004

The azacrown compounds, 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, $N-ac_3[15]aneN_3O_2(II_a)$ and 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-tripropioc acid, $N-pr_3[15]aneN_3O_2(II_b)$ were synthesized by modified methods. Potentiometry was used to determine the protonation constant of the $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$. The stability constants of complexes of the trivalent metal ions of $Ce^{3+},\;Eu^{3+},Gd^{3+},and\;Yb^{3+}$ and divalent metal ions of $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ with the ligands $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$ have been determined at $25{\pm}0.1^{\circ}C$ in 0.1 M $NaClO_4$ solution by potentiometric methods. The metal ion affinities of the two triazamacrocyclic ligands with three pendant acetate or propionate groups are compared to those obtained for the similar ligands, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, and 1,7-dioxa-4,10,13- triazacyclopentadecane-N,N',N''-tripropioc acid. The trends in stability of complexes for different metal ions due to changes in the nitrogen position of the donor atoms of the ligand are discussed.

• Journal of the Korean Chemical Society
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• v.54 no.5
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• pp.515-522
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• 2010

A relation between antimicrobial activities and the formation constants of solid complexes of Cu(II), Ni(II), Co(II), Mn(II) and Fe(III) with tridentate Schiff base ligand, 4-hydroxy-3(1-{2-(benzylideneamino)-phenylimino}-ethyl)-6-methyl-2Hpyran-2-one (HL) derived from o-phenylene diamines, dehydroacetic acid (DHA) and p-chloro benzaldehyde have been studied. The ligand and metal complexes were characterized by elemental analysis, conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, $^1H$-NMR, UV-vis and mass spectra. From the analytical data, the stiochiometry of the complexes was found to be 1:2 (metal:ligand) with octahedral geometry. The molar conductance values suggest the nonelectrolytic nature of metal complexes. The X-ray diffraction data suggests monoclinic crystal system for Ni(II) and orthorhombic crystal system for Cu(II) and Co(II) complexes. The IR spectral data suggest that the ligand behaves as tridentate ligand with ONN donor atoms sequence towards central metal ion. Thermal behavior (TG/DTA) and kinetic parameters calculated by Coats-Redfern method suggests more ordered activated state in complex formation. The protonation constants of the complexes were determined potentiometrically in THF:water (60:40) medium at $25^{\circ}C$ and ionic strength ${\mu}=0.1\;M$ ($NaClO_4$). Antibacterial activities in vitro were performed against Staphylococcus aureu and Escherichia coli. Antifungal activities were studied against Aspergillus Niger and Trichoderma. The effect of the metal ions and stabilities of complexes on antimicrobial activities are discussed.

• Journal of the Korean Chemical Society
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• v.47 no.1
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• pp.13-18
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• 2003

The effect of ultrasonic decomposition was introduced to develop a pretreatment method for the analysis of potassium ion in human urine by potentiometry. N-(4’-benzo-15-crown-5)-anthracene-9-imine, which has a good selectivity coefficient for potassium against ammonium, was used as an ion-selective material for the determination of potassium in urine with relatively high concentration of $NH_4{^+}$. Protenis in urine be removed by 85.1% when the sample acidified with 1.0 M $HNO_3$ was preteated for 100 s by sonication. Potential response of the membrane electrode in the pretreated urine had a slope of 54.6(${\pm}0.2,\;n=5$) mV/decade over the linear range of log $[K^+]$=-5~-1(r=0.9997). When an oxidant, $H_2O_2$, was addwd to the urine sonicated with $HNO_3$, the deproteinization increased 10% more than that in case if only $HNO_3$ and then the maximum ratio of ca. 95% was obtained. Moreover, the Nernstian slope for $K^+$ added to the urinary sample increased to 56.7(${\pm}0.1,\;n=3$) mV/decade. When the calibration curves were measured, the slopes did not vary even after the electrode was successively used 20 times with ultrasonic cleaning. The results showed that an ultrasonic pretreatment method provides simplicity in use, reduced treatment time and improved potentiometric characteristics of the membrane as the method effectively removes ca. 95% of proteins in urine.

• Analytical Science and Technology
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• v.13 no.4
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• pp.466-473
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• 2000

The complex formation constants (${\beta}_{MLn}$) of potassium and various sodium-selective neutral carriers in solvent polymeric membranes have been determined using solvent polymeric membrane-based optodes and ion-selective electrodes (ISEs). Two different types of PVC-based membranes containing the H^+selective chromoionophore (ETH 5294) with and without a sodium ionophore (4-tert-bntylcalix[4]arenetetraacetic acid tetraethyl ester, ETH 2120, bis[(12-crown-4)methyl] dodecylmethylmalonate or monensin methyl ester) were prepared and their optical responses to either the changes in alkali metal cation (e.g., sodium and potassium) concentrations at a fixed pH (0.05 M Tris-HCl, pH 7.2) or varying pH at a fixed alkali metal cation concentration (0.1 M) were measured. The same type of membranes were also mounted in conventional electrode body and their potentiometric responses to varying pH at a fixed alkali metal cation concentration (0.1 M) were measured. The complex formation constants of the ligand could be calculated from the calibration plots of the relative absorbance vs. the activity ratios of cation and proton ($a_{M^+}/a_{H^+}$) and of the emf vs. pH. It was confirmed that the ratio values of the complex formation constants for the primary and interfering ions are closely related to the experimental selectivity coefficients of ISEs.

