마크로고리 화합물을 운반체로 하는 액체막을 통한 이온의 운반에 관한 연구 (제1보). Dibenzo-18-Crown-6-(DBC)/$H_2O-CHCl_3-H_2O$계에서 칼륨이온의 운반 메카니즘

윤창주,이심성,구창현,김시중,Yoon, Chang-Ju,Lee, Shim-Sung,Koo, Chang-Hyun,Kim, Si-Joong 대한화학회 1984 대한화학회지 Vol.28 No.3

칼륨이온이 dibenzo-18-crown-6(DBC)에 의해 $H_2O-CHl_3-H_2O$액체막을 통하여 운반되는 속도를 10가지 칼륨염의 농도를 변화시키면서 $25^{\circ}C$에서 측정하였다. 운반속도는 농도와 음이온의 특성에 크게 의존했으며 농도효과로 부터 피크르산칼륨의 경우에는 이온쌍 형성으로 인하여 1.0 ${\times}10^{-3}$M을 전후하여 각기 다른 양상을 보였다. 이온의 운반과정은 다단계 착물반응 및 확산과정에 의한 것으로 운반 메카니즘을 체계화하기 위해 비균질성 액체막의 각상에서 갖는 화학종의 에너지 장벽모델을 제시하였다. 또한 이를 음이온의 수화자유 에너지와의 관계를 비교함으로써 새로이 7단계 운반과정을 제시하고 그 운반 메카니즘을 고찰하였다. The transport rates of $K^+$ion through CHCl$_3$ liquid membrane containing dibenzo-18-crown-6(DBC) as a carrier molecule have been determined at $25^{\circ}C$. The transport rates depend highly on the ion concentration and on the nature of anion. It is concluded that $K^+$ions are transported in the form of ion-pair. In the case of potassium picrate, however, it is found that the transport proceeds with the formation of the incomplete ion-pair in the concentration less than 1.0 ${\times}10^{-3}$M of picrate, while with the complete formation of ion-pair in the concentration more than 1.0 ${\times}10^{-3}$M of picrate. Seven steps of the transport process are suggested and they can be illustrated in terms of energy barrier model as a function of the position of ionic species in the membrane.

마크로고리 화합물을 운반체로 하는 액체막을 통한 이온의 운반에 관한 연구 (제2보). 유기액체막 운반체를 통한 수소이온의 운반

윤창주,이심성,김영희,김시중,Yoon, Chang-Ju,Lee, Shim-Sung,Kim, Young-Hee,Kim, Si-Joong 대한화학회 1984 대한화학회지 Vol.28 No.3

Dibenzo-18-crown-6(DBC) 및 dicyclohexyl-18-crown-6(DCC)를 이온의 운반체로 하는 여러 유기액체막을 통해 수소이온의 운반속도를 25$^{\circ}$C에서 측정하였다. 운반속도는 용매의 유전상수에 크게 영향을 받는데 이를 액체막 내부에서 이온 화학종이 가진 Born의 포텐셜 에너지 장벽을 들어 고찰하였다. 또한 음이온의 크기도 운반속도에 영향을 주었는데 이는 Born식으로 부터 새로이 유도된 이론적인 결과와 잘 일치하였다. The transport rates of $H^+$ ion by DBC and DCC as carrier molecules through organic liquid membranes were determined at 25$^{\circ}$C. The transport rates depend highly on the dielectric constants of membrane solvents and these results were discussed in terms of Born's potential energy barrier methods. The sizes of anions also affect the transport rates and these results were well explained theoreticlly by extended Born's equation.

질소-산소 주게 거대고리 화합물의 분자간 수소결합에 관한 NMR 연구

윤창주,김정,김시중,Chang Ju Yoon,Jeong Kim,Si Joong Kim 대한화학회 1985 대한화학회지 Vol.29 No.2

클로로포름 용액에서 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane(cryptand 22), 1,7-diaza-4,10,13-trioxacyclopentadecane(cryptand 21), 1,12,15-triaza-5,8-dioxa-3,4:9,10-dibenzocycloheptadecane ($N_3O_2$) 및 1,12-diaza-5,8-dioxa-3,4:9,10-dibenzocyclotetradecane ($N_2O_2$)의 분자간 수소결합을 $^1H$-nmr 분광법으로 여러 온도에서 조사하였다. 묽은 용액에서 이 화합물들은 -NH기를 통한 수소결합에 의하여 이합체를 형성한다. 수소결합형성에 대한 평형상수 값의 크기는 cryptand 22 > cryptand 21 > $N_3O_2$ > $N_2O_2$의 순위이었다. 이 평형에는 분자구조의 대칭성과 분자내의 -NH기의 수와 위치가 영향을 미치고 있었다. The intermolecular hydrogen bondings of 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane(cryptand 22), 1,7-diaza-4,10,13-trioxacyclopentadecane(cryptand 21), 1,12,15-triaza-5,8-dioxa-3,4:9,10-dibenzocycloheptadecane ($N_3O_2$) and 1,12-diaza-5,8-dioxa-3,4:9,10-dibenzocyclotetradecane ($N_2O_2$) have been studied in chloroform solutions by $^1H$-nmr spectrometry at various temperatures. The molecules dimerize each other with the hydrogen bonds through N-H groups in the dilute solutions. The formation constants of the hydrogen bonds are in the order of cryptand 22 > cryptand 21 > $N_3O_2$ > $N_2O_2$. It appears that the constants depend on the molecular symmetry, the number of N-H group, and the localization of N-H groups in the molecule.

