37 , 200 rpm - 九州大学学術情報リポジトリ

吸着剤

Scheme 2-1 : (a) , (b)

(R1-N=C=N-R2: EDC, R-NH2: glycine methyl ester)

[Adapted with permission from Journal of Chemical Engineering of Japan, 46, 450–454 (2013).

2-2-3.

1000 ppm Wako Pure Chemical Industries (Osaka, Japan)

0.1M HEPES 0.1 M HNO₃ 1 M 10 M NaOH

pH Fig. 2-4

5 mL 10 mg 30 vortex mixer 30ºC

60 160 rpm 5800g 10

0.20 µm

pH pHeq pH HM-60 G, DKK-TOA Co.

ICP ICP-AES, Optima 5300 DV, PerkinElmer Inc.

Fig. 2-4

E. coli CH3OH

1 % HCl E. coli

E. coli

H⁺

E. coli

H₂N R

E. coli + H⁺ +

(a)

(b)

(A) (Q: mg/g) Eq. (2-1) (2-2) Ci

ppm C_e ppm V: L M

2-2-4. FT-IRによる吸着残渣および化学修飾大腸菌の分析

Dy³⁺ 100 ppm pH 4

Dy pH 4

4 cm^-1 4000–700 cm^-1 FT-IR Spectrum 65, PerkinElmer Co.

FT-IR

Eq. (2-1) A= C_i – C_e

C_i

Eq. (2-2) Q= V(C_i – C_e)

2-3. 結果および考察

2-3-1. 吸着率の経時変化

Figure 2-5 Nd³⁺ Dy³⁺ Lu³⁺

Fig. 2-5 Nd³⁺, Dy³⁺ Lu³⁺ (A) (pH: 4.0, : 30 , C_i: 5 ppm)

0 0.2 0.4 0.6 0.8 1

0 10 20 30 40

A [-]

Time [min]

Nd Dy Lu

2-3-2. 吸着率に対するpHの影響

Figure 2-6 (Pm) pH

5 Figure 2-6

tetrad effect ^[18]

[19–, 21]

Sc³⁺ pH

Fig. 2-6 (A) pH

( : 30ºC, C_i: 5 ppm) 0

0.2 0.4 0.6 0.8 1

Sc Y La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

A [-]

Rare earth elements

pH 0 pH 1 pH 2 pH 3 pH 4

30 Figure 2-7 Y³⁺ Nd³⁺ Dy³⁺ Lu³⁺ pH

pH 0–2

pH pH 4

pH pH

(pK_a) pK_a

pH 0–1

Fig. 2-7 Y³⁺, Nd³⁺, Dy³⁺ Lu³⁺ (A) pH : 30ºC, Ci: 5 ppm

0 0.2 0.4 0.6 0.8 1

0 1 2 3 4 5

A [-]

pH_eq

Y Nd Dy Lu

31 2-3-3. 吸着残渣のFT-IRによる分析

Dy³⁺ 100 ppm pH 4

Dy pH 4

FT-IR 4000 2000 cm^-1 3700 3000 cm^-1

3000 2800 cm^-1 N-H O-H C-H

2000 700 cm^-1 Fig. 2-8

1654 cm^-1 1540 cm^-1 I

II 1450–1394 cm^-1 C-O

O-H

1234 cm^-1 1075 cm^-1 pH 4

1178 cm^-1 1043 cm^-1

Fig. 2-8 (b) pH 4

pH 4 Dy

1400–1300 cm^-1 C-O O-H

Fig. 2-8 (c) Dy³⁺

Fig. 2-8 FT-IR : (a) , (b) pH 4 , (c) pH 4 Dy

2-3-4. 大腸菌のカルボキシル基のエステル化およびアミド化のFT-IRによる確認

FT- IR

4000 2000 cm^-1 3700 3000 cm^-1 3000 2800 cm^-1 N-H O-H C-H

2000 700 cm^-1 Fig. 2-9

FT-IR Fig. 2-9 (a)

1654 cm^-1

1540 cm^-1 I II 1450–1394 cm^-1

C-O O-H

1234 cm^-1 1075 cm^-1

FT-IR Fig. 2-9 (b) (c)

1450–1400 cm^-1

1730 cm^-1 C=O

T [%] !

