Simulations of alkali metal ion extraction ability using spirobenzopyran derivatives bearing a monoazacrown ether moiety were conducted by molecular dynamics calculation. Previously, our simulation studies had revealed the effects of the alkyl chain length in the spirobenzopyran derivatives on extractability towards alkali metal ions. In this research, the counter anion effects on liquid-liquid extraction were investigated by using 1,2-dichloroethane as an organic phase. The results show that the metal ions were more easily extracted into the organic phase when hydrophobic anions such as picrate and phenolate ions were used as counter anions than when hydrophilic anions such as nitrate and chloride ions were used, regardless of the metal ions and the crown ring size. This tendency is theoretically supported as the general anion effect.

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We have developed a novel property estimation equation with a group contribution scheme for molecular properties (boiling points), in the standard condition using a three layers perceptron type neural network and are equipped MolWorks™ with it. 142 groups are newly defined as a set to reproduce the differences of isomers and to realize more accurate predictions than are available with usual methods. 765 data of molecular boiling points are selected for training of the neural network. 953 data were applied to evaluate the efficiency of the equation. The correlation of observed and predicted molecular boiling points by this work is better than the values obtained by Joback's equation. The equation is applicable to estimate a wide thermal range, including high and low temperature regions. Furthermore, the equation well reproduces the differences of boiling points for not only ortho-, meta-, and para- isomers but also for cis- and trans-isomers.

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　光反応理論、不斉合成そして太陽エネルギー蓄積で興味のもたれる2-ピリドン(1)の光励起による不斉フォトピリドン(2)の生成実験と、その光反応のエネルギーと立体化学変化について主に半経験的量子化学計算を用いた動的解析(MO解析)を行った。　先ず不斉な新規なイミドアミドホスト(l)-3などを調製し、水素結合錯体1a・(l)-3などとして光反応し、不斉な(R)-2aなどの合成を行った。次に1の光励起一重項(S₁)1*のMO解析は、1*が非平面なenantiomer平衡体(1*_Φ(+)と1*_Φ(-):ΔE_K≒8-9kcal/mol)として存在すること、また3種のポテンシャルエネルギー面(PES)を求め、1*_Φ(+)はr_3-6≒2.0A付近の失活で(R)-2になることを示した。1・(l)-3の光反応での(R)-2の生成は、1・(l)-3のS₁励起では1*_Φ(+)・(l)-3となり、r_3-6の減少と失活で、(R)-2・(l)-3となり、それとなることが示された。そこで(d)-3利用の場合のMO解析を行い、1・(d)-3からは1*_Φ(-)・(d)-3を経て (S)-2が生成することを示した。また著名なBachらのホスト6による1→(R)-2の光反応もMO解析し、検証した。　さらに1⇔2の大きなエネルギー蓄積、置換基効果そして触媒作用をMO解析し、新しい太陽エネルギー蓄積系を提案した。

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An accurate method for the numerical solution of the eigenvalue problem of the second-order ordinary differential equation for the central-Force-Field problem in quantum mechanics is presented. Firstly, initial values for the eigenvalue and eigenfunction are obtained by using the discretized matrix eigenvalue method. Secondly, the eigenvalue and eigenfunction are solved by using the shooting method. Highly accurate solutions around zero are obtained by using the formal solution of power series expansion. Similarly, highly accurate solutions around infinity are obtained using asymptotic series expansion. These formal solutions are used for the initial value or guess for the shooting method. The initial value problem is solved highly accurately by using the higher-order linear multistep method based on the method of constructing the optimal operators. The eigenvalue is properly corrected by using Ridley’s formula and highly accurate numerical differentiation, integration, and a suitable choice of matching point. The efficiency of the present method is demonstrated by its application to bound states for the Coulomb potential, the Hulthén potential, the Yukawa potential and the Hellmann potential in the central-force-field problems.

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近年、化学データを数学的・統計的手法により解析する「ケモメトリクス」が盛んに用いられるようになってきた。しかし、日本の大学の化学教育の場ではほとんど取り上げられていない。Microsoft Excel (Excel)を用いたケモメトリクス計算のシリーズ3回目として、重回帰による定量分析をExcelワークシート上で行う方法を開発した。ケモメトリクスによる解析がしばしば必要となる吸光スペクトルを想定して議論を進めるため、スペクトル生成用のワークシートを作成する。生成したスペクトルを用いて、Lambert-Beer則を応用した重回帰(LBA)および一般的な取り扱いの重回帰(MLR)による定量計算法をExcelワークシート上で行う。これら2つの方法について定量性能の比較を行い、LBAはスペクトルのノイズに対して、MLRは未知成分の存在に対して耐性があると示唆された。

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