Spectroscopic studies on tungstoheteropoly anions functionalized
by amino acids
M. Mirzaei*, a, H. Eshtiagh-Hosseini a, M. Arefian a, F. Akbarnia a, F. Miri a, S. Edalatkar –
Moghadam b and M. Shamsipur c
a
Department of Chemistry, Ferdowsi University of Mashhad, 91775-1436 Mashhad, Iran
e-mail: mirzaeesh@um.ac.ir,bDepartment of Chemistry , Shar-e Rey Branch , Islamic Azad
University,Tehran , Iran, c Department of Chemistry, Razi University, Kermanshah, Iran
Fig S1. IR spectra of synthesized K6P2W18O62
1
The procedure for the synthesis of Gly-Ala.P2 (12)wasaccomplished by dissolving 0.3 g (0.06
mmol) of presynthesized P2W18O62 in acetonitrile,0.048 g (0.54 mmol)alanine in 4 ml
ethanol and 4 drops of HCl (2N),then a soloution of 0.032 g (0.42 mmol)glycine in 4 ml
ethanol added dropwisely to first solution. The result solution was refluxed for 4 hours in
90°C.Slow evaporation of the solvent at room temperature led toBlock blue crystals after
about three months.
a
b
Fig S2. IR spectrum (a) and HNMR (b) of Ala-Gly.P2
The procedure for the synthesis ofGly-Gln.P2 (13) was identical to that of 12, but 0.027 g
(0.36 mmol) glycine in 10 ml distilled water and 0.71 g (0.48 mmol) glutamine in 4 ml H2O,
added to a solution of 0.3g (0.06mmol) P2.after some days block blue crystals of 13 appeared.
a
2
b
c
Fig S3. IR spectrum(a), 1HNMR(b) and 13CNMR of Gly-Gln.P2
Theprocedure for the synthesis of Gly-Ala.P2 (12)wasaccomplished by dissolving 0.93 g
(2.84mmol) of Na2WO4 in 30 ml distilled water and 1ml H3PO4 (85%). Then 0.76 g (8.52
mmol)alanine and 1.59 g (5.52 mmol) sodium glutamate added to first solution. pH adjusted
to 3 by HCl (2N)and stirred for 30 minutes.
a
3
c
b
Fig S4. IR spectrum(a), 1HNMR(b) and 13CNMR(c) of Ala-Gln.P2
The procedure for the synthesis ofGln-Asn.P2 (14) was identical to that of 12, but 0.033 g
(0.24mmol) glutamine in 3ml ethanol and 1 drop HCl (2N), added to a solution of 0.3g
(0.06mmol) P2 in 9 ml acetonitrile. Then a solution of 0.033g (0.84mmol) asparagine in 3ml
ethanol and 1ml HCl added to previous solution. After some days block blue crystals of 14
appeared.
a
4
c
b
Fig S5. IR spectrum(a), 1HNMR(b) and 13CNMR(c) of Gln-Asn.P2
The procedure for the synthesis of Gly.P2 (17) accomplished by dissolving 0.06 g (0.8mmol)
glycine in 2ml HCl (2N)added to solution of 0.303g (0.06mmol) P2 in 10 ml distilled water.
Then stirred 3 hours at room temperature. After some months block yellow crystals of 17
appeared.
5
Fig S6. IR spectrum of Gly.P2
The procedure for the synthesis of Gly-Thr.P2 (15) was identical to that of 12, but 0.014 g
(0.12 mmol) threonine in 3ml ethanol and 1 drop HCl (2N), added to a solution of 0.2g
(0.04mmol) P2 in 6 ml acetonitrile. Then a solution of 0.012g (0.12mmol) glycine in 3ml
ethanol and 1ml HCl added to previous solution. After 20 days greenish crystals of 15
appeared.
a
b
c
Fig S7. IR spectrum(a), 1HNMR(b) and 13CNMR(c) of Gly-Thr.P2
6
The procedure for the synthesis of Ala-Asp.P2 (11) was identical to that of 12, but 0.018 g
(0.2 mmol) alanine and 0.017g (0.12mmol) aspartic acid in 4 ml HCl (2N), added to a
solution of 0.102g (0.02mmol) P2 in 6 ml acetonitrile and refluxed for 4 hours in 90°C. After
a few monthsyellowish crystalsappeared.
a
b
c
Fig S8. IR spectrum(a), 1HNMR(b) and 13CNMR(c) of ASp-Ala.P2
7
a
b
Fig S9. IR spectra of P5 (a) and IR spectra in 600-1200 cm-1 (b)
8
The procedure for the synthesis of Asp-Ala.P5 (1) wasaccomplished by dissolving
presynthesized [Na(H2O)P5W30O110]14- anion (P5)in 10 ml distilled water,0.041 g (0.46
mmol)alanine in 4 ml ethanol and 4 drops of HCl (2N)added to first solution, then a solution
of 0.061g (0.45 mmol)aspartic acid in 5 ml ethanol added dropwisely to above solution. The
result solution was refluxed for 3 hours in 90°C. Slow evaporation of the solvent at room
temperature led to block colorless crystals after 45 days.