Wavenumbers [cm

^-1

]

(a)

(b) (c)

1450 1394 1330 1234 1075 10431178

Fig. 2-9 (b) Fig. 2-9 (b)

1450–1400 cm^-1 Fig. 2-9 (c)

Fig. 2-9 FT-IR : (a) , (b) , (c)

600!

800!

1000!

1200!

1400!

1600!

1800!

2000!

T [%] !

Wavenumbers [cm

^-1

]

(a) (b)

(c)

1730 1394 1234 1075 1032

2-3-5. 大腸菌のカルボキシル基のエステル化およびアミド化の希土類金属の吸着に対する影響

Nd³⁺ Dy³⁺ Lu³⁺ 5 ppm

3 Dy³⁺ Fig. 2-10

pH Dy³⁺

Fig. 2-10 Esterification

pH 2-4 Fig. 2-10

Amidation

pH 0–1 pH 2–4

Fig. 2-10 Dy³⁺ ( : 30ºC, Ci: 5 ppm) 0

0.2 0.4 0.6 0.8 1

-1 0 1 2 3 4 5

A [-]

pH_eq

Wild type Esterification Amidation

35 2-3-6. (Q_max)

Nd³⁺ Dy³⁺ Lu³⁺

1–300 ppm pH 4 Langmuir

Langmuir Eq. (2-3)

Fig. 2-11 C_e ppm Q_eq

mg/g Q_max mg/g K_ad: L/mg Nd³⁺ Dy³⁺

Lu³⁺ 30.9 32.7 43.8 mg/g

Table 2-4

Eq. (2-3)

Fig. 2-11 Nd Dy Lu ( : 30ºC, pHeq=4)

Q

_eq

= Q

_max

K

_ad

C

1+ K

_ad

C

0 10 20 30 40 50

0 50 100 150 200 250

Q [mg/ g]

C_e [ppm]

Nd Dy Lu

Table 2-4 (Q_max)

Q_max (mg/g)

E. coli d³⁺ 30.9

E. coli Dy³⁺ 32.7

E. coli Lu³⁺ 43.8

Azacrown ether*

Amberlite XAD-4 resin^a Nd³⁺ 9.2 [22]

b Nd³⁺ 16.2 [23]

b Dy³⁺ 23.7 [23]

b Lu³⁺ 21.2 [23]

DTPA** ^c Nd³⁺ 28 [24]

*:monoaza dibenzo 18-crown-6 ether; **: diethylenetriaminepentaacetic acid a: pH 4.5; b: pH 1.0; c: pH 6

37 2-4.

pH pH 4

FT-IR

pH 0–1 pH 2–4

38 2-5.

[1] , , , (2008)

[2] JOGMEC NEWS, 27 (2011)

[3] U.S. Geological Survey, Mineral commodity summaries 2015, U.S. Geological Survey, 128–129 (2015) [4] U.S. Department of Energy, Critical Materials Strategy, U.S. Department of Energy, 44–48 (2011) [5] Y. Takahashi, X. Châtellier, K.H. Hattori, K. Kato, D. Fortin, Adsorption of rare earth elements onto

bacterial cell walls and its implication for REE sorption onto natural microbial mats, Chem. Geol., 219, 53–67 (2005)

[6] Y. Takahashi, M. Yamamoto, Y. Yamamoto, K. Tanaka, EXAFS study on the cause of enrichment of heavy REEs on bacterial cell surfaces, Geochim. Cosmochim. Ac., 74, 5443–5462 (2010)

[7] T. Tsuruta, Accumulation of rare earth elements in Various Microorganisms, J. Rare Eerth., 25, 526–532 (2007)

[8] N. Das, D. Das, Recovery of rare earth metals through biosorption: An overview, J. Rare Eerth., 31, 933–941 (2013)

[9] H. Moriwaki, H. Yamamoto, Interactions of microorganisms with rare earth ions and their utilization for separation and environmental technology, Appl. Microbiol. Biot., 97, 1–8 (2013)

