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«A template-directed synthetic approach to halogen-bridged mixed-valence platinum complexes on artificial peptides in solution a Kentaro Tanaka,a,b ...»

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To a solution of RSO3 H (570 mg, 1.03 mmol) in methanol (1.0 cm3 ) was added a solution of NaOH (42.0 mg, 1.05 mmol) in methanol (1.0 cm3 ) at room temperature. The resulting precipitate was dissolved in methanol and the remaining insoluble matter was filtered off. The solvent of the filtrate was removed under reduced pressure and dried in vacuo. The crude material (611 mg) was purified by recrystallization with methanol/2-propanol (1:1, 5 cm3 ) to afford RSO3 Na (357 mg, 60%) as a colorless liquid (Found: C, 62.68; H, 10.93. C 30 H61 NaO6 S requires C, 62.90; H, 10.73); δH(500 MHz;

CD3 OD; Me4 Si) 3.70 (t, J = 6.2 Hz, 2H, -CH2 SO3 Na), 3.58 (m, 1H, methine), 3.53-3.42 (m, 8H, 2 ×

-CH2 OCH2 -), 2.89 (m, 2H, -CH2 CH2 CH2 SO3 Na), 2.02 (m, 2H, -CH2 CH2 SO3 Na), 1.56 (m, 4H, 2 ×

-CH2 CH2 OCH2 CH-), 1.37-1.29 (m, 36H, 2 × CH3 (CH2 )9 -), 0.90 (t, J = 6.9 Hz, 6H, 2 × CH3 (CH2 )9 -);

m/z (ESI-TOF) 595.48 (M + Na+. C 30 H61 Na2 O6 S requires 595.40).

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Synthesis of Pt(II) complex-bearing peptides [1a-d(Pt(II)(en))n](RSO3)2n: (n = 2, 3, 9, 10) To a solution of [1a-d(Pt(II)(en))n ](CF3 COO)2n : (n = 2, 3, 9, 10) in methanol was added RSO3 Na (2n equiv) at room temperature. After stirring for 12 h at room temperature, the solvent was removed under reduced pressure and dried in vacuo. The residue was washed with water (3 times), reprecipitated with methanol/acetone or dichloromethane/acetone and lyophilized to obtain [1a-d(Pt(II)(en))n ](RSO3 )2n (1a; 94%, 1b; 48%, 1c; 94%, 1d; 72%) as a colorless foam (for [1a(Pt(II)(en))2 ](RSO3 )4 Found: C, 53.41; H, 9.61; N, 4.92. C 156 H325 N13 O37 Pt2 S4 requires C, 53.63; H, 9.38; N, 5.21, for [1b(Pt(II)(en))3 ](RSO3 )6 Found: C, 53.70; H, 9.38; N, 5.11. C 233 H485 N19 O55 Pt3 S6 requires C, 53.56; H, 9.67; N, 4.87, for [1c(Pt(II)(en)) 9 ](RSO3 )18 Found: C, 52.50; H, 9.35; N, 4.73.

C 695 H1445 N55 O163 Pt9 S18 ·21H2 O requires C, 52.52; H, 9.43; N, 4.85, for [1d(Pt(II)(en))10 ](RSO3 )20 Found: C, 53.65; H, 9.65; N, 4.74. C772 H1605 N61 O181Pt10 S20 requires C, 53.81; H, 9.39; N, 4.96);

δH(500 MHz; CD3 OD; Me4 Si) for [1a(Pt(II)(en))2 ](RSO3 )4 4.51-4.02 (m, 8H, 2 × -NCH2 CO-, 2 ×

-OCH2 CO-), 3.77-3.69 (m, 12H, 2 × -OCH2 CHNH 2, 4 × -CH2 SO3 ), 3.64-3.41 (m, 68H, 2 ×

-OCH2 CH2 N-, 2 × -OCH2 CH2 OCH2 CH2 O-, 2 × -NHCH2 CH2 O-, 8 × -OCH2 CHO- (RSO3 ), 4 ×

-OCH2 CHO- (RSO3 ), 8 × -CH2 OCH2 CHO- (RSO3 )), 3.11 (br, 2H, 2 × -OCH2 CHNH2 ), 2.93-2.89 (m, 8H, 4 × -CH2 CH2 CH2 SO3 ), 2.79-2.77 (br, 2H, 2 × -CHCHHNH2 ), 2.69-2.63 (m, 10H, 2 ×

