Supplementary Figure S1. 1 H and 13 C-DEPT NMR spectra of initial product,12-no-edf, in CDCl 3 at room temperature. The ratio of the 2,2-12-BTBA and

Transcription

1 Supplementary Figure S1. 1 and 13 C-DEPT NMR spectra of initial product,12-no-edf, in CDCl 3 at room temperature. The ratio of the 2,2-12-BTBA and 3,3-12-BTBA isomers is approximately 17:83. 1

2 3,3-12-BTBA 2,2-12-BTBA Supplementary Figure S2. Two-dimensional 1-13 C SQC spectrum of 3,3-12-BTBA and 2,2-12-BTBA in 12-No-EDF in CDCl 3 at room temperature with an enlarged inset. 2

3 3,3-12-BTBA 2,2-12-BTBA Supplementary Figure S3. Two-dimensional 1-13 C MBC spectrum of of 3,3-12-BTBA and 2,2-12-BTBA in 12-No-EDF in CDCl 3 at room temperature with an enlarged inset. 3

4 a b Supplementary Figure S4. (a) 1 and (b) 13 C DEPT-135 NMR spectra of 12-EDFNP in CDCl 3 at room temperature 4

5 a ydrogen bonded C- b c Supplementary Figure S5. 1 NMR spectra of (a)14-edfnp, (b)16-edfnp and (c)18-edfnp in CDCl 3 at room temperature. 5

6 Supplementary Figure S6. Two-dimensional 1-13 C SQC pectrum of 12-EDFNP in CDCl 3 at room temperature. 6

7 Supplementary Figure S7. Two-dimensional 1-13 C SQC pectrum of 12-EDFNP (Region A) in CDCl 3 at room temperature. 7

8 Supplementary Figure S8. Two-dimensional 1-13 C MBC pectrum of 12-EDFNP in CDCl 3 at room temperature. 8

9 Supplementary Figure S9. Two-dimensional 1-13 C MBC spectra (Region B and C) of 12-EDFNP in CDCl 3 at room temperature. The signals related to the minor product of 2,3-diacylglycero-bisphenol-glycerol (4%) is in green. The signals related to few reactants, 2,2'-12-BTBA (1%) and 3,3'-12-BTBA (15%), are in orange and pink respectively. 9

10 2-monoacylglycerol groups with collective proton motion in 12-EDPNP Supplementary Figure S10. Two-dimensional 1-13 C MBC spectrum (Region B and C) of 2-monoacylglycerol moieties derived from 2,2'-12-BTBA and 2,3-12-BTBA in CDCl 3 at room temperature 10

11 11 R R f e a b d c g h X e a b c d f g h 2,3-BTBA molecules in 12-EDPNP Supplementary Figure S11. Two-dimensional 1-13 C MBC spectrum (Region B and C) of 2,3-12-BTBA in CDCl 3 at room temperature

12 R R R R b b b b 2,2'-12-BTBA in EDFNPs with collective proton motion 2,3-12-BTBA in EDFNPs with collective proton motion R R R R R R b b b b b Free 2,3-diacylglycerol, glycerol bisphenol A Free 3,3'-12-BTBA Free 2,2'-12-BTBA Supplementary Figure S12. 1 NMR spectra of (a) 12-No-EDF: Initial product by epoxy ring opening reaction, (b) 12-EDFNP: Product obtained after further treatment of 12-No-EDF with ammonium persulfate at 150 C for 38 hours and (c) product obtained after further treatment of 12-No-EDF with sodium carbonate at 150 C for 38 hours. 12

13 a 3-monoacylglycerol with 2-alkoxy radical intermediate 2-monoacylglycerol with 3-alkoxy radical, Total energy (h) Relative energy (kcal/mol) b 3-monoacylglycerol intermediate 2-monoacylglycerol Total energy (h) Relative energy (kcal/mol) Supplementary Figure S13. Calculation results at M06-2X/cc-pVDZ level for the energies differences (in kcal/mol) of the 3-monoacylglycerol, intermediates and 2-monoacylglycerol moieties in the 3,2-acyl migration through (a) alkoxy radical passway and (b) hydroxyl passway. 13