[10] X. Shuxia, Z. Shimin, C. Ke, H. Jinfeng, L. Huashan, W. Kun, Biosorption of La³⁺and Ce³⁺ by Agrobacterium sp. HN1, J. Rare Eerth., 29, 265–270 (2011)

[11] R. C. Oliveira, C. Jouannin, E. Guibal, O. G. Jr., Samarium(III) and praseodymium(III) biosorption on Sargassum sp.: Batch study, Process Biochem., 46, 736–744 (2011)

[12] E. I. Cadogan, C.-H. Lee, S. R. Popuri, Facile synthesis of chitosan derivatives and Arthrobacter sp.

biomass for the removal of europium(III) ions from aqueous solution through biosorption, Int. Biodeter.

Biodegr., 102, 286–297 (2015)

[13] H. Moriwaki, R. Masuda, Y. Yamazaki, K. Horiuchi, M. Miyashita, J. Kasahara, T. Tanaka, H.

Yamamoto, Application of freeze-dried powders of genetically engineered microbial strains as adsorbents for rare earth metal ions, ACS Appl. Mater. Interfaces, 8, 26524–26531 (2016)

[14] D. Sadovsky, A. Brenner, B. Astrachan, B. Asaf, R. Gonen, Biosorption potential of cerium ions using Spirulina biomass, J. Rare Eerth., 34, 644–652 (2016)

[15] X. Pan, W. Wu, J. Lü, Z. Chen L. Li, W. Rao, X. Guan, Biosorption and extraction of europium by Bacillus thuringiensis strain, Inorg. Chem. Commun., 75, 21–24 (2017)

[16] S. Lin, G. D. Rayson, Impact of surface modification on binding affinity distributions of datura innoxia biomass to metal ions, Environ. Sci. Technol., 32, 1488–1493 (1998)

[17] D. G. Hoare, D. E. Koshland Jr., A method for the quantitative modification and estimation of carboxylic acid groups in proteins, J. Biol. Chem., 242, 2447–2453 (1967)

[18] , , (2010)

[19] J. S. Preston, Solvent extraction of metals by carboxylic acids, Hydrometallurgy, 14, 171–188 (1985) [20] F. Kubota, M. Goto, F. Nakashio, Extraction of rare earth metals with 2-ethylhexyl phosphonic acid

mono-2-ethylhexyl ester in the presence of diethylenetriaminepentaacetic acid in aqueous phase, Solvent Extr. Ion Exch., 11, 437–453 (1993)

[21] K. Shimojo, H. Naganawa, J. Noro, F. Kubota, M. Goto, Extraction behavior and separation of lanthanides with a diglycol amic acid derivative and a nitrogen-donor ligand, Anal. Sci., 23, 1427–1430 (2007)

[22] S. R. Dave, H. Kaur, S. K. Menon, Selective solid-phase extraction of rare earth elements by the chemically modified Amberlite XAD-4 resin with azacrown ether, React. Funct. Polym., 70, 692–698 (2010)

[23] T. Ogata, H. Narita, M. Tanaka, Adsorption behavior of rare earth elements on silica gel modified with diglycol amic acid, Hydrometallurgy, 152, 178–182 (2015)

[24] S. D. N. Almeida, H. E. Toma, Neodymium(III) and lanthanum(III) separation by magnetic nanohydrometallurgy using DTPA functionalized magnetite nanoparticles, Hydrometallurgy, 161, 22–28 (2016)

40 3

3-1.

3-1-1.

4 4 3

2 4

]

1 ]

3 Table 3-1 ^[1]

] 2]

3 4 3 [

] 2 4

Table 3-1 ^[1]

41 3-1-1-1.