-CHCHHNH2, 2 × NH2 CH2 CH2 NH2 ), 2.07-2.01 (m, 8H, 4 × -CH2 CH2 SO3 ), 1.96 (m, 3H, Ac), 1.59-1.54 (m, 16H, 8 × -CH2 CH2 OCH2 CHO-), 1.35-1.30 (m, 144H, 8 × CH3 (CH2 )9 -), 0.90 (m, 24H, 8 × CH3 (CH2 )9 -), for [1b(Pt(II)(en))3 ](RSO3 )6 4.51-4.01 (m, 12H, 3 × -NCH2 CO-, 3 × -OCH2 CO-), 3.75-3.69 (m, 18H, 3 × -OCH2 CHNH2, 6 × -CH2 SO3 ), 3.64-3.41 (m, 102H, 3 × -OCH2 CH2 N-, 3 ×

-OCH2 CH2 OCH2 CH2 O-, 3 × -NHCH2 CH2 O-, 12 × -OCH2 CHO- (RSO3 ), 6 × -OCH2 CHO- (RSO3 ), 12 × -CH2 OCH2 CHO- (RSO3 )), 3.10 (br, 3H, 3 × -OCH2 CHNH2 ), 2.92-2.89 (m, 12H, 6 ×

-CH2 CH2 CH2 SO3 ), 2.77 (br, 3H, 3 × -CHCHHNH2 ), 2.69-2.63 (m, 15H, 3 × -CHCHHNH2, 3 × NH2 CH2 CH2 NH2 ), 2.06-2.01 (m, 12H, 6 × -CH2 CH2 SO3 ), 1.96-1.95 (m, 3H, Ac), 1.59-1.53 (m, 24H, 12 × -CH2 CH2 OCH2 CHO-), 1.35-1.29 (m, 216H, 12 × CH3 (CH2 )9 -), 0.90 (m, 36H, 12 × CH3 (CH2 )9 -), S16 Electronic Supplementary Information for Dalton Transactions This journal is © The Royal Society of Chemistry 2007 for [1c(Pt(II)(en))9 ](RSO3 )18 4.53-4.07 (m, 36H, 9 × -NCH2 CO-, 9 × -OCH2 CO-), 3.75-3.70 (m, 54H, 9 × -OCH2 CHNH2, 18 × -CH2 SO3 ), 3.64-3.42 (m, 306H, 9 × -OCH2 CH2 N-, 9 ×

-OCH2 CH2 OCH2 CH2 O-, 9 × -NHCH2 CH2 O-, 36 × -OCH2 CHO- (RSO3 ), 18 × -OCH2 CHO- (RSO3 ), 36 × -CH2 OCH2 CHO- (RSO3 )), 3.13 (br, 9H, 9 × -OCH2 CHNH2 ), 2.94-2.90 (m, 36H, 18 ×

-CH2 CH2 CH2 SO3 ), 2.79 (br, 9H, 9 × -CHCHHNH2 ), 2.69-2.64 (m, 45H, 9 × -CHCHHNH2, 9 × NH2 CH2 CH2 NH2 ), 2.08-2.02 (m, 36H, 18 × -CH2 CH2 SO3 ), 1.96-1.91 (m, 3H, Ac), 1.59-1.54 (m, 72H, 36 × -CH2 CH2 OCH2 CHO-), 1.35-1.29 (m, 648H, 36 × CH3 (CH2 )9 -), 0.92-0.89 (m, 108H, 36 × CH3 (CH2 )9 -), for [1d(Pt(II)(en))10 ](RSO3 )20 4.53-4.07 (m, 40H, 10 × -NCH2 CO-, 10 × -OCH2 CO-), 3.75-3.70 (m, 60H, 10 × -OCH2 CHNH2, 20 × -CH2 SO3 ), 3.64-3.42 (m, 340H, 10 × -OCH2 CH2 N-, 10 ×