14 Supplementary Figure S14. Measurements of the hydrodynamic diameter of n-edfnps (n = 12, 14, 16 and 18) by dynamic light scattering experiment. 14

15 a b Supplementary Figure S15. Measurements of the fluorescence lifetime of (a) 12-No-EDF excited at 329 nm, (b) 12-EDFNP excited at 360 nm. 15

16 Supplementary Figure S16. (a) Synthesis of 17-EDFNP based on straric acid. (b) 1 NMR spectra of 17-No-EDF. (c) 1 NMR spectra of 17-EDFNP. 16

17 Supplementary Figure S17. (a) Synthesis of 16- BGE-EDFNP based on n-butyl glycidyl. (b) 1 NMR spectra of 16-BGE-No-EDF. (c) 1 NMR spectra of 16-BGE-EDFNP. 17

18 Supplementary Figure S18. DSY 1 NMR 2D spectra for 18-EDFNP in CDCl 3 at room temperature. 18

19 Supplementary Figure S19. Calculation results at M06-2X/cc-pVDZ level for the energies differences (in kcal/mol) of (a) optimized geometry of 2-monoacylglycerol, (b) individual molecules with optimized geometries for 2-monoacylglycerol trimer and (c) optimized geometry of hydrogen bonded 2-monoacylglycerol trimer and its top and bottom views. (d) ptimized geometry of 3-monoacylglycerol trimer. The unit of bond length is angstrom. 19

20 a + n n=11or12 relux in MeCN (N 4 ) 2 S 2 8 diacylglycerol-bisphenol d e n m c b a c b a f g h a b a b c c or b a c c b a a b c b Supplementary Figure S20. (a) Synthesis of EDF-Polymer by the reaction of bisphenol A diglycidyl ether with poly(ethylene glycol) bis(carboxymethyl) ether (M n = 600) in the presence of (N 4 ) 2 S 2 8 catalyst and (b) the 1 NMR spectra in CDCl 3 at room temperature. 20

21 Supplementary Table S1. Cartesian coordinates of the optimized ground stated structure for cyclic acetyl-2-monoacylglycerolmethane trimer at the UM06-2X/6-31g(d) level Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

22 Supplementary Table S2. Cartesian coordinates of the optimized second excited stated structure for cyclic acetyl-2-monoacylglycerolmethane trimer at the TD-DFT/UM06-2X/6-31g(d) level Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

23 Supplementary Methods Materials and Measurements All reagents and solvents were used as received from commercial suppliers without further purification. Analyses for C, and N were carried out on a vario EL III elemental analyzer (Elementar Company). IR spectra were recorded using a Nicolet 6700 FT-IR spectrophotometer and the spectra were determined in a sealed liquid cell with a KBr windows (0.1mm Pathlength/0.04mL Volume) at room temperature. 1, 13C, DEPT-135, SQC, MBC and DSY NMR spectra were recorded on a Bruker AVANCE 600 Mz or Agilent 400-MR DD2 400 Mz NMR spectrometers. Photoluminescence (PL) spectra were recorded with a Varian Cary Eclipse fluorescence spectrometer. The RTEM images were taken with a JEM-2100F (JEL, Japan) operated at 200 kv and the sample was prepared by drop-casting a suspension of C 2 Cl 2 onto a quantifoil holey carbon grid. The hydrodynamic particle size is measured with dynamic light scattering (Brookhaven 90Plus, USA). Mass spectrometry experiments were performed in the positive-ion mode on a linear-type time-of-flight mass spectrometer (microflex, Bruker Daltonics) with a flight length of 1.05 m. The samples were irradiated with a 337 nm nitrogen laser at 20 z. The generated ions were accelerated at voltage of 19 kv. To obtain good signal-to-noise ratios, the laser energy was adjusted to slightly higher than the threshold and each spectrum was acquired by an average of 200 laser pulses. Standard solutions containing 10 mm 18-EDFNP were prepared in tetrahydrofuran (TF), and diluted to desired concentration by TF. α-cyano-4-hydroxycinnamic acid (CCA) solution fresh prepared in 1:2 acetonitrile/0.1 M phosphate buffer, was used as the MALDI matrices for n-edfnp. MALDI samples were prepared by mixing 1µL of analyte solution and 1 µl of matrix solution on the target and letting them dry at room temperature. The quantum yields of the n-edfnps were estimated by using Coumarin 1 as a reference standard (Coumarin 1 solution were prepared in ethanol, quantum yields = 73%). Quantum Yields are calculated using the following equation: Q = Q R I E R n 2 /I R E n 2 R, where I = Integrated fluorescence intensity, E = Extinction, n = refractive index (the index R indicates the standard). Gel permeation chromatography (GPC) was performed using a Waters apparatus (515 PLC pump, 717 autosampler, 2410 refractive index detector) and a Waters Stygel R4E column with a 1.0 ml/min flow rate of TF at 40 C and calibrated by polystyrene standards. All 23

