Organic functionalizsation of ultradispersed nanodiamond ... · Supplementary Material (ESI) for...

Supplementary Material (ESI) for Journal of Materials Chemistry This journal is (c) The Royal Society of Chemistry 2009

1

Organic functionalizsation of ultradispersed nanodiamond: Synthesis and applications Wen-Wei Zhenga, Yi-Han Hsieha, Yu-Chung Chiub, Sian-Jhu Caib, Chia-Liang Chengb,*, and Chinpiao Chena,* a Department of Chemistry, National Dong Hwa University, Shoufeng, Hualien 974, Taiwan, Republic of

China; Fax: 886-3-8630475; E-mail: [email protected] b Department of Physics, National Dong Hwa University, Hualien 974, Taiwan, Republic of China

Supplementary material

Thermogravimetric analysis (TGA)

TGA measurements were made in Al2O3 crucibles in an atmosphere of nitrogen at a heating rate of 10 K min-1 using a TGA/SDTA851e thermobalance.

Thermogravimetric analysis of ND


2

Thermogravimetric analysis of ND-1



3




4




5




6




7




8

General Experimental

All commercial reagents were used without further purification. Solvents were dried according to standard procedures. Raw ND with >95% purity was purchased from Nanostructured and Amorphous Materials, Inc., USA. Transmission FTIR spectra were obtained from KBr pellets using a Perkin Elmer Paragon 1000 FTIR spectrometer, a JASCO FT/IR 410 spectrometer and an ABB FTLA2000 FTIR spectrometer with a MCT detector (samples in vacuum, ~10-6 torr). TGA measurements were made in Al2O3 crucibles in an atmosphere of nitrogen at a heating rate of 10 K min-1 using a TGA/SDTA851e thermobalance. RGA measurements were made using a DYCOR LC series Residual Gas Analyzer (LC 200 series with UHV system, experiment background pressure: 2 x 10-7 torr). Energy-dispersive X-ray spectroscopy (EDS) was performed at SEM/EDS, JEOL JSM-7000F. X-ray diffraction analysis of the samples was carried out using an X-ray diffractometer (XRD D8 Advanced, Bruker) with Cu-Ka radiation. X-Ray Photoelectron Spectroscopy (XPS, Thermo K-Alpha) was carried out using an Al-Kα radiation source and electron energy analyzer (Energy resolution, Ag 3d5/2 peak 0.5 eV, PET 0=C-0 peak 0.85eV). The powder was pressed into an indium foil as a carrier for the measurements. 1H NMR spectra were obtained on 400 MHz, and 13C NMR spectra were obtained at 100.6 MHz using a Bruker NMR spectrometer. Chemical shifts (δ) are reported in ppm relative to CDCl3 (7.26 and 77.0 ppm respectively). Electrochemical measurements were made using a model CHI420 electrochemical workstation that was controlled by a personal computer. A three-electrode system was used to make the measurements, with a bare glassy carbon electrode as the working electrode, a saturated calomel electrode (SCE) as the reference electrode and a platinum wire as the auxiliary electrode. The measurements were made using 5.00 mL of buffer solutions. Enantiomeric excesses were determined using Lab Alliance Series III high performance liquid chromatograph (HPLC) with a chiracel OD-H chiral column (Daicel Chemical Industries, LTD). Optical rotations were measured using a JASCO P-1010 polarimeter at the indicated temperature using a sodium lamp (D line, 589 nm). Flash column chromatography was performed using MN silica gel 60 (70–230 mesh) that was purchased from Macherey-Nagel.


9

Fig.

1 F

T-IR

spec

trum

of N

D

ND

3~5

ND


10

Fig.

2 1 H

-NM

R sp

ectru

m o

f ND

N

D

3~5

ND


11

ND

3~5

ND

Fig.

3 P

owde

r XR

D p

atte

rn o

f ND


12

Fig.

4 F

T-IR

spec

trum

of N

D-1

N

D

O

OH

ND

-1(

) n


13

ND

O

OH

ND

-1(

) n

Fig.

5 1 H

-NM

R sp

ectru

m o

f ND

-1


14

ND

OH

(

) n

ND

-2

Fig.

