After briefly reviewing the historical progress of chemical database, The Chemical Factual Database Network promoted by The Science and Technology Agency of Japan is introduced. Within it, central chemical substance dictionary and thermophysical and mass spectral database systems developed by The Japan Information Center of Science and Technology are minutely explained. The most features of the chemical dictionary are its stereochemical structure treatment and automatic construction of the structures from their nomenclatures.

抄録全体を表示

Examples of the application of Molecular Mechanics (MM2) calculation in natural product syntheses using macrocyclic stereocontrolled reactions are presented. MM2 calculations and abinitio MM2 calculations have been used in predictions (or analyses) of the stereoselectivity in macrocyclic reactions such as the transannular Diels-Alder reaction of the 14-membered (E, E, E)-triene, the transannular [2, 3]-Wittig reaction of the 13-membered diallylic ethers, the cyclopropanation and the epoxidation of the 10-membered enones. Moreover molecular designing for the Bergman cyclization of the macrocyclic diynenes based on MM2 calculations are also described.

抄録全体を表示

Chemistry is the field of discussing the behavior of electrons in a molecule. Sixty years ago, the mathematical foundation for predicting the behavior of electrons was given by the quantum mechanics. Now a days, the rapid development of high speed digital computer makes it possible to perform a large scale quantum chemical calculation. Two powerful tools of the quantum chemistry reviewed here are the non-empirical molecular orbital calculation program series: GAUSSIAN and the semi-empirical one: MOPAC. Especially, the treatment of the reaction process in the MOPAC is shown in detail.

抄録全体を表示

Designing molecules has become more and more important in drug development. Computational methods for designing drugs rationally and efficiently are attracting much attention. Methods of Quantitative Structure-Activity Relationships (QSAR) represented by Hansch method seem to be excellent for lead optimization, but not for lead generation. As for lead generation, another computational method based on three-dimensional structures of molecules is expected to be useful. Theoretical calculations on stabilities, physical and chemical properties of molecules, and on molecular interactions with target macromolecules, can give useful informations which enable us to explain structure-activity relationships and to design new active structures. Computer graphics are indispensable tools for performing computer-aided durg design efficiently. We also describe about the basis and application of molecular dynamics calculation.

抄録全体を表示

The use of personal computer in chemical researches is currently excited. New approaches to produce chemical softwares for personal computer have been performed by many chemists and chemical teachers. However, the chemical softwares for a personal computer are scarecely announced in spite of important utility.
The author has studied on a software communication of chemistry for a personal computer, and published the annual reporting books ('85, '86, '87, '88) of chemical softwares serially. This paper mentions present states and circulation of personal computer softwares for chemical researches. There are primarily five cases of the softwares, which have been devoted to the problems of molecular science, data processing, chemical graphics, chemical education, and chemical instrumention & chemometrics. The best and most used hardware of personal computer is PC-9801 series by NEC in Japan.

抄録全体を表示

体重約4,130g(生殖せん指数10.7)のマボラ,Mugil cephalus,の各組織中の脂質,特に卵巣脂質に関し検討すると共に,血しょうと肝臓及び卵巣ホモジネートによるワックスエステル(WE)の合成と分解をみた。卵巣脂質含量は全湿重量の17.6%で,WEはその内約70%を占めていた。WEのほとんどは炭素鎖長30～34で,その脂肪酸部分は主に16:1及び18:1から,アルコール部分は16:0及び16:1から成り立っていた。
[1-¹⁴C]オイレン酸及び[1-¹⁴C]オレイルアルコールよりのWE合成又はオレイル[1-¹⁴C]オリエートの加水分解は共に卵巣ホモジネート(RH)中で最も活発であった。また,[1-¹⁴C]オレイン酸の還元活性もRH中で最大であった。RH中のWE合成酵素は主に,105,000×gの沈殿部分(ミクロソーム画分)及びその上清中に分布しており,ATP,CoA及びNADPHの添加により[1-¹⁴C]オレイン酸よりのWE合成は賦活された。RH及び肝臓ホモジネートと共に血しょうにおいても[1-¹⁴C]オレイン酸よりのWE合成は認められ,オレイルアルコール添加により活性はさらに高められた。
これらの結果から,マボラ卵巣中の脂肪酸よりのWE合成に直接的に関係する酵素はアシルCoA:アルコールアシルトランスフェラーゼ及び脂肪酸還元酵素であり,血しょう中のそれはレシチン:アルコールアシルトランスフェラーゼ様酵素であると考えられる。さらに,卵巣中に多量に存在するWEはふ(孵)化直後の卵の浮力獲得に関係しており独特な生化学的適応の結果であると推定した。