] 3

] [ 4

HCl HNO32] H2SO4 ]

4 4

4 ^[2] NaOH2] NH₄OH

4 4 4

4 ^[3] ] ]

3 ]

4 ]

] 2 4 Fig. 3-1 ^[1]

Fig. 3-1

(a) , (b)

42 (a)

1 ] 2]

] 4

] 4 Table 3-2

[4] glutaraldehyde epichlorohydrin

] ^{[5, 6]} 4

2 [ ] [ 4 ^{[5, 6]}

]

4 ^[7] ]

4 ^{[8, 9]}

Table 3-2 R:

[ 4

(b) ]

] 4

4 3

4 Fig. 3-1 4 ]

] 4

poly(allylamine)2] polyethylenimine poly(acrylic acid) 4 Fig. 3-2 ^[10–13]

Table 3-2 4 4 ]

] J. Mao 4

poly(allylamine) glutaraldehyde ]

PtCl₆^2- 4 4.36 ^[10]

[ pyromellitic dianhydride thiourea [ ^[14]

]

Cd²⁺2] Pb²⁺ 4 15 2] 11 4

Fig. 3-2

(a) poly(allylamine), (b) polyethylenimine, (c) poly(acrylic acid)

Table 3-2 ]

4 ]

4 ^[15] ] 4 Cu²⁺2] Cd²⁺

] 4 3

] 4

4 Fig. 3-3 M.-H. Song polyethylenimine

] Ru ^[16] polyethylenimine

2 Ru

Ru(CO)₃I₃⁻ Ru 4]

Ru 3

4 3 ]

] 4

Fig. 3-3

45 3-1-1-2.

Cr Mn Fe Co Cu Zn Mo 3

2] ] Fig. 3-2

C. Sousa 4 ^[17]

LamB 6 (His)6

Cd²⁺ (His)₆ ]

4 2 2 (His)6

Cd²⁺ 11 4 3 3

]

4 (His)6 [

4 ^[18–20] ]

] 2]

[21]

ModE Fig. 3-2

Mo ^[22] ModE W ] ModE

] W 4 ^[23]

2 [

4 D. M. Park

[24] S RsaA

Lanthanide-binding tags peptide LBT peptide ^[25]

Caulobacter crescentus C. crescentus

LBT peptide 2]

2 2 Tb³⁺

Eu³⁺ 4 LBT peptide C.

crescentus[LBT peptide

8 ]

2 [ 4 ]

]

47 3-1-2.

2 2 4 ^[26] 3

4 4 3

] 4

8 [

] 4 [ 4

]

3 ]

Fig. 3-3

48 3-1-3.

2007 K. Shimojo ]

N,N-dioctyldiglycol amic acid DODGAA; Fig. 3-4

4 pH 2–3 Fe³⁺ Al³⁺2]

Cu²⁺ 4 [27, 28]

DODGAA 3

] DODGAA

pH ]

[

DODGAA 4 4

P S 4

4 3 C N O H 3 4

] pH ]

4 C N O H 3 4

3 3

Fig. 3-4 DODGAA

C

₈

H

₁₇

C

₈

H

₁₇

N O

O

OH

O

49 3-2.

Scheme 3-1 ]

Scheme 3-1

[Reprinted from Biochemical Engineering Journal, 113, Y. Hosomomi, R. Wakabayashi, F. Kubota, N. Kamiya, M. Goto,102–106, Copyright (2016), with permission from Elsevier]

3-2-1.

3-2-1-1.

pET22b⁺ BL21 DE3 100

mg/L LB 10 mL 100 mg/L

LB 1 L 37ºC 200 rpm OD600= 0.5–0.6

4000g 20 25 mmol/L Tris-HCl pH 8.0

5800g 10 ] 3

300 mg 100 mM pH 9.0 30 mL

diglycolic anhydride Tokyo Chemical Industry Co. (Tokyo, Japan) 3.48 g

Diglycolic anhydride pH4 4

pH4pH 9.0 ] 10 M 5 M 4 diglycolic

anhydride Diglycolic anhydride 60

5800g 10 100 mmol/L pH 4.0 5800g

10 ] 3

]

50 3-2-1-2. FT-IR

100 mM pH 9.0 2]

4 cm^-1 4000–700 cm^-1 FT-IR Spectrum 65, PerkinElmer Co. ] ]

3-2-1-3.