• Applied Chemistry for Engineering
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• v.9 no.5
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• pp.734-741
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• 1998

Electrode characteristics were studied in the interface between sample solutions and $K^+$ ion selective PVC membrane electrodes containing neutral carriers, dibenzo-18-crown-6(D18Cr6) and valinomycin(Val). The effect of doping of base electrolytes, the chemical structure and the content of carrier, variation of plasticizer, membrane thickness, and concentration variation of sample solution on the response characteristics of electrode such as the measured Nernstian slope, the detection limit, the linear response range, and potentiometric selectivity coefficients, were studied. In order to synthesize the membrane D18Cr6 and Val as neutral carriers were used, and complex between the carrier and $K^+$ ions were used as active materials. PVC membrane electrodes were made of plasticizers (DBP, DOS, and DBS), the base electrolyte[potassium tetraphenylborate(KTPB)], and solvent(THF). The chemical structure of carrier D18Cr6 was best for electrode and ideal electrode characteristics were appeared especially in case of doping of TPB. The optimum carrier content was about 3.23 wt % in case of D18Cr6 and Val. DBP was best as a plasticizer. As membrane thickness decreased the electrode characteristics was improved. But its characteristics were lowered below the optimum membrane thickness because of the elution of carrier, deterioration of membrane strength, etc. In the case of D18Cr6, the selectivity coefficients by the mixed solution method for the $K^+$ ion were in the order of $NH_4{^+}>Ca^{2+}>Mg^{2+}>Na^+$.

• Analytical Science and Technology
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• v.33 no.6
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• pp.262-273
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• 2020

A fluorine content analysis method for krill oils, which is a representative oil formulation in foods, was developed in compliance with the Korea Food and Drug Ministry's "Guidelines for Validation of Testing Methods Related to Food". Using this method for krill oils, the presence of impurities was evaluated via combustion-ion chromatography (C-IC). A review of published technical data on fluorine in krill oils showed that while the traditional wet potentiometric method was typically used, it was not reliable. Moreover, there was no food testing/analysis laboratory in Korea to perform a fluorine test analysis on such an oil matrix. Therefore, we identified halogen (fluorine) tests, developed to national and international standards, and developed a test method suitable for krill oils by selecting a C-IC method that is sufficiently applicable to the oil matrix. Based on the characteristics of the oil matrix, the optimal test method was established through various experiments by reviewing the concerns related to loss and interference in the preparation and introduction of samples. The fluorine content test was carried out on 11 krill oil products that were purchased online. Most products (with the exception of only one) were found to contain less than the reporting limit obtained by the test method. Furthermore, after additional testing, a high fluorine content of approximately 2,000 ~ 3,000 mg/kg was detected on the krill surface, although the concentration varied depending on the area of the krill. A comparison with samples from two ISO/IEC 17025 testing laboratories confirmed that there was no significant difference in the statistical analysis results obtained by ANOVA among the three laboratories. A testing guide for fluorine content analysis was completed.

• Journal of the Korea institute for structural maintenance and inspection
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• v.26 no.4
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• pp.57-64
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• 2022

Chloride, which is one of the main deterioration factors in reinforced concrete structures, can degrade the performance of the structure due to chloride-induced corrosion of steel. Chloride content at steel depth or the rate of chloride penetration is necessary to determine deterioration of reinforced concrete or to calculate initiation time of steel corrosion caused by chloride attack. Chlorides in concrete are generally identified with typical two methods including chloride profiling using potentiometric titration method and discoloration method using AgNO₃ solution. The former is advantageous to estimate chloride penetration rate (diffusion coefficient in general) with measured chloride contents directly, but it is laborious. In the case of latter, while the result is obtained easily with the range of discoloration, the error may occur depending on workmanship when the depth of chloride ingress is measured. This study shows that chloride penetrated depth is evaluated with the results obtained from discoloration method through image analysis, thereby the error is minimized by workmanship. In addition, the effect of micro-crack in concrete is studied on chloride penetration. In conclusion, the depth of chloride penetration was quantified with image analysis and as it was confirmed that chlorides can rapidly penetrate through micro-cracks, caution is especially required for cracks in concrete structure.