-OCH2 CH2 OCH2 CH2 O-, 10 × -NHCH2 CH2 O-, 40 × -OCH2 CHO- (RSO3 ), 20 × -OCH2 CHO- (RSO3 ), 40 × -CH2 OCH2 CHO- (RSO3 )), 3.14 (br, 10H, 10 × -OCH2 CHNH2 ), 2.94-2.91 (m, 40H, 20 ×

-CH2 CH2 CH2 SO3 ), 2.80 (br, 10H, 10 × -CHCHHNH2 ), 2.64 (m, 50H, 10 × -CHCHHNH2, 10 × NH2 CH2 CH2 NH2 ), 2.08-2.02 (m, 40H, 20 × -CH2 CH2 SO3 ), 1.96-1.91 (m, 3H, Ac), 1.59-1.54 (m, 80H, 40 × -CH2 CH2 OCH2 CHO-), 1.35-1.30 (m, 720H, 40 × CH3 (CH2 )9 -), 0.90 (m, 120H, 40 × 2RSO3 -.

CH3 (CH2 )9 -); m/z (ESI-TOF) for [1a(Pt(II)(en))2 ](RSO3 )4 1196.84 (M C 96 H201 N13 NaO25 Pt2 S2 requires 1196.69), for [1b(Pt(II)(en))3 ](RSO3 )6 1187.02 (M - 3RSO3 -.

C 143 H299 N19 O37 Pt3 S3 requires 1187.02).

Synthesis of Pt(IV) complex-bearing peptides [1a-d(Pt(IV)Br2(en))n](RSO3)2n: (n = 2, 3, 9, 10) To a solution of [1a-d(Pt(II)(en))n ](CF3 COO)2n : (n = 2, 3, 9, 10) in ethanol was added excess bromine at room temperature. After stirring for 15 min at room temperature, the solvent and excess bromine were removed under reduced pressure and dried in vacuo. To the residue was added a solution of RSO3 Na (2n equiv) in methanol. After stirring for 4 h at room temperature, the solvent was removed under reduced pressure and dried in vacuo. The residue was washed with water (8 times) and lyophilized. The crude material was purified by reprecipitaion with acetone/methanol, S17 Electronic Supplementary Information for Dalton Transactions This journal is © The Royal Society of Chemistry 2007 methanol/diethyl ether or dichloromethane/diethyl ether to afford [1a-d(Pt(IV)Br2 (en))n ](RSO3 )2n (1a;





49%, 1b; 65%, 1c; 82%, 1d; 76% (2 steps)) as a yellow foam (for [1a(Pt(IV)Br2 (en))2 ](RSO3 )4 Found:

C, 48.88; H, 8.71; N, 4.54. C156 H325 Br4 N13 O37 Pt2 S4 requires C, 49.13; H, 8.59; N, 4.77, for [1b(Pt(IV)Br2 (en))3 ](RSO3 )6 Found: C, 49.00; H, 8.83; N, 4.47. C233 H486 Br6 N19 O55 Pt3 S6 requires C, 49.18; H, 8.59; N, 4.68, for [1c(Pt(IV)Br2 (en))9 ](RSO3 )18 Found: C, 47.94; H, 8.72; N, 4.44.

C 695 H1445 Br18 N55 O163 Pt9 S18 ·27H2 O requires C, 47.86; H, 8.66; N, 4.42, for [1d(Pt(IV)Br2 (en))10 ](RSO3 )20 Found: C, 49.02; H, 8.64; N, 4.37. C 772 H1605 Br20 N61 O181 Pt10 S20 requires C, 49.24; H, 8.59; N, 4.54); δH(500 MHz; CD3 OD; Me 4 Si) for [1a(Pt(IV)Br2 (en))2 ](RSO3 )4 4.61-4.10 (m, 8H, 2 × -NCH2 CO-, 2 × -OCH2 CO-), 3.94-3.91 (m, 2H, 2 × -OCHHCHNH2 ), 3.78-3.75 (m, 2H, 2 × -OCHHCHNH2 ), 3.70 (t, J = 6.2 Hz, 8H, 4 × -CH2 SO3 ), 3.63-3.39 (m, 70H, 2 × -OCH2 CHNH2, 2 ×