1000 ppm Wako Pure Chemical Industries (Osaka, Japan)

0.1M HEPES ] 0.1 M HNO3 1 M 10 M NaOH

] pH 2.5 mL 5 mg

30 vortex mixer 38 30ºC 60 160 rpm

5800g 10 0.20 µm

pH pH_eq pH HM-60 G, DKK-TOA Co.

ICP ICP-AES, Optima 5300 DV, PerkinElmer Inc.

(A)2] (Q: mg/g) Eq. (3-1) (3-2) Ci

ppm Ce ppm V: L M

Eq. (3-1) A= C_i – C_e

C_i

Eq. (3-2) Q= V(C_i – C_e)

51 3-2-2.

3-2-2-1. FT-IR

100 mM pH 9.0 2

] 4000 700 cm^-1 FT-IR ]

Fig. 3-5 4000 2000 cm^-1 3

3700 3000 cm^-1 3000 2800 cm^-1 N-H O-H2] C-H

4 2000 700 cm^-1 ]

I2] II 41653 cm^-12] 1540 cm^-1 1460 cm^-1 1410 cm^-1

O-H 4

41240 cm^-12] 1075 cm^-1

2 1140 cm^-1 C-O-C

4 Fig. 3-5 (c) 4

2] pH 9

FT-IR 3 ]

] 4

Fig. 3-5 FT-IR

(a) , (b) pH 9 , (c)

[Reprinted from Biochemical Engineering Journal, 113, Y. Hosomomi, R. Wakabayashi, F. Kubota, N. Kamiya, M. Goto,102–106, Copyright (2016), with permission from Elsevier]

3-2-2-2. pH

Nd³⁺ Dy³⁺ Lu³⁺ 2] Fe³⁺ Al³⁺ Cu²⁺ 5 ppm

2] pH

pH Fig. 3-6 Nd³⁺ Dy³⁺ Lu³⁺

3 Fe³⁺ Al³⁺ Cu²⁺ 2

2 2 4

2] pH 4

4 3 4 pH 2

4 4 3 DODGAA

[28]

3 4 pH1–2

4 ]

]

4 4 3 Al³⁺2] Cu²⁺

4 3

Fig. 3-6 pH 30 °C , C_i = 5 mg/L

(a) , (b)

[Reprinted from Biochemical Engineering Journal, 113, Y. Hosomomi, R. Wakabayashi, F.

Kubota, N. Kamiya, M. Goto,102–106, Copyright (2016), with permission from Elsevier]

2] 2 Fe³⁺4 4 3

4 Fe³⁺ 3

[29] 3 Fe³⁺ ] ^{[30, 31]}

D2EHPA Fe³⁺ Fe²⁺ 4

[30] 4 Fe³⁺ Fe²⁺ Fe

]

pH 28 Kd [32] Eq. (3-3)] Eq. (3-4)]

β_REEs/Al2] β_REEs/Cu

M1 M24

Kd βM1/M2 1 4 βM1/M2 4 1]

[ 0 M1 M2

pH 28 βREEs/Al2] βREEs/Cu Fig. 3-7 ] pH 22] 3

2 βREEs/Al2] βREEs/Cu 4 [ ] 4 3

Equation (3-4)] β 41] 4

4 ] Cu²⁺ Al³⁺ ]

3 4

Eq. (3-3)

K

= (C

– C

) V C

M

β

REEs/(Al or Cu)

= K

_dREEs

K

d (Al or Cu)

Eq. (3-4)

Fig. 3-7 pH REEs/Al REEs/Cu

(a), (c): (b), (c):

[Reprinted from Biochemical Engineering Journal, 113, Y. Hosomomi, R. Wakabayashi, F. Kubota, N. Kamiya, M. Goto,102–106, Copyright (2016), with permission from Elsevier]

55 3-2-2-3. (Q_max)

Nd³⁺ Dy³⁺2] Lu³⁺

pH 3 Langmuir

Langmuir Eq. (3-5)

