奎宁-冠醚组合型手性固定相直接拆分氨基酸的机理

合成了一种新型奎宁-冠醚组合型手性固定相(QN-CR CSP)并用于氨基酸手性对映体的直接拆分,该固定相对12种氨基酸对映体有良好的手性拆分能力。基于氨基酸手性识别中离子交换和络合的协同作用,建立了一种新型的等温吸附模型。通过迎头特殊点洗脱法(FACP)测定色氨酸(Trp)在不同金属离子添加剂条件下的等温吸附线,验证了模型的合理性。流动相中的Li⁺、Na⁺、K⁺等金属离子与氨基酸竞争固定相中的冠醚络合位点,随着金属离子与冠醚的络合作用力和络合吸附平衡常数增大,固定相对Trp的手性拆分能力下降。该模型的建立对理解氨基酸在此类固定相中的手性保留行为以及固定相结构的进一步优化具有重要意义。     

TRANSFER MECHANISM OF QUININE DRUG ACROSS THE OIL/WATER (O/W) INTERFACE

The transfer phenomena of quinine drug at the aqueous 1,2- dichloroethane (DCE)interface have been studied by the current- scanning polarography. The relationships be-tween the wave height and pH of aqueous phase, concentration of quinine as well as therate of water drop are discussed. The effect of supporting electrolyte, buffer solution andthe nature of organic solvent on the polarographic wave is studied. The transfer char-acteristics of quinine in aqueous phase and in organic phase are compared, The mono- pro-tonated and diprotonated quinines can both transfer at the interface so as to produce twopolarographic waves. The transfer process of quinine at the interface is simultaneouslycontrolled by diffusion and reestablishment of the disturbed protonated equilibrium ofquinine. A further investigation is made by chronopotentiometry. On the basis of thetheoretical analysis, the formulae of the limiting current are derived and discussed. Thetheoretical results are in agreement with the experimental ones.     

新型双功能手性硫脲小分子催化剂的合成及其在Michael加成反应中的应用

奎宁和手性氨基醇通过硫脲片段组合,合成了4个新型的具有多氢键供体的双功能手性硫脲类小分子催化剂(5a～5d),其结构经1H NMR,13C NMR,IR和HR-MS表征。以查尔酮为底物,硝基甲烷为亲核试剂,考察了5a～5d在Michael加成反应中的催化活性和对映选择性。结果表明,以Na2CO3为碱,三氯甲烷为溶剂,5c为催化剂,于室温反应24 h,加成产物4-硝基-1,3-二苯基丁烷-1-酮的收率69%,对映选择性86%。     

Quinine Esters with 1,2-Azole,Pyridine and Adamantane Fragments

An efficient method of producing quinine derivatives via reaction of acylation with 4,5-dichloroisothiazole-3-, 5-arylisoxazole-3-, adamantane- and hydrochlorides of pyridine-3- and pyridine-4-carbonyl chlorides was developed. All synthesized compounds were tested for antiviral, antimicrobial and analgesic activity. The most pronounced antibacterial activity was shown by the compounds 2e, 3b, 3c and 3e with isoxazole and pyridine fragments. It was found that most of the tested compounds showed significant analgesic activity reducing the pain response of animals to the irritating effect of acetic acid.     

New Synthetic Quinoline (Qui) Derivatives as Novel Antioxidants and Potential HSA’s Antioxidant Activity Modulators—Spectroscopic Studies

The antioxidant activity of drugs, as well as the influence of drugs on the activity of endogenous antioxidant mechanisms in the human body is of great importance for the course of the disease and the treatment process. Due to the need to search for new therapeutic methods, the study of newly synthesized substances with potential therapeutic activity is necessary. This study aimed to designate some properties and characteristic parameters of new, synthetic quinoline three derivatives—1-methyl-3-allylthio-4-(4′-methylphenylamino)quinolinium bromide (Qui1), 1-methyl-3-allylthio-4-(3′-hydroxyphenylamino)quinolinium bromide (Qui2) as well as 1-methyl-3-allylthio-4-(4′-hydroxyphenylamino)quinolinium bromide (Qui3), including their antioxidant properties, as well as to analyse their activity as the potential modulators of Human Serum Albumin (HSA) antioxidant activity. In order to achieve the goal of the study, spectroscopic methods such as UV-Vis and circular dichroism (CD) spectroscopy have been used and based on the obtained data only slight and probably some surface interaction of quinoline derivatives (Qui1–Qui3) with HSA have been observed. The effect of Qui1–Qui3 on the HSA secondary structure was also insignificant. All analysed quinine derivatives have antioxidant activity against ABTS cation radical, in turn against DPPH radical, only Qui3 has noticeable antioxidant potential. The highest reduction potential by Qui3 as well as (Qui3 + HSA)_complex has been shown. Qui3 mixed with HSA has mostly the synergistic effect against DPPH, ABTS and FRAP, while Qui1 and Qui2 in the presence of HSA mostly have a synergistic and additive effect towards ABTS, respectively. Based on the obtained results it can be concluded that Qui2 and Qui3 can be considered potential modulators of HSA antioxidant activity.