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Study of the interaction of polyols with polymers containing n-substituted [(4-boronophenyl)methyl]-ammonio groups
Carbohydrate Research, 43 (1975) 215-224 @ Elsevier Scientific Publishing Company,
STUDY
OF THE INTERACTION
CONTAINING
AMMONIO
IV-SUBS’lTI-UTED
Amsterdam - Printed in Eel&m
OF PQLYOLS
WITH
POLYMERS
[(4-BORONOPHENYL)METHYL]-
GROUPS
AracANDm M.YURKEVICH, IVETTAI.KOLODKRYA,ELENAA.IVANOV~, AND ELENAI. PICI-IUZHKINA The All-Union Scientific Research Vitamin Institute, 117246 Moscow
(U.S.S.R.)
(Received February 6th, 1975; accepted for publication, April 23rd, 1975)
ABSTRACl-
Polymers,
based
on
dextran
and
cellulose,
having
2-([(4_boronophenyl)-
methyl]-ethylammonio)ethyl and -diethylammonio}ethyl groups were prepared. It was shown that these polymers could be employed for absorption of cis-ciiol compounds. The polymers were found to be highly specific towards polyols, carbohydrates, nucleosides, and nucleotides over a wide range of PH. The polymer based on DEAE-Sephadex A-25 was used in separating nucleosides, and in fractionating mononucleotides and carbohydrates. The chromatographic behavior of carbohydrates is delined by their structure and conformation, which are also responsible for dilTerent stabilities of the boronic complexes generated. INTRODUCTION
Most dials are known to afford cyclic complexes only with arylboronic* anions having coordination number 4.
acid
OH
/
Al-B \
OH
In general, the larger the degree of dissociation of the arylboromc acid, the wider the range of pH in which the formation of complexes with cis-diols occurs. Thus, adenosine affords the most stable complexes with phenylboro_mc acid (PI& 8.86) in the range of pH 7.5, (4-metbylphenyl)b oronic acid (pK, 10.0)at pH8.0, and (3nitrophenyl)boronic acid (pK, 7.30) at1 pH 7.0. Similar results were obtained in the study of complexes of phenylboronic, (3-nitrophenyl)boronic, and (4-methoxypheny1)boror.k acids with carbohydrate?. *Editor’s note. The nomenclattire employed Guicie, Section ZV, 76 (1972) paragraph 239.
in this article is based on that in Chem. Abstr. Index
BORON-CONTAINING
POLYMERS
223
formamide (3 ml). The reaction was conducted under a stream of argon for 4.5 h at 60”, and then for 12 h at 18-20”. The polymer was treated as described in the previous experiment. Found: B, 0.48% ; capacity, 0.45 mequiv. g-l. EBAE-celhdose. Tributylamine (0.4 ml) and tris[4-(bromomethyl)phenyl]boroxin (0.5 g) were added to a suspension of U-(2-aminoethyl)cellulose (2.0 g) in IV&-dimethylformamide (9 ml). The mixture was stirred under a stream of argon for 12 h at 100’; then, treatment similar to that described for the Sephadexes was performed. Found: B, 0.23% ; capacity, 0.2 mequiv. g- ‘. Determination of absorption of mtcleotides on DEBAE-Sephadexes. - (a) The ligand solution (l-2 ml), having a 2:3 ratio of mequiv. of B per mmole of nucleoside, was added to DEBAE-Sephadex A-25 (10 mg) swollen in 0.2 ml of 0.01~ buffer of appropriate pH (TEAB