24 calculations were performed at the National Center for igh-performance Computing facility by using the Gaussian 09, Revision C.01 package 31. The TD-DFT calculations were performed by using TD-DFT/UM06-2X/6-31g(d) method based on the optimized structure of the second excited state of the cyclic acetyl 2-monoacylglycerolmethane trimer at the UM06-2X/6-31g(d) level. Because the first excited state (S 1 ) is the dark state and the second electronic state (S 2 ) with a large oscillator strength is responsible for the strong UV absorption. Cartesian coordinates of the optimized ground and excited state geometry structures of cyclic hydrogen bonded acetyl-2-monoacylglycerolbenzene trimer are listed in Supplementary Tables S1 and S2. Synthesis and characterization of 3,4,5-tris(n-alkyloxy) benzoic acid (n= 12, 14, 16 and 18). General method for the synthesis of ethyl-3,4,5-tris(n-alkyloxy)benzoate The title compounds were synthesized according to a known procedure 32 and the preparation of ethyl-3,4,5-tris(dodecyloxy)benzoate has been selected as a representative example because the same procedure was systematically used for all the members of the series. A solution of Gallic acid ethyl ester (5.01 g, mmol), K 2 C 3 (17.43 g, mmol) and KI (catalytic amount) in acetone (100 ml) was reflux at 60 C for 0.5 h then a solution of C Br (20.66 g, mmol) was added. The reaction mixture was stirred for 5 days. The solvent was removed under reduced pressure. The white solid was washed with Ethyl acetate (3 x 100 ml) and dried under vacuum to give pure product (17.95 g, 90%). 1 NMR(300 Mz, CDCl 3 ): δ 7.23 (s, 2), 4.34 (q, 2, J = 7.2 z), 3.97 (m, 6), 1.78 (m, 6), 1.48 (m, 6), 1.36 (t, 3, J = 7.1 z), 1.29 (m, 48), 0.86 (t, 9, J = 6.6 z). General method for the synthesis of 3,4,5-tris(n-alkyloxy) benzoic acid The title compounds were synthesized according to a known procedure 32 and the preparation of 3,4,5-tris(dodecyloxy)benzoic acid has been selected as a representative example because the same procedure was systematically used for all the members of the series. To a solution of ethyl 3,4,5-tris(dodecyloxy)benzoate (3.13 g, 4.46 mmol) in Et (70 ml) was added K (2.96 g, mmol) and the reaction was reflux at 80 C for 10h, then the solution was cooled to room 24