경기도 섬유패션 산업의 대내·외 환경변화 분석을 통한 산업구조 고도화 정책방안 - 벤더와의 분업화체계 와해에 따른 근원적 현안의 해결 중심으로 -

윤창주 ( Yoon Chang Ju ),정진 ( Jeong Jin ) 한국의류산업학회 2017 한국의류산업학회지 Vol.19 No.2

In the textile industry located in Gyeonggi-do, 85% of small-sized firms have less than 10 employees; in addition, the most of them are characterized by a vendor relying specialization system that conducts foundry from the vendor that managed marketing, textile design·development, and quality checks according to unit stream. The breakaway of these vendors accelerated over the last 7 years; however, industry survival is at stake because the specialization system and orders have collapsed. The following four main policies must be implemented to overcome industry hardship. Policies have been derived from survey and analysis (present condition and trends) from industrial statistics and related policies in advanced and developing countries. First, a policy to promote cooperation between small-sized foundry unit-streams. Second, unification of the marketing support function with a textile design and development·support system. Third, the introduction of policy support-management system customized according to developmental stages (tall process→fabric production→sales→clothing production·sales). Fourth, foundation of a control tower that puts these tasks in a vehicle and runs them and the division of roles with the central government. We must propel main tasks to manifest the developmental potential (develop eco-friend dyeing and processing technologies, change to the young next CEO in business environment, and grow the of knit market) of the Gyeonggi Textile Industry in a short period to present a condition where these four main policies are running.

Ln^{3+}$-DMF계의 ^1H $-NMR 연구 (Ⅰ). DMF 분자의 교환과 CHO기의 양성자 화학적이동

이미경,윤창주,최영상,Mi-Kyung Lee,Chang-Ju Yoon,Young-sang Choi 대한화학회 1992 대한화학회지 Vol.36 No.3

Ln$(NO_3)_3$/DMF 상자성 용액의 양성자 선-나비와 화학적이동을 240 K부터 380 K 사이에서 측정하였다. 이들 데이터로부터 DMF 분자의 CHO기에 대한 배위구 교환속도와 열역학 교환파라미터를 추출하였다. 1/$T_2$ 와 ${\Dellta}{\omega}$ 데이터의 온도의존성을 자세하게 분석하고 고찰하여 결과를 정리하였다. 분석의 결과를 살펴보면 짝짓지 않은 전자 스핀이 몇몇 $Ln^{3+}$이온에서 첫 배위구를 넘어 퍼지면서 bulk 용매의 DMF 분자로 스칼라이완의 기여를 제공하는 것 같다. Proton lineshapes and chemical shifts of paramagnetic solutions of Ln$(NO_3)_3$ in DMF have been measured over the temperature range 240K to 3807K. Solvation sphere exchange rates and the thermodynamic exchange parameters for CHO group of the DMF molecules have been extracted from these data. The results were established through a detailed analysis and discussion of the temperature depending data of the 1/$T_2$ and ${\Dellta}{\omega}$ data were analyzed in detail, and it has been found that delocalization of the unpaired electron spin from some $Ln^{3+}$ ion to DMF molecules beyond the first solvation shell would occur, giving rise to a scalar relaxation contribution in the bulk solvent.