or sodium acetate in acetic acid), or in hydrochloric acid. The mixture was stirred for l-2 h and filtered. The capacity of the polymer was determined by measurement of the optical absorbance of the titrate at 260 nm (see Table I). (6) The ligand solution (3 ml), having a 5:7 ratio of mequiv. of B per mmole of l&and, was added to DEBAE-Sephadex LH-20 (100 mg) swollen in 1 ml of ImM TEAB, pH 7.15. The mixture was stirred for 2-3 h, and filtered, and the polymer was washed with the same buffer until minimal optical absorbance of the washings was achieved. Chromatography of D-arabirzono- and D-gh&2ono-iactones. - A solution o D-arabinono-@lactone (5 mg) in 0.1 ml of 0.01~ sodium acetate-acetic acid buffer (pH 5.0) was placed on the column with 100 mg of the polymer in the same buffer. Elution with the same buffer afforded a peak with 3.49 mg of D-arabinonolactone (70% of the original sample), ZIP =2.0 ml, v, = 7.0 ml. Elution with 0.1~ acetate buffer, pH s-0, gave the peak for D-arabinonic acid (25-30%) (13 ml). The same absorption conditions were used for D-gluconolactone. Two peaks were eluted in the way just described. Yield of the tist fraction, 18% of the original quantity (D-glucono-l,IIactone), 0, = 2.3 ml, v, = 13 ml. The initial compound (-75%) was eluted with 0.1~ acetate buffer (pH 5.0) (see Fig. 1). REFERENCES 1 2 3 4 5 6 7 8 9 10 11 12
E. A. IVANOVA, I. I. KOLODKINA, AND A. M. YURKE~ICH, 2h. Obshch. Khim., 41 (1971) 455-459. S. A. BARKER, A. K. CHOPRA, B. W. HA?T, AND P. J. SOMERS,Carbohydr. Res., 26 (1973) 33-40. J. P. LOFUND AND J. 0. EDWARDS, J. Org. Chem., 24 (1959) 769-774. K. TORSELL, J. H. MCLENDON. AND G. F. SOMERS,Acfa Chem. Stand.. 12 (1958) 1373-1385. E. I. PICH;ZHKINA, I. I. KO~OD~A, AND A. k. YURKEVICH, Zh: Ob$zch.sKhim., 43 (1973) 2275-2277. 3. SoLhis AND H. DEUEL, Chimia, 1 I (1957) 311. H. L. WEITH, J. L. WIEBEHS, AND P. T. GILHAM, BiocIzemistry, 9 (1970) 4396-4401. S. A. BARKER, B. W. Hm-r, P. J. SOMERS, AND R.R. WOODBURY, Carbohydr Xe,s., 26 (1973) 55-64. K. RESKE AND H. Sc~orr, Angelo. Chem. Int. Ed. Engl., 12 (1973) 417-418. Brit. Pat. 936,039 (1963). I. I. KOLODIUNA, E. I. PICHUZHKIXA, E. A. IVANOVA, AND A. M. YURKEVICH, Avtorskoe svidet., No. 406,841 (1973); Byul. Izobret. i Tovarnykfz Znakov, No. 46 (1973). H. Z. SOMMER,H. I. LIPP, AND L. L. JACKSON, J. Org. Gem., 36 (1971) 824-828.
224
A. M. YURKEVICH,
I. 1. KOLODKINA,
E. A. IVANOVA,
E. I. PICHUZHKINA
13 E. A. IVANOVA, I. I. KOLODKINA, AND A. M. YURICEVICH,Zh. Obshch.Khim., 44 (1974)430-434. 14 J. M. GORNER, J. Inorg. Nucl. Chem., 32 (1970) 3545-3548; P. J. AN’TI~~NEN, Suom. KemistiIehti B, 31 (1958) 255-260. 15 J. B~ESEICEN, Aduan. Carbobydr. Chem., 4 (1949) 189-210. 16 H. CA_WA~, S. PASSERON,M. DANKERT, AND E. &CONDO, J. Cbromatogr., 18 (1965) 342-348. 17 G. R. KENNEDY AND M. J. How, Curbobydr. Res., 28 (1973) 13-19. 18 Z. DIXIE, J. Biol. Chem., 181 (1949) 379-392. 19 N. SPENCER, 3. Chromatogr., 30 (1967) 566-571. 20 E. A. PETEFCSONAND H. A. SOBER, Biocbem. Prep., 8 (1961) 3942.