25 temperature and the precipite was filtered. To a solution of precipite in TF (50 ml) was added Cl (1 M, 10 ml) and the reaction was reflux at 80 C for 2h. The TF/ 2 solution was partitioned between ether and the organic extract was washed with brine (2 x 50 ml), dried over MgS 4 and filtered, and the solvent removed. The crude product is recrystallized twice from C 2 Cl 2 /Ethanol, and a white solid is obtained (3.08 g, 91%). 1 NMR(300 Mz, CDCl 3 ): δ= 7.29 (s, 2), 4.00 (m, 6), 1.75 (m, 6), 1.46 (m, 6), 1.26 (m, 48), 0.85 (t, 9, J = 6.6 z); analysis (calcd., found for C ): C (76.50, 76.45), (11.65, 11.56). Synthesis of 17-No-EDF (3,3-17-BS and 2,3-17-BS). A solution of bisphenol A diglycidyl ether (2.34 g, 6.87 mmol) and octadecanoic acid (3.91 g, mmol) in mix-solvent of acetonitrile (40 ml) and xylene (20 ml) was reflux at 85 C for 24h. The solvent was removed under reduced pressure. The crude product was recrystallized twice from acetonitrile, and a white solid is obtained (4.81 g, 77%) which is composed of 3,3-17-BS and 2,3-17-BS positional isomers. 1 NMR (400Mz, CDCl 3 ): δ 7.11 (d, 4, J = 8.4 z), 6.79 (d, 4, J = 8.4 z), 5.18 (d, 0.31, J = 6.8 z), 4.27 (m, 2.97), 4.20 (m, 2), 4.06 (d, 0.82, J = 5.2 z), 3.96 (m, 3.32), 3.96 (d, 0.58, J = 5.2 z), 2.33 (t, 4,, J = 7.6 z), 1.61 (b, 10), 1.23 (b, 56), 0.86 (t, 6, J = 6.8 z); 13 C NMR (100 Mz, CDCl 3 ): δ 174.0, 156.2, 143.8, 127.8, 114.0, 72.7, 68.7, 66.2, 65.2, 62.1, 41.7, 34.3, 33.6, 31.9, 31.0, 29.4, 24.9, 22.7, 14.1; MS (MALDI-TF): [M+Na] +. Synthesis of 17-EDFNP. The17-No-EDF (2.21 g, 0.32 mmol) and ammonium persulfate (0.07 g, 0.32 mmol) were heated and stirred under N 2 at 140 C for 38 h. The crude product was then disolved in C 2 Cl 2 and filtered. The filtrate was dried under vacuum to give a brown product with a yield of 64% (4.00 g) which is composed of 2,2-17-BS, 2,3-17-BS, 3,3-17-BS and 2,3-17-diacylglycerol-bisphenol-glycerol isomers, 25

26 and no any non-acyl migrated side product is found. 1 NMR (400Mz, CDCl 3 ): δ 7.09 (s, 4), 6.77 (d, 4, J = 7.2 z), 5.35 (m, 1), 5.25 (b, 0.8), (m, 8.2), (m, 4), (m, 10), (m, 56), 0.86 (t, 6, J = 6.0 z); 13 C NMR (100 Mz, CDCl 3 ): δ 173.2, 156.1, 143.5, 127.7, 113.9, 84.0, 70.6, 69.5, 68.7, 66.2, 62.4, 47.4, 41.7, 34.3, 34.1, 31.1, 29.3, 24.9, 22.7, Synthesis of 16-BGE-No-EDF (3-16-BTBA, 3-butoxy-2-hydroxypropyl 3,4,5-tris(hexadecyloxy)benzoate). A solution of butyl glycidyl ether (5.36 g, mmol) and 3,4,5-tris(hexadecyloxy) benzoic acid (3.47 g, 4.12 mmol) in mix-solvent of acetonitrile (50 ml) and xylene (5ml) was reflux for 24 h. The solvent was removed under reduced pressure and the crude product was purified by silica gel column chromatography using hexane and EtAc as eluent to afford pure 3-butoxy-2-hydroxypropyl-3,4,5-tris(hexadecyloxy)benzoate in 55% combined yield (2.13 g). 1 NMR (400Mz, CDCl 3 ): δ 7.24 (s, 2), 4.35 (m, 2), 4.09 (m, 1), 3.98 (m, 6), 3.50 (m, 4), 1.81 (d, 1, J = 6.4 z), 1.75 (m, 6), 1.55 (m, 2), 1.45 (m, 6), 0.88 (m, 12); 13 C NMR (100 Mz, CDCl 3 ): δ 170.6, 166.6, 152.8, 143.0, 142.7, 124.3, 123.8, 108.5, 108.3, 73.8, 73.5, 71.5, 71.4, 70.0, 69.1, 66.2, 62.9, 31.9, 31.6, 30.3, 29.5, 26.1, 22.6, 19.2, 14.0, 13.8; MS (MALDI-TF): [M+Na] +. Synthesis of 16-BGE-EDFNP.The mixture of previous product (0.64 g, 0.65 mmol) and ammonium persulfate (0.02 g, 0.09 mmol) were heated and stirred under N 2 at 140 C for 38 h. The crude product was then disolved in C 2 Cl 2 and filtered. The filtrate was dried under vacuum to give a brown solid with a yield of 96% (0.61 g) which is composed of 3-butoxy-2-hydroxypropyl-3,4,5-tris(hexadecyloxy)benzoate, 1-butoxy-3-hydroxypropan-2-yl 3,4,5-tris(hexadecyloxy)benzoate, 3-butoxypropane-1,2-diyl bis(3,4,5-tris(hexadecyloxy)benzoate) and 3-butoxypropane-1,2-diol isomers, and no any non-acyl migrated side product is found. 1 NMR (400Mz, CDCl 3 ); δ 7.22 (m, 2), 5.53 (b, 0.08), 5.33 (m, 0.48), 5.18 (b, 26