-OCH2 CH2 N-, 2 × -OCH2 CH2 OCH2 CH2 O-, 2 × -NHCH2 CH2 O-, 8 × -OCH2 CHO- (RSO3 ), 4 ×

-OCH2 CHO- (RSO3 ), 8 × -CH2 OCH2 CHO- (RSO3 )), 3.31-3.30 (2H, 2 × -CHCHHNH2 ), 3.07-2.96 (m, 10H, 2 × -CHCHHNH2, 2 × NH2 CH2 CH2 NH2 ), 2.91-2.88 (m, 8H, 4 × -CH2 CH2 CH2 SO3 ), 2.05-1.99 (m, 8H, 4 × -CH2 CH2 SO3 ), 1.96-1.95 (m, 3H, Ac), 1.59-1.53 (m, 16H, 8 × -CH2 CH2 OCH2 CHO-), 1.39-1.29 (m, 144H, 8 × CH3 (CH2 )9 -), 0.90 (m, 24H, 8 × CH3 (CH2 )9 -), for [1b(Pt(IV)Br2 (en))3 ](RSO3 )6 4.63-4.11 (m, 12H, 3 × -NCH2 CO-, 3 × -OCH2 CO-), 3.93 (br, 3H, 3 ×

-OCHHCHNH2 ), 3.78-3.76 (m, 3H, 3 × -OCHHCHNH2 ), 3.70 (t, J = 6.2 Hz, 12H, 6 × -CH2 SO3 ), 3.63-3.39 (m, 105H, 3 × -OCH2 CHNH2, 3 × -OCH2 CH2 N-, 3 × -OCH2 CH2 OCH2 CH2 O-, 3 ×

-NHCH2 CH2 O-, 12 × -OCH2 CHO- (RSO3 ), 6 × -OCH2 CHO- (RSO3 ), 12 × -CH2 OCH2 CHO- (RSO3 )), 3.31-3.30 (3H, 3 × -CHCHHNH2 ), 3.07-2.98 (m, 15H, 3 × -CHCHHNH2, 3 × NH2 CH2 CH2 NH2 ), 2.91-2.88 (m, 12H, 6 × -CH2 CH2 CH2 SO3 ), 2.05-1.99 (m, 12H, 6 × -CH2 CH2 SO3 ), 1.96-1.95 (m, 3H, Ac), 1.58-1.53 (m, 24H, 12 × -CH2 CH2 OCH2 CHO-), 1.35-1.29 (m, 216H, 12 × CH3 (CH2 )9 -), 0.91-0.88 (m, 36H, 12 × CH3 (CH2 )9 -), for [1c(Pt(IV)Br2 (en))9 ](RSO3 )18 4.62-4.11 (m, 36H, 9 ×

-NCH2 CO-, 9 × -OCH2 CO-), 3.93 (br, 9H, 9 × -OCHHCHNH2 ), 3.79-3.77 (m, 9H, 9 ×

-OCHHCHNH2 ), 3.70 (t, J = 6.2 Hz, 36H, 18 × -CH2 SO3 ), 3.63-3.39 (m, 315H, 9 × -OCH2 CHNH2, 9 × -OCH2 CH2 N-, 9 × -OCH2 CH2 OCH2 CH2 O-, 9 × -NHCH2 CH2 O-, 36 × -OCH2 CHO- (RSO3 ), 18 ×

-OCH2 CHO- (RSO3 ), 36 × -CH2 OCH2 CHO- (RSO3 )), 3.31-3.30 (9H, 9 × -CHCHHNH2 ), 3.07-3.00 (m, 45H, 9 × -CHCHHNH2, 9 × NH2 CH2 CH2 NH2 ), 2.92-2.89 (m, 36H, 18 × -CH2 CH2 CH2 SO3 ), 2.05-1.99 (m, 36H, 18 × -CH2 CH2 SO3 ), 1.96-1.95 (m, 3H, Ac), 1.59-1.53 (m, 72H, 36 × -CH2 CH2 OCH2 CHO-), 1.35-1.29 (m, 648H, 36 × CH3 (CH2 )9 -), 0.90 (m, 108H, 36 × CH3 (CH2 )9 -), for [1d(Pt(IV)Br2 (en))10 ](RSO3 )20 4.62-4.13 (m, 40H, 10 × -NCH2 CO-, 10 × -OCH2 CO-), 3.93 (br, 10H, 10 × -OCHHCHNH2 ), 3.79 (br, 10H, 10 × -OCHHCHNH2 ), 3.70 (t, J = 6.2 Hz, 40H, 20 × -CH2 SO3 ), 3.63-3.39 (m, 350H, 10 × -OCH2 CHNH2, 10 × -OCH2 CH2 N-, 10 × -OCH2 CH2 OCH2 CH2 O-, 10 ×