Q_m mg/g K_L: L/mg

] Fig. 3-8 Table 3-3 Langmuir

R² 2] Langmuir

] Nd³⁺ Dy³⁺2] Lu³⁺ 2 R² 40.97 3

4 Langmuir 4

KL [33] 2 KL

Lu³⁺ > Dy³⁺ > Nd³⁺ 3 4 [

4 DODGAA

4 3

Table 3-3 Langmuir R²

[Reprinted from Biochemical Engineering Journal, 113, Y. Hosomomi, R. Wakabayashi, F. Kubota, N. Kamiya, M. Goto,102–106, Copyright (2016), with permission from Elsevier]

Chemically modified E. coli Unmodified

E. coli ^[26]

R² KL (L/mg) Qm (mg/g) Qm (mg/g)

Nd³⁺ 0.988 0.0197 81.3 30.9

Dy³⁺ 0.974 0.0392 70.2 32.7

Lu³⁺ 0.978 0.0494 70.5 42.7

Eq. (3-5)

Q = Q

K

C

1+ K

C

Nd³⁺ Dy³⁺2] Lu³⁺ Qm 81.3 70.22] 70.5 mg/g

2.63 2.152] 1.65 4 3

] ]

[ 4

Fig. 3-8 Nd³⁺ Dy³⁺ Lu³⁺ ( : 30ºC, pHeq= 3)

[Reprinted from Biochemical Engineering Journal, 113, Y. Hosomomi, R. Wakabayashi, F.

Kubota, N. Kamiya, M. Goto,102–106, Copyright (2016), with permission from Elsevier]

57 3-2-3.

4 4

]

Nd³⁺ Dy³⁺ Lu³⁺ 2] Fe³⁺ Al³⁺ Cu²⁺

pH 2–3 4 DODGAA

4 4 pH 2–3

4 4

Al³⁺2] Cu²⁺ βREEs/Al2] βREEs/Cu

β_REEs/Al2] β_REEs/Cu ] 4 3

4 ]

4 3

2 Langmuir KL2] Qm

KL Lu³⁺ > Dy³⁺ > Nd³⁺

[ 4 DODGAA

4 Langmuir

2.5 4 3 4

]

58 3-3.

]

4 3

4 4

4 4 4

4 4 3

pKa 3.54 4

pH 3 4

4 pH 3

4 ]

4 8 pH ]

4 3 4

] Scheme 3-2

] ] ]

Nd³⁺ Dy³⁺2] Lu³⁺

Al³⁺ Cu²⁺ [

Scheme 3-2

H₂N NH₂

NH2 H2N

H₂ C H

C CH2 HN

O O

OH O E.#coli#cell#surface

Physical coating, pH 3

H₂ C H

C CH2 HN

O O

OH O H₂

C H C CH2 HN

O O

OH O

NH2 NH₂ E.#coli#cell#surface

m n-m

H₂ C H

C CH2 HN

O O

OH O H₂

C H C CH2 HN

O O

NH O

NH2 NH2

E.#coli#cell#surface

EDC _m

n-m

59 3-3-1.

3-3-1-1.

(1) polyallylamine hydrochloride3 HCl

polyallylamine hydrochloride M. W.= 15000 50.3 wt%; Nittobo medical Co. Ltd. (Tokyo, Japan)

5.0 mL 15 mL Wako Pure Chemical Industries (Osaka,

Japan) pH413 1 MWCO= 3500 Da;

Spectra/Por3; Spectrum Laboratories, Inc. (California, USA) 2 L 72

72 HCl4 polyallylamine ^[35] polyallylamine

PAA ¹H NMR ]

Polyallylamine (PAA): ¹H NMR (300 MHz, D2O): δ 1.11–1.52 (3H, CH2CH(CH2NH2), δ 2.59 (2H, CH₂CH(CH₂NH₂)

(2) polyallylamine

polyallylamine

1 step ] ^[27] Scheme 3-3

PAA 310.9 mg 5 mL 0.1 mol/L NaHCO3 (pH 8.0) 3 diglycolic anhydride Tokyo Chemical Industry Co. (Tokyo, Japan) 12.2 g 4 mL dimetylsulfoxide

4 Diglycolic anhydride

pH4 4 pH4pH 8.0 ] 10 M

4 8 MWCO= 3500 Da

72 72

polymer 1 ¹H NMR ]

Polymer 1: ¹H NMR (300 MHz, D2O): δ 1.25–1.79 (3H, CH2CH(CH2NHCO), δ 3.22 (2H, CH2CH(CH2NHCO), δ 4.01 (2H, NHCOCH2O), δ 4.08 (2H, CH2COOH)

60 Scheme 3-3 polymer 1

3-3-1-2.

