9-[(1,4,7,10-tetraazacyclododecan-1-yl)methyl]acridine | 158732-54-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 9-[(1,4,7,10-tetraazacyclododecan-1-yl)methyl]acridine
• 英文别名: (9-Acridinyl)methyl-cyclen；9-(1,4,7,10-tetrazacyclododec-1-ylmethyl)acridine
• CAS: 158732-54-8
• 化学式: C₂₂H₂₉N₅
• 分子量: 363.506
• InChiKey: OQINTNWYDZLCSZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  52.2
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  9-[(1,4,7,10-tetraazacyclododecan-1-yl)methyl]acridine 、 zinc(II) chloride 以 乙醇 为溶剂， 生成 [Zn(ACR)]Cl₂
  参考文献：
  名称：

  Selective Binding of Zn²⁺ Complexes to Human Telomeric G-Quadruplex DNA

  摘要：

  The Zn-2+ complex of 5-(1,4,7,10-tetraazacyclododecan-1-ylsulfonyl)-N,N-dimethylnaphthalen-1-amine, Zn(DSC), binds selectively to the biologically relevant human telomeric (H-Telo) G-quadruplex. An increase in the Zn(DSC) dansyl group fluorescence with a simultaneous shift in emission is consistent with the complex binding to H-Telo. The H-Telo G-quadruplex has two binding sites for Zn(DSC) with binding constants in the low micromolar range (2.5 mu M). Isothermal calorimetric titrations confirm low micromolar dissociation constants with a 2:1 stoichiometry. The interaction between H-Telo and Zn(DSC) is highly pH-dependent, consistent with binding to the unpaired thymines in the G-quadruplex loops. As a result, Zn(DSC) selectively binds to H-Telo over duplex DNA. In contrast to Zn-2+, Fe-2+ and Co-2+ do not complex to the DSC macrocycle appreciably under the conditions of the experiment. The Cu-2+ complex of DSC does not interact measurably with the H-Telo G-quadruplex. Interestingly, the H-Telo-Zn(DSC) adduct self-assembles from its individual components at physiological pH and 100 mM KCl. The self-assembly feature, which is specific for the Zn-2+ ion, suggests that this system may be viable as a Zn-2+ sensor. Pentanucleotides were studied in order to better describe the binding of Zn(DSC) to thymine sequences. NMR studies were consistent with the binding of Zn(DSC) to thymine-containing oligonucleotides including CCTCC, CTTCC, and CTCTC. Studies showed that the dansyl group of Zn(DSC) interacts with thymines in CTTCC. Fluorescence spectroscopy and ITC data indicate that Zn(DSC) forms 2:1 adducts with thymines that are spaced (CTCTC) but not tandem thymines (CTTCC). These data are consistent with one Zn(DSC) complex binding to two separate loops in the G-quadruplex. A second Zn-2+ complex containing an acridine pendent, Zn(ACR), binds tightly to pentanucleotides with both tandem and spaced thymines. Zn(ACR) indiscriminately binds to both H-Telo and duplex DNA

  DOI：

  10.1021/ic501484p
• 作为产物：
  描述：

  9-溴甲基丫啶 、 轮环藤宁 以 乙腈 为溶剂， 生成 9-[(1,4,7,10-tetraazacyclododecan-1-yl)methyl]acridine
  参考文献：
  名称：

  ZnII-Cyclen 作为超分子探针用于标记碳纳米管上的胸苷核苷

  摘要：

  功能化碳纳米管 (CNT) 的有机化学面临的一大挑战是对其结构及其物理化学性质的表征。在这项工作中，我们报告了利用吖啶衍生的 ZnII-cyclen 复合物作为多齿配体来识别胸苷衍生的多壁碳纳米管衍生物 (Td-MWCNTs)。ZnII-cyclen 识别的有效性已通过组合分析技术得到证实，例如 Kaiser 测试、TGA-MS、IR、X 射线光发射光谱、TEM、UV/Vis 吸收和荧光光谱。综上所述，不同的表征技术明确显示了 ZnII-cyclen 复合物对核苷的 1:1 识别，允许准确估计存在于 CNT 表面上的 Td 部分。

  DOI：

  10.1002/ejoc.201300075

文献信息

• Novel "Multipoint" Molecular Recognition of Nucleobases by a New Zinc(II) Complex of Acridine-Pendant Cyclen (Cyclen = 1,4,7,10-Tetraazacyclododecane)
  作者：Mitsuhiko Shionoya、Takuya Ikeda、Eiichi Kimura、Motoo Shiro