a
b
c
Fig S10. IR spectra (a), 1HNMR (b) and 13CNMR of Asp-Ala.P5
9
The procedure for the synthesis of Gly-Ala.P5 (1) was accomplished by dissolving 0.3g (0.03
mmol)P5 in 10 ml distilled water, 0.018 g (0.02 mmol) glycine and 0.022g (0.02 mmol)
alanine were mixed with each other, pH adjusted to 3 by HCl (2N) and then refluxed for 3
hours in 90°C.14 days later block colorless crystals of 2 appeared.
a
b
c
Fig S11. IR spectra (a), 1HNMR (b) and 13CNMR of Gly-Ala.P5
10
The procedure for the synthesis of Gly-Gln.P5 (3)
was identical to that of 1 but, 0.015 g (0.2 mmol) glycine in 5ml ethanol and 1 drop HCl
(2N), added to a solution of 0.1g (0.01mmol) P5 in 10 ml distilled water. Then a solution of
0.016g (0.11mmol) glutamine in 3ml ethanol and 1ml HCl added to previous solution and
refluxed for 3 hours in 90°C.After some months block colorless crystals of 3 appeared.
a
b
Fig S12. IR spectra (a), 1HNMR (b) of Gly-Gln.P5
11
The procedure for the synthesis of Asn-Gln.P5 (4)
was identical to that of 1 but, 0.051 g (0.34 mmol) glutamine in 2ml H2O added dropwisely
to a solution of 0.2g (0.02mmol) P5 in 5 ml distilled water. Then a solution of 0.045g
(0.34mmol) asparagine in 2ml H2O and 1ml HCl added to previous solution and refluxed for
3 hours in 90°C. After 2 months block colorless crystals of 3 appeared.
a
b
Fig S13. IR spectra (a), 1HNMR (b) of Asn-Gln.P5
12
Meth-Cys.P5 (5) was prepared by mixing 3 solutions as follows; 0.008g (0.5mmol)
methionine in 2 ml H2O, 0.019g (0.15mmol) cysteine in 5 ml H2O and 1ml HCl (2N) and
0.2g (0.02mmol)P5 in 5 ml H2O. Then refluxed as before.2 weeks later needle like yellow
crystals appeared.
a
b
Fig S14. IR spectra (a), 1HNMR (b) of Meth-Cys.P5
13
Ala-Leu.P5 (6) was prepared exactly as 5 but, 0.21g (0.16mmol) leucine in 4 ml H2O, 0.014g
(0.01mmol) alanine in 2 ml H2O and 1ml HCl (2N) and 0.2g (0.02mmol)P5 in 5 ml H2O.pH
adjusted to3 by HCl (2N). Then refluxed as before. 3 months later block colorless crystals
appeared.
a
b
Fig S15. IR spectra (a), 1HNMR (b) of Ala-Leu.P5
14
To prepare Arg-Leu.P5 (7) 0.021g (0.16 mmol) leucine in 2ml H2O added dropwisely to a
solution of 0.2g (0.02mmol) P5 in 5 ml distilled water. Then a solution of 0.028g (0.16mmol)
arginine in 2ml H2O and 1ml HCl(2N) added to previous solution and refluxed for 3 hours in
90°C.
a
b
Fig S16. IR spectra (a), 1HNMR (b) of Arg-Leu.P5
15
The procedure to synthesize Ala-Thr.P5 (8) was identical to that of 5 but, 0.028g (0.31mmol)
alanine in 2ml H2O, 0.038g (0.31mmol) threonine in 2 ml H2O and 0.2g (0.02mmol)P5 in 5
ml H2O were mixed. pH adjusted to 3 by HCl (2N). Then refluxed as before. After a few
months block colorless crystals appeared.
a
b
c
Fig S17. IR spectra (a), 1HNMR (b) and 13CNMR of Ala-Thr.P5
16
To synthesize procedures for Cys.P5 (9) and Leu.P5 (10) are just the same except for the
amount of cysteine and leucine; 0.017g (0.14mmol) cysteine for 9 and 0.036g (0.27mmol)
leucine for 10, dissolved in 2 ml H2O, then refluxed 3 hours in 90°C. About 2 month later
needle like yellow crystals appeared for both of them.
a
b
Fig S18. IR spectra (a), 1HNMR (b) of Cys.P5
17
a
b
Fig S19. IR spectra (a), 1HNMR (b) of Leu.P5
18