6 F

T-IR

spec

trum

of N

D-2


15

ND

OC

D3

(

) nN

D-7

Fig.

7 F

T-IR

spec

trum

of N

D-7


16

Cl

OO

Fig.

8 1 H

-NM

R sp

ectru

m o

f 6-(

chlo

ro-h

exyl

oxy)

-tetra

hydr

opyr

an


17

Cl

OO

Fig.

9 13

C-N

MR

spec

trum

of 6

-(ch

loro

-hex

ylox

y)-te

trahy

drop

yran


18

Cl

OO

Fig.

10

FT-I

R sp

ectru

m o

f 6-(

chlo

ro-h

exyl

oxy)

-tetra

hydr

opyr

an te

trahy

drop

yran


19

ND

OO

O(

) n

ND

-3

Fig.

11

FT-I

R sp

ectru

m o

f ND

-3


20

Fig.

12

FT-I

R sp

ectru

m o

f ND

-4

ND

OO

H(

) n

ND

-4


21

ND

OO

H(

) n

ND

-4

Fig.

13

1 H-N

MR

spec

trum

of N

D-4


22

ND

OO

CD

3(

) nN

D-5

Fig.

14

FT-I

R sp

ectru

m o

f ND

-5


23

ND

OO

CD

2CD

3(

) n

ND

-6

Fig.

15

FT-I

R sp

ectru

m o

f ND

-6


24

ND

OO

Ms

(

) nN

D-8

Fig.

16

FT-I

R sp

ectru

m o

f ND

-8


25

ND

OO

SSH

O

O O

(

) nN

D-1

7

Fig.

17

FT-I

R sp

ectru

m o

f ND

-17


26

Fig.

18

FT-I

R sp

ectru

m o

f ND

-18

ND

OO

OC

l

O

(

) n

ND

-18


27

ND

OO

OC

l

O

(

) n

Fig.

19

FT-I

R sp

ectru

m o

f aci

d ch

lorid

e of

ND

-18


28

ND

OO

OO O

SH

O

O

O

S

ND

-19

(

) n

Fig.

20

FT-I

R sp

ectru

m o

f ND

-19


29

Fig.

21

FT-I

R sp

ectru

m o

f ND

-16

ND

ON

H2

(

) nN

D-1

6


30

ND

ON

H2

(

) nN

D-1

6

Fig.

22

Pow

der X

RD

pat

tern

of N

D-1

6


31

ND

OF

(

)

n

ND

-9

Fig.

23

FT-I

R sp

ectru

m o

f ND

-9


32

ND

OC

l(

)n

ND

-10

Fig.

24

FT-I

R sp

ectru

m o

f ND

-10


33

ND

OB

r(

) nN

D-1

1

Fig.

25

FT-I

R sp

ectru

m o

f ND

-11


34

ND

OI

(

) n

ND

-12

Fig.

26

FT-I

R sp

ectru

m o

f ND

-12


35

ND

OC

N(

) n

ND

-13

Fig.

27

FT-I

R sp

ectru

m o

f ND

-13


36

ND

OSH

(

) nN

D-1

5

Fig.

28

FT-I

R sp

ectru

m o

f ND

-15


37

ND

ON

3(

)n

ND

-14

Fig.

29

FT-I

R sp

ectru

m o

f ND

-14


38

ND

OO

O

Fmoc

HN

(

) nN

D-2

0

Fig.

30

FT-I

R sp

ectru

m o

f ND

-20


39

ND

OO

O

NH

2

(

)n

ND

-21

Fig.

31

FT-I

R sp

ectru

m o

f ND

-21


40

ND

OO

ON H

ON

HFm

oc(

)

n

ND

-22

Fig.

32

FT-I

R sp

ectru

m o

f ND

-22


41

ND

OO

ON H

ON

H2

(

) n

ND

-23

Fig.

33

FT-I

R sp

ectru

m o

f ND

-23


42

Fig.

34

1 H-N

MR

spec

trum

of b

enzy

l est

er o

f 2

O

OH N

ON H

O

2


43

O

OH N

ON H

O

2

Fig.

35

FT-I

R sp

ectru

m o

f ben

zyl e

ster

of 2


44

Fig.

36

1 H-N

MR

spec

trum

of 3

N Boc

O

OH

HO

3


45

Fig.