  DOI：10.1021/ja00088a021

  日期：1994.5

  A zinc(II) complex of acridine-pendant cyclen, 4.2ClO(4) (cyclen = 1,4,7,10-tetraazacyclododecane, 1), has been designed and synthesized as a new ''multipoint'' nucleobase receptor molecule in aqueous solution at physiological pH and compared with a Zn-II pendantless cyclen complex 2 recently discovered (ref 9) as a highly selective host for dT (deoxythymidine) and U (uridine). The strong acidity of Zn-II in 2 is retained in 4; the water at the fifth coordination site has a pK(a) value of 7.46 +/- 0.02, L-Zn-OH2 reversible arrow L-Zn-OH-. Interaction of 4 with a variety of nucleosides has been studied by potentiometric pH titration, H-1 and C-13 NMR, IR, UV-vis, and fluorescence spectroscopy. The effects of the acridine functionality in 4 are (i) an enhanced 1:1 association with N(3)-deprotonated dT (log K = 7.2 +/- 0.1 at 25 degrees C and I = 0.10 (NaNO3)) and its congeners, implying an additional acridine-thymine aromatic stacking interaction; (ii) a different interaction mode with dG (2'-deoxyguanosine) (log K = 5.0 +/- 0.1 for the N(1)-deprotonated form and 4.1 +/- 0.1 for the free form) while no interaction was observed with 2, but 4 does not interact at all with the nucleosides dA (2'-deoxyadenosine) and dC (2'-deoxycytidine); and (iii) high selectivity for dT among all of the DNA nucleosides in aqueous solution. The strong ''multipoint'' recognition of 4 with dT is proven by IR, NMR, and the X-ray analyses of an isolated 1:1 ternary complex of 4 with N(3)-deprotonated 1-methylthymine, 10.ClO4.2H(2)O. The X-ray crystal analysis of 10.ClO4.2H(2)O shows a distorted square-pyramidal N-5-coordinate structure with a strong interaction between the Zn-II and the N(3'')-deprotonated anion of the pyrimidine ring (Zn(1)-N(3'') = 1.987(4) Angstrom). The carbonyl oxygen O(2'') of the pyrimidine ring forms a hydrogen bond directly with a cyclen N(10)-H group (O(2'')-N(10) = 2.881(5) Angstrom), while the other O(4'') binds indirectly with a diagonal N(4)-H group via a water molecule. As postulated from the enhanced stability for the 4-dT complex, a strong cofacial stacking interaction is found between the acridine (at C(1'), C(2'), C(4'), C(4a'), and C(9a')) and the pyrimidine ring with the plane-to-plane separation ranging from 3.285 to 3.419 Angstrom.Crystals of 10.ClO4.2H(2)O (C28H40N7O8Cl1Zn1) are C-centered monoclinic, space group C2/c (#15) with a = 15.312(3) Angstrom, b = 21.920(3) Angstrom, c 18.774(2) Angstrom, beta = 101.68 (1)degrees, V = 6171 (1) Angstrom(3), and Z = 8. Full-matrix least-squares refinement converged at R = 0.062 and R(W) = 0.093 for 3573 independent reflections. A ternary complex 1 1 composed of 4 and the free form of dG was isolated by mixing 4 and dG in CH3CN-H2O. The X-ray crystal analysis of 11.2BF(4).2.5H(2)O shows a distorted square-pyramidal N-2-coordinate structure containing the fifth coordination from N(7'') of the dG purine ring to Zn-II (Zn(1)-N(7'') = 2.04(1) Angstrom). The carbonyl oxygen O(6'') of the purine ring forms a hydrogen bond with a cyclen N(4)-H group O(6'')-N(4), 3.01 (1) Angstrom). A strong cofacial stacking interaction between the acridine (at C(1'), C(2'), C(3', C(4'), and C(4a')) and the purine ring greatly helps to stabilize the complex. Crystals of 11.2BF(4).2.5H(2)O (C32H47N10O6.5B2F8Zn1) are monoclinic, space group P2(1) (#4) with a = 10.892(4) Angstrom, b = 21.230(2) Angstrom, c = 17.465(2) Angstrom, beta = 101.19(1)degrees, V = 3974(1) Angstrom(3), and Z = 4. Full-matrix least-squares refinement converged at R = 0.083 and R(W) = 0.104 for 4473 independent reflections.