METHOD FOR DETERMINATION OF PHOSPHATE ANION-CATION ASSOCIATION CONSTANTS FROM P-31 CHEMICAL-SHIFTS

METHOD FOR DETERMINATION OF PHOSPHATE ANION-CATION ASSOCIATION CONSTANTS FROM P-31 CHEMICAL-SHIFTS
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DOI:
10.1021/ic00172a017
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发表时间:
1984-01-01
影响因子:
4.6
通讯作者:
PRIGODICH, RV
PRIGODICH, RV
中科院分区:
化学2区
文献类型:
--
作者:
HAAKE, P;PRIGODICH, RV

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我们报告了一种实验方法,利用仔细测量磷-31化学位移的变化,以确定缔合常数。磷酸盐一价阴离子和二价阴离子的化学位移,在阳离子的存在下测量,并参考内标,反映化学位移的变化,由于协会和可以relatedquantitatively的缔合常数。用这种方法我们得到了双阳离子-磷酸根单阴离子缔合常数的可靠值,甚至弱的单阳离子-磷酸根单阴离子缔合常数也被测得。例如,与磷酸二甲酯单阴离子缔合的常数对于Mg 2+为3.6 M-1,对于Na+为0.29 M-1。测定了磷酸二甲酯阴离子、cAMP阴离子、磷酸乙酯阴离子和AMP阴离子与Mg ~(2+)、Ca ~(2+)、Li ~+、Na ~+、K ~+和胍离子的缔合常数。
We report an experimental method that utilizes careful measurements of the changes in phosphorus-31 chemical shifts to determine association constants. Chemical shiftsof phosphate monoanions and dianions, measured in the presence of cations and referenced to an internal standard, reflect chemical shift changes due to association and can be relatedquantitatively to the association constants. By this method we have obtained reliable values for dication-phosphatemonoanion association constants; even the weak monocation-phosphate monoanion association constants have been measured. For example, the constants for association to dimethyl phosphate monoanion are 3.6 M-1 for Mg2+ and 0.29 M-1 for Na+. Constants have been measured for theassociation of the dimethyl phosphate anions, the cAMP anion, the ethyl phosphate dianion, and the AMP dianion to Mg2+, Ca2+, Li+, Na+, K+, and guanidinium ions.