Sakoda M, Hiromi K
J Biochem. 1976 Dec;80(6):1335-41. doi: 10.1093/oxfordjournals.jbchem.a131406.
A novel method is proposed to determine deductively and uniquely the values of three parameters, a, b, and c in a fractional function of the form, y=a+bx/(c+x) where x and y are experimentally obtainable variables. This type of equation is frequently encountered in chemistry and biochemistry involving relaxation kinetics. The method of least squares with the Taylor expansion is employed for direct curve fitting of observed data to the fractional function. Approximate values of the parameters, which are always necessary prior to commending the above procedure, can be obtained by the method of rearrangement after canceling the denominator of fractional functions. This procedure is very simple, but very effective for estimating provisional values of the parameters. Deductive and unique determination of the parameters involved in the fractional function shown above can be accomplished for the first time by the combination of these two procedures. This method is extended to include the analysis of relaxation kinetic data such as those of temperature-jump method where the determination of equilibrium concentrations of reactants in addition to the three parameters is also necessary.
提出了一种新颖的方法,用于演绎地、唯一地确定形如(y = a + \frac{bx}{c + x})的分式函数中三个参数(a)、(b)和(c)的值,其中(x)和(y)是可通过实验获得的变量。这种类型的方程在涉及弛豫动力学的化学和生物化学中经常遇到。采用带有泰勒展开的最小二乘法将观测数据直接拟合到分式函数。在进行上述步骤之前,总是需要参数的近似值,可通过消除分式函数分母后的重排方法获得。这个过程非常简单,但对于估计参数的临时值非常有效。通过将这两个过程相结合,首次可以实现对上述分式函数中涉及的参数进行演绎性和唯一性的确定。该方法被扩展到包括对弛豫动力学数据的分析,如温度跃变法的数据,在这种情况下,除了这三个参数外,还需要确定反应物的平衡浓度。