(1)

pET22b⁺ BL21 DE3 100

mg/L LB 10 mL 100 mg/L

LB 1 L 37ºC 200 rpm OD600= 0.5–0.6

4000g 20 5800g 10 ]

3 polymer

(2) polymer 1

45 mL 902.6 mg polymer 1 pH 3.0 ] 1 mol/L HCl

pH 454.7 mg 2

1-(3- dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC; Tokyo Chemical Industry Co.)

4.99 g pH 4.75 1 mol/L NaOH 2

5800g 10 0.1 mol/L HCl pH 4.0 5800g 10

] 2 5800g 10 ]

] polymer 1

H₂ C H

C CH₂ HN

O O

OH O

H₂ C H

C CH₂ NH₂ _n

+

O O

61 3-3-1-3.

1000 ppm Wako Pure Chemical Industries (Osaka, Japan) [ Nd³⁺

Dy³⁺2] Lu³⁺ Nd³⁺ Dy³⁺2] Lu³⁺ Nd(NO3)3 6H2O 99.9 ; Kishida Chemical Co., Ltd. (Osaka, Japan) Dy(NO3)3 5H2O 99.9%; Kishida Chemical Co., Ltd.

Lu(NO₃)₃ nH₂O 99.5%, Wako Pure Chemical Industries 0.1M HEPES ]

0.1 M HNO3 1 M 10 M NaOH ] pH

2.5 mL 5 mg 30 vortex mixer 38 30ºC

60 160 rpm 5800g 10

0.20 µm

pH pHeq pH HM-60 G, DKK-TOA Co.

ICP ICP-AES, Optima 5300 DV, PerkinElmer Inc.

(A)2] (Q: mg/g) Eq. (3-1) (3-2)3

1 mol/L HNO3 5 mL

Eq. (3-6)3 Ci (ppm) Ce

(ppm) Cd (ppm)

3-3-1-4.

2] 4 cm^-1 4000–700 cm^-1 FT-IR

Spectrum 65, PerkinElmer Co. ] polymer 1

Dy³⁺ 100 ppm pH 3 2

] Dy pH 3 FT-IR ]

SEM SS550, Shimadzu Co., Ltd. (Kyoto, Japan) ] 20.0 kV 1000

Eq. (3-6)

D = C

– C

C

62 3-3-2.

3-3-2-1.

2] 4000–700 cm^-1 FT-IR ]

polymer 1 Fig. 3-9(a)2] (b) 4000

2000 cm^-1 2 3700 3000 cm^-1 3000

2800 cm^-1 N-H O-H2] C-H 4 2000 700 cm^-1

]

I2] II 41655 cm^-12] 1550 cm^-1 1460

cm^-1 1400 cm^-1 O-H 4

41240 cm^-12] 1075 cm^-1

polymer 1 2 1140 cm^-1

4 Fig. 3-9 (b)

] polymer 1 4

Fig. 3-9 FT-IR

(a) , (b) polymer 1 , (c) pH 3 , (d) pH 3

500 1000

1500 2000

2500 3000

3500 4000

T (%)

Wavenumber (cm^-1)

(a)

(b)

(c) (d)

2] polymer 1 SEM ]

Fig. 3-10 2 2–5 µm 4

3 ] polymer 1 2

Fig. 3-10 SEM

(a) , (b) polymer 1

10 µm 10 µm

(a) (b)

64 3-3-2-2.

Figure 3-11 Dy³⁺ ] polymer 1

5 4 3 4

4 4 2

] 4 4 4

Fig. 3-11 Dy³⁺ A

(pH: 2.0, : 30 , Ci: 5 ppm)

0 0.2 0.4 0.6 0.8 1

0 10 20 30 40 50 60

A (-)

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