-NHCH2 CH2 O-, 40 × -OCH2 CHO- (RSO3 ), 20 × -OCH 2 CHO- (RSO3 ), 40 × -CH2 OCH2 CHO- (RSO3 )), 3.31-3.30 (10H, 10 × -CHCHHNH2 ), 3.06-2.96 (m, 50H, 10 × -CHCHHNH2, 10 × NH2 CH2 CH2 NH2 ), S18 Electronic Supplementary Information for Dalton Transactions This journal is © The Royal Society of Chemistry 2007 2.91-2.88 (m, 40H, 20 × -CH2 CH2 CH2 SO3 ), 2.05-1.98 (m, 40H, 20 × -CH2 CH2 SO3 ), 1.96-1.95 (m, 3H, Ac), 1.59-1.53 (m, 80H, 40 × -CH2 CH2 OCH2 CHO-), 1.35-1.29 (m, 720H, 40 × CH3 (CH2 )9 -), 0.90 (m, 120H, 40 × CH3 (CH2 )9 -); m/z (ESI-TOF) for [1a(Pt(IV)Br2 (en))2 ](RSO3 )4 1356.67 (M - 2RSO3 -.

C 96 H201 Br4 N13 NaO25 Pt2 S2 requires 1356.52), for [1b(Pt(IV)Br2 (en))3 ](RSO3 )6 1346.89 (M - 3RSO3 -.

C 143 H299 Br6 N19 O37 Pt3 S3 requires 1346.85).

Lipophilic mononuclear Pt complexes ([Pt(II)(en)2 ](RSO3 )2 and [Pt(IV)Br2 (en)2 ](RSO3 )2 ) were prepared according to Scheme S4.

Scheme S4 Preperation of lipophilic mononuclear Pt complexes.

Synthesis of [Pt(II)(en)2](RSO3)2 To a solution of [Pt(II)(en)2 ]Br2 (30.0 mg, 63.1 µmol) in water (0.5 cm3 ) was added RSO3 Na (65.1 mg, 114 µmol) at room temperature. After shaking for 4 h at 55 °C with an ultrasonic cleaning machine, the suspension was centrifuged and the precipitate was lyophilized. The residue was dissolved in methanol/water (1:1, 0.4 cm3 ) and again shaken for 4 h at 55 °C with an ultrasonic cleaning machine.

S19 Electronic Supplementary Information for Dalton Transactions This journal is © The Royal Society of Chemistry 2007 The suspension was centrifuged and the precipitate was washed with methanol/water (1:1, 3 × 0.2 cm3 ) and lyophilized to obtain [Pt(II)(en)2 ](RSO3 )2 (50.1 mg, 62%) as a white solid (Found: C, 54.13;

H, 9.96; N, 3.89. C 64 H138 N4 O12 PtS2 requires C, 54.32; H, 9.83; N, 3.96); δH(500 MHz; CDCl3 ; Me4 Si) 5.57 (br, 8H, 2 × NH2 CH2 CH2 NH2 ), 3.74 (t, J = 6.4 Hz, 4H, 2 × -CH2 SO3 ), 3.65-3.61 (m, 2H, 2 × methine), 3.52-3.46 (m, 8H, 4 × -OCH2 CHO-), 3.45-3.39 (m, 8H, 4 × -CH2 OCH2 CHO-), 3.01-2.98 (m, 4H, 2 × -CH2 CH2 CH2 SO3 ), 2.67 (s, 8H, 2 × NH2 CH2 CH2 NH2 ), 2.17-2.11 (m, 4H, 2 × -CH2 CH2 SO3 ), 1.56-1.52 (m, 8H, 4 × -CH2 CH2 OCH2 CHO-), 1.31-1.26 (m, 72H, 4 × CH3 (CH2 )9 -), 0.88 (t, J = 6.9 Hz, 12H, 4 × CH3 (CH2 )9 -); m/z (ESI-TOF) 864.61 (M - 2RSO3 -. C 34 H77 N4 O6 PtS requires 864.52).