물, Dioxane-물 및 Ethanol-물의 混合溶媒에서의 Hydrogen Cupferrate의 酸解離常數의 決定

김시중,윤창주,장인순,Kim, Si-Joong,Yoon, Chang-Ju,Chang, In-Soon 대한화학회 1966 대한화학회지 Vol.10 No.3

The glass electrode was empirically calibrated in dioxane-and ethanol-water mixed solvents, by means of which the pH-meter reading could be converted to stoichiometric hydrogen ion concentration. By the potentiometric titration method, the thermodynamic dissociation constants of hydrogen cupferrate (HCup) with variations of ionic concentration in aqueous solution were determined, and by the extrapolation of the constants the new thermodynamic $pK_a$ value, 3.980${\pm}$0.006, at zero ional concentration was obtained. The thermodynamic dissociation constants of HCup in dioxane-and ethanol-water solution were also potentiometrically determined with the changes in composition of organic solvents at 0.01 and 0.05 of the ionic strength(${mu}$) and 25 $^{\circ}C$. The empirical formula of the constants with mole fraction(n) of the organic solvent are as follow: Dioxane-water solution. $pK_a$= 12.96n + 4.10 at ${\mu}$ = 0.01, n = 0.0228∼0.171 $pK_a$= 12.05n + 4.23 at ${\mu}$ = 0.05, n= 0.0228∼0.171 Ethanol-water solution, $pK_a$= 4.0ln + 4.26 at ${\mu}$= 0.01, n= 0.0395∼0.262 $pK_a$= 3.83n + 4.34 at ${\mu}$= 0.05, n= 0.0395∼0.262

사염화탄소 중에서 Thiopropionamide와 N,N-Dimethylalkylamide사이의 수소결합에 관한 분광학적 연구

김병철,윤창주,송규석,최영상,Byung-Chul Kim,Chang-Ju Yoon,Kyuseok Song,Young Sang Choi 대한화학회 1989 대한화학회지 Vol.33 No.2

사염화탄소 용액중에서 thiopropionamide(TPA)와 N,N-dimethylalkylamides(DMF, DMA, DMP)간의 수소결합에 관한 열역학적 상수를 구하기 위하여 TPA의 근적외선 영역의 흡수띠 중에서 $ν_a+amide II$조합띠를 사용하여 5${\sim}$55$^{\circ}C$ 범위에서 실험하였다. TPA 단위체와 수소결합을 하고 있는 TPA의 혼합 흡수띠를 Lorentzian-Gaussian product function을 사용하여 개개의 띠로 분리하였다. 컴퓨터로 분해하여 얻은 개개의 흡수띠의 면적을 사용하여 단위체 및 1 : 1 복합체의 농도를 계산하였고 이로부터 평형상수를 구하였다. 열역학적 상수들은 온도의존 흡수띠를 분석하여 구하였다. TPA와 DMF, DMA 및 DMP간의 1 : 1 복합체의 ${\Delta}$$H^{\circ}$는 각각 -12.5, -13.5, -14.1kJ/mol이었고.${\Delta}$$S^{\circ}$는 각각 -15.2, -17.9, -22.3kJ/mol${\cdot}$deg이었다. The $ν_a+amide II$ combination band of thiopropionamide has been recorded for investigation of Hydrogen bonding between thiopropionamide (TPA) and N,N-dimethylalkylamide (DMF, DMA and DMP) in carbon tetrachloride over the range of $5^{\circ}$ to $55^{\circ}$. The combination band of monomeric TPA and hydrogen-bonded TPA can be resolved by Lorentzian-Gaussian product function into monomeric TPA and hydrogen-bonded TPA with amides. The association constants ($K_1$) for the hydrogen-bonded TPA were calculated by the concentrations of the monomeric TPA and the hydrogen-bonded TPA obtained from the computer resolved absorption bands. Thermodynamic parameters for the Hydrogen bonding have been evaluated by the analysis of the temperature dependent spectra. The ${\Delta}$$H^{\circ}$ of hydrogen-bonded TPA with DMF, DMA and DMP have been found to be-12.5, -13.5 and -14.1 kJ/mol, respectively. The corresponding ${\Delta}$$S^{\circ}$for the above system were -15.2, -17.9 and -22.3 J/mol${\cdot}$deg, respectively.

$^{113}Cd$NMR 분광법에 의한 Cd(II)-$N_2O_3$계 거대고리 리간드 착물 형성의 반응 메카니즘

김정,윤창주,유한준,김시중,Kim, Jeong,Yoon, Chang-Ju,Yoo, Han-Jun,Kim, Si-Joong 대한화학회 1995 대한화학회지 Vol.39 No.4

Methanol-물 및 2-Propanol-물의 混合溶媒에서의 Hydrogen Cupferrate의 酸解離常數의 決定

김시중,윤창주,장인순,Si-Joong Kim,Chang-Ju Yoon,In-Soon Chang 대한화학회 1966 대한화학회지 Vol.10 No.3