STUDY
OF THE INTERACTION
CONTAINING
AMMONIO
IV-SUBS’lTI-UTED
Amsterdam - Printed in Eel&m
OF PQLYOLS
WITH
POLYMERS
[(4-BORONOPHENYL)METHYL]-
GROUPS
AracANDm M.YURKEVICH, IVETTAI.KOLODKRYA,ELENAA.IVANOV~, AND ELENAI. PICI-IUZHKINA The All-Union Scientific Research Vitamin Institute, 117246 Moscow
(U.S.S.R.)
(Received February 6th, 1975; accepted for publication, April 23rd, 1975)
ABSTRACl-
Polymers,
based
on
dextran
and
cellulose,
having
2-([(4_boronophenyl)-
methyl]-ethylammonio)ethyl and -diethylammonio}ethyl groups were prepared. It was shown that these polymers could be employed for absorption of cis-ciiol compounds. The polymers were found to be highly specific towards polyols, carbohydrates, nucleosides, and nucleotides over a wide range of PH. The polymer based on DEAE-Sephadex A-25 was used in separating nucleosides, and in fractionating mononucleotides and carbohydrates. The chromatographic behavior of carbohydrates is delined by their structure and conformation, which are also responsible for dilTerent stabilities of the boronic complexes generated. INTRODUCTION
Most dials are known to afford cyclic complexes only with arylboronic* anions having coordination number 4.
acid
OH
/
Al-B \
OH
In general, the larger the degree of dissociation of the arylboromc acid, the wider the range of pH in which the formation of complexes with cis-diols occurs. Thus, adenosine affords the most stable complexes with phenylboro_mc acid (PI& 8.86) in the range of pH 7.5, (4-metbylphenyl)b oronic acid (pK, 10.0)at pH8.0, and (3nitrophenyl)boronic acid (pK, 7.30) at1 pH 7.0. Similar results were obtained in the study of complexes of phenylboronic, (3-nitrophenyl)boronic, and (4-methoxypheny1)boror.k acids with carbohydrate?. *Editor’s note. The nomenclattire employed Guicie, Section ZV, 76 (1972) paragraph 239.
in this article is based on that in Chem. Abstr. Index
BORON-CONTAINING
POLYMERS
223
formamide (3 ml). The reaction was conducted under a stream of argon for 4.5 h at 60”, and then for 12 h at 18-20”. The polymer was treated as described in the previous experiment. Found: B, 0.48% ; capacity, 0.45 mequiv. g-l. EBAE-celhdose. Tributylamine (0.4 ml) and tris[4-(bromomethyl)phenyl]boroxin (0.5 g) were added to a suspension of U-(2-aminoethyl)cellulose (2.0 g) in IV&-dimethylformamide (9 ml). The mixture was stirred under a stream of argon for 12 h at 100’; then, treatment similar to that described for the Sephadexes was performed. Found: B, 0.23% ; capacity, 0.2 mequiv. g- ‘. Determination of absorption of mtcleotides on DEBAE-Sephadexes. - (a) The ligand solution (l-2 ml), having a 2:3 ratio of mequiv. of B per mmole of nucleoside, was added to DEBAE-Sephadex A-25 (10 mg) swollen in 0.2 ml of 0.01~ buffer of appropriate pH (TEAB or sodium acetate in acetic acid), or in hydrochloric acid. The mixture was stirred for l-2 h and filtered. The capacity of