27 0.02), 4.65 (m, 0.16), 4.39 (m, 0.72), 4.12 (m, 0.17), 3.97 (m, 6.94), 3.76 (m, 0.71), 3.66 (m, 1.09), 3.56 (m, 1.07), 3.41 (m, 1.56), 1.78 (m, 6), 1.40 (m, 82), 0.86 (t, 6, J = 7.2 z); 13 C NMR (100 Mz, CDCl 3 ): δ 166.6, 152.8, 142.6, 124.3, 108.2, 76.6, 73.5, 71.6, 71.4, 70.1, 69.2, 69.0, 31.9, 31.6, 30.3, 29.5, 26.0, 22.6, 19.2, 14.1, The method for the synthesis of EDF-Polymer A solution of bisphenol A diglycidyl ether (3.02 g, 8.87 mmol) and poly(ethylene glycol) bis(carboxymethyl) ether with a number-average molecular weight about 600 ( 5.11g, 8.85 mmol) in mix-solvent of acetonitrile (40 ml) and xylene (20ml) was reflux at 85 C for 24 h. The solvent was removed under reduced pressure. The crude product was recrystallized twice from acetonitrile, and a gel-type product is obtained (6.82 g, 82%). Gel-type product (3.14g) and ammonium persulfate (0.10 g, 0.43 mmol) were heated and stirred under N 2 at 150 C for 38 h. The crude product was then disolved in C 2 Cl 2 and filtered. The filtrate was dried under vacuum to give a brown product with a yield of 92% (2.89 g) which is composed of 2-monoacylglycerol, 3-monoacylglycerol and diacylglycerol moieties, and no any non-acyl migrated side product is found. 1 NMR (400 Mz, CDCl 3 ): δ = 7.09 (d, J = 8.0 z), 6.77 (d, J = 8.0 z), 5.41 (b), 5.27 (m), 4.71 (b), 4.51 (b), (m), 3.97 (b), 3.84 (b), 3.78 (b), 3.61 (b), 3.44 (b), 3.31 (b), 2.81 (m), 2.72 (b), (m, 12), 1.60 (b); 13 C NMR (100 Mz, CDCl 3 ): δ 171.5, 156.3, 143.5, 113.9, 77.3, 73.5, 72. 5, 71.8, 71.7, 70.9, 69.1, 68.0, 65.9, 63.7, 63.0, 61.6, 58.8, 41.7, 31.0; The molecular weight of the EDF-Polymer was estimated by gel permeation chromatography and the number average molecular weight (M n ) of the EDF-Polymer was approximately 12,000 Da. 27

28 Supplementary References. 31. Gaussian, Revision C.01; Gaussian, Inc.: Wallingford, CT (2009). 32. Serrette, A. G., Lai, C. K. & Swager, T. M. Complementary Shapes in Columnar Liquid Crystals: Structural Control in omo- and eteronuclear Bimetallic Assemblies, Chem. Mater. 6, (1994). 28