抄録全体を表示

近年,各種産業において高純度の水が必要とされており水中の微量有機物の除去に関心が高まっている。純水の製造にはイオン交換樹脂は不可欠であるが,前報で報告したように純水製造に用いられる代表的強酸性陽イオン交換樹脂(SACER)から微量有機物が溶出してくる事がわかった。そこで本研究ではこのSACERからの溶出物の除去について検討した。
ゲル型と多孔性の強塩基性陰イオン交換樹脂(SBAER)によるSACER溶出液の吸着等温線を測定したところ,ゲル型樹脂による吸着量は多孔性樹脂よりも大きな値を示した。また,SBAERカラムに溶出液を通液しその流出液のゲル〓過クロマトグラフィー(GFC),逆相クロマトグラフィー(RPC)を測定したところ,分子量約5,000以上の高分子量成分と極性が高い分子量186以下の成分が残存した。つぎにカラム処理を行ったカラム流出液について4種の炭素系吸着剤による吸着処理を行ったところ40%～65%の除去率が得られSBAERでは除去できない溶出成分の炭素系吸着剤による吸着処理は有効であり,特に細孔径50Å以下の細孔が吸着に寄与していることが示唆された。

抄録全体を表示

CDCl₃中,3種のトリグリセリド[C₃H₅(OCOR)₃ここでR=CH₃, n-C₃H₇, n-C₁₇H₃₅]のC-C-C結合のまわりのコンホーメーションをプロトンNMRと分子力学計算(改良QCMP/MM2力場計算法)によって検討した。両手法によって求めたコンホーメーションの割合は良く一致した。アシル基の鎖の長さに関係なく,グリセリン単位の3つの酸素はゴーシュ型である。もっとも好ましいコンホーメーションは,C-C-C結合についてtrans-trans配置であり,可能な低エネルギーのコンホーメーションの約20%を占めることが分かった。非等時性のメチレンプロトンとグリセリン単位に及ぼすアシル鎖の長さの影響についてEd(fod)₃存在下のランタニド誘起シフトによって明確にした。

抄録全体を表示

The affinities of eight kinds of carbamate pesticides, MIPC, BPMC, PHC, MTMC, XMC, MPMC, MCC and NAC, with bovine serum albumin, BSA, were examined, and their transport behavior was investigated with BSA as a carrier through a liquid membrane system consisting of a hexane source phase (I), a BSA sulution phase (1/15 phosphate buffer) and a hexane receiving phase (II). All these pesticides showed affinity toward BSA, suggesting involvement of the -NHCOO- group in their binding to BSA. The ratio of the BSA-binding form/free-form was high for MCC and XMC, and relatively lower for the others. An inverse correlation was observed between this ratio and the partition coefficient in a water/n-octanol system. The rate constant of pesticide transport from the haxane phase (I) to the water phase was defined as k₁ and that from the water phase to the haxane phase (II) as k₂. Positive correlations were observed between k₁ and water/hexane partition coefficient, and inverse correlations were found between k₂ and the partition coefficient with and without added BSA. It is thus evident that the transport behavior of carbamate pesticides across a water membrane is governed primarily by partition coefficients between water and the hexane phase and that the addition of BSA accelerates the transport of pesticides in the case of lower partition coefficients. Essentially the same was found for steroidhormones in a previous paper. In the case of a lower partition coefficient, the k₁ process is a rate-determining step in the transport system, while the rate-determining is changed to the k₂ process with increase of the partition coefficient.

抄録全体を表示

The effects of several synergists along with a mixed tocopherols concentrate (m-Toc) on the oxidative deterioration of a high linoleic margarine were compared with those of phenolic antioxidants. The margarine was prepared with blended vegetable oils, mainly safflower oil, whose levels of linoleic and oleic acids were 54.8 and 19.6% to the total fatty acids, respectively. Stability of the margarine against oxidative deterioration was evaluated based on changes in the peroxide value and vitamin A and β-carotene content during storage at 20°C.
1) On oxidation of high linoleic margarine, each tested amino acid except L-proline (Pro) enhanced the effect of m-Toc in the order of L-histidine (His)>L-cystine (Cys)>L-tryptophane (Trp)>glycine. The addition of His or Cys along with m-Toc was the most effective and comparable to that of dibutylhydroxytoluene (BHT) alone. In contrast, L-ascorbyl stearate (AS) and Pro lessened the effect of m-Toc.
2) The effects of synergists along with m-Toc on the stability of vitamin A or β-carotene in the margarine were essentially the same as those on oxidation. The effect of His along with m-Toc, in particular, was superior to that of BHT alone.
3) Amino acids, such as His, Cys or Trp, clearly showed protective effects on the loss of Toc, particularly α-Toc in the margarine, but no effect was observed in AS. BHT and t-butyl-hydroquinone were also somewhat effective.

抄録全体を表示