5-O-咖啡酰奎宁酸新碱金属盐的抗氧化/促氧化、亲脂性、微生物和光谱特性研究。
The Study of Anti-/Pro-Oxidant, Lipophilic, Microbial and Spectroscopic Properties of New Alkali Metal Salts of 5-O-Caffeoylquinic Acid.
机构信息
Department of Chemistry, Biology and Biotechnology, Bialystok University of Technology, Wiejska 45E Str., 15-351 Bialystok, Poland.
Faculty of Forestry, Bialystok University of Technology, Pilsudskiego 1A Str., 17-200 Hajnowka, Poland.
出版信息
Int J Mol Sci. 2018 Feb 4;19(2):463. doi: 10.3390/ijms19020463.
Lithium, sodium, potassium, rubidium and caesium salts of 5--caffeoylquinic acid (chlorogenic acid, 5-CQA) were synthesized and described by FT-IR (infrared spectroscopy), FT-Raman (Raman spectroscopy), UV (UV absorption spectroscopy), ¹H (400.15 MHz), C (100.63 MHz) NMR (nuclear magnetic resonance spectroscopy). The quantum-chemical calculations at the B3LYP/6-311++G** level were done in order to obtain the optimal structures, IR spectra, NBO (natural bond orbital) atomic charges, HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) orbitals and chemical reactivity parameters for 5-CQA and Li, Na and K 5-CQAs (chlorogenates). The DPPH (α, α-diphenyl-β-picrylhydrazyl) and FRAP (ferric reducing antioxidant power) assays were used for the preliminary estimation of the antioxidant properties of alkali metal chlorogenates and chlorogenic acid. In the DPPH assay the EC parameter were equal to 7.39 μM for 5-CQA and was in the range of 4.50-5.89 μM for salts. The FRAP values for two different concentrations (5 and 2.5 μM) of the studied compounds were respectively 114.22 and 72.53 μM Fe for 5-CQA, whereas for salts they were 106.92-141.13 and 78.93-132.00 μM Fe. The 5-CQA and its alkali metal salts possess higher antioxidant properties than commonly applied antioxidants (BHA, BHT, l-ascorbic acid). The pro-oxidant action of these compounds on trolox oxidation was studied in the range of their concentration 0.05-0.35 μM. The lipophilicity (log) of chlorogenates and chlorogenic acid was determined by RP-HPLC (reverse phase-high performance liquid chromatography) using five different columns (C8, PHE (phenyl), CN (cyano), C18, IAM (immobilized artificial membrane)). The compounds were screened for their in vitro antibacterial activity against , , , and antifungal activity against . The 5-CQA possessed lower antibacterial (minimal inhibitory concentration, MIC = 7.06 mM) and antifungal (MIC = 14.11 mM) properties than its alkali metal salts (MIC values: 6.46-2.63 mM and 12.91-5.27mM, respectively). The synthesized chlorogenates possessed better antioxidant, lipophilic, antimicrobial as well as lower pro-oxidant properties than the ligand alone. Moreover, a systematic change of the activity of alkali metal salts along the series Li→Cs suggests that there are correlations between the studied biological properties. The type of metal cation in the carboxylate group of chlorogenate is crucial for the activity of studied compounds.
5--咖啡酰奎宁酸（绿原酸，5-CQA）的锂、钠、钾、铷和铯盐通过傅里叶变换红外光谱（FT-IR）、傅里叶变换拉曼光谱（FT-Raman）、紫外光谱（UV 吸收光谱）、¹H（400.15 MHz）、C（100.63 MHz）NMR（核磁共振光谱）进行了合成和描述。为了获得 5-CQA 和 Li、Na 和 K 5-CQAs（绿原酸盐）的最佳结构、IR 光谱、NBO（自然键轨道）原子电荷、HOMO（最高占据分子轨道）和 LUMO（最低未占据分子轨道）轨道和化学反应性参数，在 B3LYP/6-311++G**水平上进行了量子化学计算。使用 DPPH（α，α-二苯基-β- picrylhydrazyl）和 FRAP（铁还原抗氧化能力）测定法初步估计了碱金属绿原酸盐和绿原酸的抗氧化性能。在 DPPH 测定中，5-CQA 的 EC 参数等于 7.39 μM，盐的范围为 4.50-5.89 μM。两种不同浓度（5 和 2.5 μM）研究化合物的 FRAP 值分别为 5-CQA 的 114.22 和 72.53 μM Fe，而对于盐，它们分别为 106.92-141.13 和 78.93-132.00 μM Fe。5-CQA 及其碱金属盐具有比常用抗氧化剂（BHA、BHT、抗坏血酸）更高的抗氧化性能。研究了这些化合物在 trolox 氧化范围内的促氧化剂作用，浓度范围为 0.05-0.35 μM。使用五种不同的色谱柱（C8、PHE（苯基）、CN（氰基）、C18、IAM（固定化人工膜））通过反相高效液相色谱法（RP-HPLC）确定了绿原酸盐和绿原酸的亲脂性（log）。对化合物进行了体外抗菌活性测试，对 、 、 、 ，以及对 、 、 、 的抗真菌活性进行了筛选。5-CQA 的抗菌（最小抑菌浓度，MIC = 7.06 mM）和抗真菌（MIC = 14.11 mM）性质低于其碱金属盐（MIC 值：6.46-2.63 mM 和 12.91-5.27mM，分别）。与配体相比，合成的绿原酸盐具有更好的抗氧化、亲脂性、抗菌以及较低的促氧化剂特性。此外，碱金属盐沿系列 Li→Cs 的活性的系统变化表明，所研究的生物学特性之间存在相关性。在绿原酸盐的羧酸盐基团中金属阳离子的类型对研究化合物的活性至关重要。
Zotero 插件