37

13C

-NM

R sp

ectru

m o

f 3

N Boc

O

OH

HO

3


46

N Boc

O

OH

HO

3

Fig.

38

FT-I

R sp

ectru

m o

f 3


47

Fig.

39

FT-I

R sp

ectru

m o

f ND

-24

ND

OO

N H

CO

OH

(

) nN

D-2

4


48

ND

OO

N H

CO

OH

(

) nN

D-2

4

Fig.

40

FT-I

R sp

ectru

m o

f ND

-24


49

Fig.

41

1 H-N

MR

spec

trum

of 4

OH

O

NO

24


50

Fig.

42

13C

-NM

R sp

ectru

m o

f 4

OH

O

NO

24


51

OH

O

NO

24

Fig.

43

FT-I

R sp

ectru

m o

f 4


52

Fig.

44

1 H-N

MR

spec

trum

of 5

OO

HN

O2

5


53

Fig.

45

13C

-NM

R sp

ectru

m o

f 5

OO

HN

O2

5


54

OO

HN

O2

5

Fig.

46

FT-I

R sp

ectru

m o

f 5


55

Fig.

47

1 H-N

MR

spec

trum

of 6

OO

HN

O2

6


56

Fig.

48

13C

-NM

R sp

ectru

m o

f 6

OO

HN

O2

6


57

OO

HN

O2

6 Fig.

49

FT-I

R sp

ectru

m o

f 6


58

Fig.

50

1 H-N

MR

spec

trum

of 7

OO

HC

N

7


59

Fig.

51

13C

-NM

R sp

ectru

m o

f 7

OO

HC

N

7


60

OO

HC

N

7

Fig.

52

FT-I

R sp

ectru

m o

f 7


61

Fig.

53

1 H-N

MR

spec

trum

of 8

OO

H

CN

8


62

Fig.

54

13C

-NM

R sp

ectru

m o

f 8

OO

H

CN

8


63

OO

H

CN

8

Fig.

55

FT-I

R sp

ectru

m o

f 8


64

Fig.

56

1 H-N

MR

spec

trum

of 9

OO

H

Cl

9


65

Fig.

57

13C

-NM

R sp

ectru

m o

f 9

OO

H

Cl

9


66

OO

H

Cl

9

Fig.

58

FT-I

R sp

ectru

m o

f 9


67

Fig.

59

1 H-N

MR

spec

trum

of 1

0

OO

HO

CH

3

10


68

Fig.

60

13C

-NM

R sp

ectru

m o

f 10

OO

HO

CH

3

10


69

Fig. 63 HPLC analysis of 2-[Hydroxy-(4-nitro-phenyl)-methyl]-cyclohexanone (4).

(Chiralcel OD-H column, hexane:2-propanol = 9:1, 0.5 mL/min, 254 nm UV detector)

OO

HO

CH

3

10

Fig.

62

FT-I

R sp

ectru

m o

f 10


70

a) 82.3% ee (Table 1; entry 14)

b) racemic (4)


(Chiralcel OD-H column, hexane:2-propanol = 9:1, 0.5 mL/min, 254 nm UV detector) a) 87.3% ee (Table 2; entry 1)

OHO

NO24


71

b) racemic (5)



O OH NO2

5


72

b) racemic (6)

Fig. 66 HPLC analysis of 3-[Hydroxy-(2-oxo-cyclohexyl)-methyl]-benzonitrile (7).


O OHNO2

6


73

b) racemic (7)

Fig. 67 HPLC analysis of 4-[Hydroxy-(2-oxo-cyclohexyl)-methyl]-benzonitrile (8).


O OHCN

7


74

b) racemic (8)

Fig. 68 HPLC analysis of 2-[(4-Chloro-phenyl)-hydroxy-methyl]-cyclohexanone (9).


O OH

CN8


75

b) racemic (9)

Fig. 69 HPLC analysis of 2-[Hydroxy-(2-methoxy-phenyl)-methyl]-cyclohexanone (10).


O OH

Cl9


76

b) racemic (10)

O OH OCH3

10

Organic functionalizsation of ultradispersed nanodiamond ... · Supplementary Material (ESI) for...

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