The glass electrode was empirically calibrated in methanol-and 2-propanol-water mixed solvents, by means of which the pH-meter reading could be converted to stoichiometric hydrogen ion concentration. The thermodynamic dissociation constants of hydrogen cupferrate in methanol-and 2-propanol-water solution were potentiometrically determined with the changes in composition of organic solvents at 0.01 and 0.05 of the ionic strength and 25$^{\circ}C$. The empirical formula of the constants with mole fraction (n) of the organic solvent are as follow: methanol-water solution $pK_a$= 2.24n + 4.29 at ${\mu}$ = 0.01 n = 0.0476∼0.642 $pK_a$ = 2.35n + 4.38 at ${\mu}$ = 0.05 n= 0.0446~0.642 2-propanol-water solution $pK_a$= 5.50n + 4.48 at ${\mu}$ = 0.05 n = 0.0253~0.259 The relationships between $pK_a$ of acetic acid, propionic acid and HCup and dielectric constant of some mixed solvents were discussed. It would be considered that the factors effecting $pK_a$ value of weak acid in mixed-solvent are not only dielectric constants but acid-base character and solvation effect of the solvent, etc.

질소-산소 주개 거대고리 화합물-금속착물의 수용액에서의 안정도상수

김정,윤창주,박휴범,김시중,Jeong Kim,Chang-Ju Yoon,Hyu-Bum Park,Si-Joong Kim 대한화학회 1991 대한화학회지 Vol.35 No.2

고리를 구성하는 원자의 수가 15개에서 18개인 디아자 크라운계의 고대고리 화합물인 1,12-diaza-3, 4 : 9, 10-dibenzo-5, 8-dioxacyclopentadecane(NtnOenH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-hydroxy-5,9-dioxacyclohexadecane(NtnOtnH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-15-hydroxy-5,9-dioxacyclohexadecane(Ntn(OH)OtnH$_4$), 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdienH$_4$) and 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane(NtnOdienH$_4$)의 양성자화와 금속이온과의 착물 형성을 전위차적정법과 핵자기 공명법으로 연구하였다. 양성자화상수는 크라운 에테르의 염기도를 예측하는데 상용하였다. 본 연구에서 사용한 거대고리 화합물의 염기도 순서는 NenOdienH$_4$ < Ntn(OH)OtnH$_4$ < NtnOenH$_4$ < NtnOtnH$_4$ < NtnOdienH$_4$였다. 염기도의 이와 같은 변화를 거대고리에 대한 치환기와 양성자화가 일어날 때의 고리의 비틀림 정도로 설명하였다. 금속이온과의 착물 형성에 대한 안전도상수는 전이금속이온에 대해서는 Co(II) < Ni(II) < Cu(II) < Zn(II)순이었으며, 중금속이온에 대해서는 Cd(II) < pb(II) < Hg(II)의 순이었다. 금속 착물 형성에 대한 이와 같은 안정도상수의 변화에는 Co(II), Ni(II) 및 Cu(II) 착물의 경우 리간드 고리의 크기가 영향을 미치고 있었으며, Zn(II), Cd(II), pb(II) 및 Hg(II) 착물의 경우에는 리간드의 염기도가 주로 영향을 미치고 있었다. 후전이금속 착물에 대한 $^1$H와 $^{13}$C 핵자기공명 분광법에서는 고리의 질소원자가 산소원자보다 금속이온에 더 큰 친화력을 가짐을 알 수 있었고, 금속이온과 착물을 형성할 때에 고리의 평면성이 상실되고 있음도 밝혀졌다. The protonation and the metal ion complexation of 15 to 18 membered diaza crown ether such as 1,12-diaza-3, 4 : 9, 10-dibenzo-5, 8-dioxacyclopentadecane(NtnOenH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-hydroxy-5,9-dioxacyclohexadecane(NtnOtnH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-15-hydroxy-5,9-dioxacyclohexadecane(Ntn(OH)OtnH$_4$), 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdienH$_4$) and 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane(NtnOdienH$_4$) were studlied by potentiometry and NMR spectroscopy. The protonation constants were used to predict basicity of crown ethers. The sequence of the basicity was NenOdienH$_4$ < Ntn(OH)OtnH$_4$ < NtnOenH$_4$ < NtnOtnH$_4$ < NtnOdienH$_4$. Changes on the basicity were explained in terms of the effects of substituents and the degree of twistness of the macrocyclic ring. The sequence of the complex stabilities were Co(II) < Ni(II) < Cu(II) < Zn(II) for the transition metal complexes and Cd(II) < pb(II) < Hg(II) for the post-transition metal complexes. These changes on the stabilities were dependent on the basicity of the ligand and cavity size of the ring. For the heavy post-transiton metal complexes and Zn(Ⅱ) complex, the former factor was predominent and for the other transition metal complexes, the latter was affected on the stabilities. $^1$H and $^{13}$C-NMR studies for heavy post-transition metal complexes indicated that the nitrogen atom has greater affinity on metal ions than oxygen atom and the planarity of the rings was losed by the complexation with metal ions.