Synthesis of [Pt(IV)Br2(en)2](RSO3)2

To a solution of [Pt(IV)Br2 (en)2 ]Br2 (50.0 mg, 78.8 µmol) in methanol (1.0 cm3 ) was added RSO3 Na (81.2 mg, 142 µmol) at room temperature. After stirring for 40 h at room temperature, the solvent was removed under reduced pressure and dried in vacuo. The residue was washed with water (0.7 cm3 ) and acetone/water (1:3, 2 × 0.4 cm3 ), and then lyophilized. The crude material (92.3 mg) was recrystallized by methanol/2-propanol (1:10, 5.5 cm3 ) to give [Pt(IV)Br2 (en)2 ](RSO3 )2 (60.6 mg, 54%) as a yellow solid (Found: C, 48.65; H, 8.75; N, 3.45. C64 H138 Br2 N4 O12 PtS2 requires C, 48.81; H, 8.83;

N, 3.56); δH(500 MHz; CD3 OD; Me4 Si) 3.70 (t, J = 6.2 Hz, 4H, 2 × -CH2 SO3 ), 3.60-3.56 (m, 2H, 2 × methine), 3.53-3.50 (m, 8H, 4 × -OCH2 CHO-), 3.48-3.42 (m, 8H, 4 × -CH2 OCH2 CHO-), 3.04-2.99 (m, 8H, 2 × NH2 CH2 CH2 NH2 ), 2.91-2.88 (m, 4H, 2 × -CH2 CH2 CH2 SO3 ), 2.05-1.99 (m, 4H, 2 ×

-CH2 CH2 SO3 ), 1.58-1.53 (m, 8H, 4 × -CH2 CH2 OCH2 CHO-), 1.35-1.29 (m, 72H, 4 × CH3 (CH2 )9 -), 0.90 (t, J = 7.0 Hz, 12H, 4 × CH3 (CH2 )9 -); m/z (ESI-TOF) 1025.47 (M - 2RSO3 -. C 34 H77 N4 NaO6 PtS requires 1025.36).

–  –  –

Fig. S1 Photometric titration spectra of [1b(Pt(IV)Br2 (en))3 ](RSO3 )6 with [1a(Pt(II)(en))2 ](RSO3 )4 in CH2 Cl2 at 293 K (l = 1). [[1b(Pt(IV)Br2 (en))3 ](RSO3 )6 ] = 12.5 µM. [[1a(Pt(II)(en))2 ](RSO3 )4 ] = 0.0, 2.5, 5.0, 7.5, 10, 12.5, 15, 17.5, 20, 25, 37.5 and 50 µM.

–  –  –

Fig. S2 Photometric titration spectra of [1d(Pt(IV)Br2 (en))10 ](RSO3 )20 with [1c(Pt(II)(en))9 ](RSO3 )18 in CH2 Cl2 at 293 K (l = 1). [[1d(Pt(IV)Br2 (en))10 ](RSO3 )20 ] = 2.5 µM. [[1c(Pt(II)(en))9 ](RSO3 )18 ] = 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5 and 5.0 µM.

–  –  –

Fig. S3 1 H NMR titration spectra of [1a(Pt(IV)Br2 (en))2 ](RSO3 )4 (5 mM) with [Pt(II)(en)2 ](RSO3 )2 in CD2 Cl2 at 293 K. ▼ is the peak of methylene groups of ethylenediamine in [1a(Pt(IV)Br2 (en))2 ](RSO3 )4.

–  –  –

References

1. L. Zhang, G. S. Kauffman, J. A. Pesti, J. Yin, J. Org. Chem., 1997, 62, 6918-6920.

2. A. W. Schwabacher, J. W. Lane, M. W. Schiesher, K. M. Leigh, C. W. Johnson, J. Org. Chem., 1998, 63, 1727-1729.

3. F. Basolo, J. C. Bailar, Jr., B. R. Tarr, J. Am. Chem. Soc., 1950, 72, 2433-2438.

4. G. W. Watt, R. E. McCarley, J. Am. Chem. Soc., 1957, 79, 3315-3317.

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