the polymer was determined by measurement of the optical absorbance of the titrate at 260 nm (see Table I). (6) The ligand solution (3 ml), having a 5:7 ratio of mequiv. of B per mmole of l&and, was added to DEBAE-Sephadex LH-20 (100 mg) swollen in 1 ml of ImM TEAB, pH 7.15. The mixture was stirred for 2-3 h, and filtered, and the polymer was washed with the same buffer until minimal optical absorbance of the washings was achieved. Chromatography of D-arabirzono- and D-gh&2ono-iactones. - A solution o D-arabinono-@lactone (5 mg) in 0.1 ml of 0.01~ sodium acetate-acetic acid buffer (pH 5.0) was placed on the column with 100 mg of the polymer in the same buffer. Elution with the same buffer afforded a peak with 3.49 mg of D-arabinonolactone (70% of the original sample), ZIP =2.0 ml, v, = 7.0 ml. Elution with 0.1~ acetate buffer, pH s-0, gave the peak for D-arabinonic acid (25-30%) (13 ml). The same absorption conditions were used for D-gluconolactone. Two peaks were eluted in the way just described. Yield of the tist fraction, 18% of the original quantity (D-glucono-l,IIactone), 0, = 2.3 ml, v, = 13 ml. The initial compound (-75%) was eluted with 0.1~ acetate buffer (pH 5.0) (see Fig. 1). REFERENCES 1 2 3 4 5 6 7 8 9 10 11 12
E. A. IVANOVA, I. I. KOLODKINA, AND A. M. YURKE~ICH, 2h. Obshch. Khim., 41 (1971) 455-459. S. A. BARKER, A. K. CHOPRA, B. W. HA?T, AND P. J. SOMERS,Carbohydr. Res., 26 (1973) 33-40. J. P. LOFUND AND J. 0. EDWARDS, J. Org. Chem., 24 (1959) 769-774. K. TORSELL, J. H. MCLENDON. AND G. F. SOMERS,Acfa Chem. Stand.. 12 (1958) 1373-1385. E. I. PICH;ZHKINA, I. I. KO~OD~A, AND A. k. YURKEVICH, Zh: Ob$zch.sKhim., 43 (1973) 2275-2277. 3. SoLhis AND H. DEUEL, Chimia, 1 I (1957) 311. H. L. WEITH, J. L. WIEBEHS, AND P. T. GILHAM, BiocIzemistry, 9 (1970) 4396-4401. S. A. BARKER, B. W. Hm-r, P. J. SOMERS, AND R.R. WOODBURY, Carbohydr Xe,s., 26 (1973) 55-64. K. RESKE AND H. Sc~orr, Angelo. Chem. Int. Ed. Engl., 12 (1973) 417-418. Brit. Pat. 936,039 (1963). I. I. KOLODIUNA, E. I. PICHUZHKIXA, E. A. IVANOVA, AND A. M. YURKEVICH, Avtorskoe svidet., No. 406,841 (1973); Byul. Izobret. i Tovarnykfz Znakov, No. 46 (1973). H. Z. SOMMER,H. I. LIPP, AND L. L. JACKSON, J. Org. Gem., 36 (1971) 824-828.
224
A. M. YURKEVICH,
I. 1. KOLODKINA,
E. A. IVANOVA,
E. I. PICHUZHKINA
13 E. A. IVANOVA, I. I. KOLODKINA, AND A. M. YURICEVICH,Zh. Obshch.Khim., 44 (1974)430-434. 14 J. M. GORNER, J. Inorg. Nucl. Chem., 32 (1970) 3545-3548; P. J. AN’TI~~NEN, Suom. KemistiIehti B, 31 (1958) 255-260. 15 J. B~ESEICEN, Aduan. Carbobydr. Chem., 4 (1949) 189-210. 16 H. CA_WA~, S. PASSERON,M. DANKERT, AND E. &CONDO, J. Cbromatogr., 18 (1965) 342-348. 17 G. R. KENNEDY AND M. J. How, Curbobydr. Res., 28 (1973) 13-19. 18 Z. DIXIE, J. Biol. Chem., 181 (1949) 379-392. 19 N. SPENCER, 3. Chromatogr., 30 (1967) 566-571. 20 E. A. PETEFCSONAND H. A. SOBER, Biocbem. Prep., 8 (1961) 3942.