高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (10): 1924.doi: 10.7503/cjcu20150128
张江华, 吕英, 贾红亮, 宋银银, 孙晓霞, 柴敦宵, 王兰英()
收稿日期:
2015-02-04
出版日期:
2015-10-10
发布日期:
2015-09-14
作者简介:
联系人简介: 王兰英, 女, 博士, 教授, 博士生导师, 主要从事功能分子合成及应用研究. E-mail:基金资助:
ZHANG Jianghua, LÜ Ying, JIA Hongliang, SONG Yinyin, SUN Xiaoxia, CHAI Dunxiao, WANG Lanying*()
Received:
2015-02-04
Online:
2015-10-10
Published:
2015-09-14
Contact:
WANG Lanying
E-mail:wanglany@nwu.edu.cn
Supported by:
摘要:
以含有活性甲基的杂环季铵盐和N-甲基-3-吲哚甲醛为原料, 在哌啶催化下合成了6种新型的双N-烷基化吲哚二甲川菁染料C1~C6; 采用紫外-可见光谱(UV-Vis)、 氢核磁共振谱(1H NMR)、 红外光谱(IR)和高分辨率质谱(HRMS)对6种染料进行了结构表征; 利用X射线单晶衍射法测定了染料C1和C5的晶体结构. 研究了6种染料在不同溶剂中的光谱性质, 结果表明, 染料C1~C6在不同溶剂中的最大吸收波长处在370.0~521.0 nm之间, 发射波长处在466.4~600.8 nm之间, 摩尔消光系数在0.80×104~3.92×104 L·mol-1·cm-1范围内; 研究了6种染料在近生理条件下分别与DNA、 牛血清蛋白(BSA)、 溶菌酶、 淀粉酶、 牛血红蛋白和糜蛋白酶的相互作用, 结果表明, 染料C3~C5的荧光量子产率随着DNA浓度的增加而增大; 探究了染料C5和C6的细胞毒性和细胞染色性能, 结果显示, 在实验应用的剂量及时间下, 染料C5和C6对人类神经胶质瘤细胞(A172)几乎没有毒性, 且主要对细胞核染色, 可以作为潜在的观察细胞的荧光试剂.
中图分类号:
TrendMD:
张江华, 吕英, 贾红亮, 宋银银, 孙晓霞, 柴敦宵, 王兰英. 吲哚二甲川菁的合成、 晶体结构、光谱性质及生物应用. 高等学校化学学报, 2015, 36(10): 1924.
ZHANG Jianghua, LÜ Ying, JIA Hongliang, SONG Yinyin, SUN Xiaoxia, CHAI Dunxiao, WANG Lanying. Synthesis, Crystal Structure and Spectral Properties of Six Indole Dimethine Cyanines as Well as Their Biological Application†. Chem. J. Chinese Universities, 2015, 36(10): 1924.
Dye | Appearance | Yield(%) | m. p./℃ | HRMS ESI(calcd.), m/z | UV-Vis (MeOH), λmax/nm | IR(KBr), |
---|---|---|---|---|---|---|
C1 | Orange red acicular crystal | 56 | 236—237 | 305.1097 (305.1107) | 472.0 | 3067, 2926, 2854, 1599, 1571, 1499, 1445, 1304, 1217, 1162, 1127, 1071, 973, 833, 810, 749 |
C2 | Yellow solid | 65 | >300 | 302.1636 (302.1652) | 378.0 | 3019, 2987, 1616, 1506, 1452, 1371, 1251, 1182, 989, 813, 736 |
C3 | Red solid | 81 | 275—276 | 299.1532 (299.1543) | 506.0 | 3050, 2973, 1585, 1519, 1457, 1396, 1346, 1295, 1247, 1193, 1118, 993, 833, 744 |
C4 | Dark red powder | 52 | 246—247 | 333.1139 (333.1153) | 493.0 | 3097, 3035, 1589, 1509, 1457, 1305, 1220, 1182, 1114, 964, 846, 740 |
C5 | Red acicular crystal | 77 | 256—257 | 299.1540 (299.1543) | 481.0 | 3033, 3000, 1594, 1513, 1459, 1342, 1303, 1164, 1114, 966, 842, 744 |
C6 | Red solid | 82 | 245—246 | 365.2002 (365.2012) | 490.0 | 3025, 2971, 1567, 1502, 1452, 1394, 1338, 1292, 1227, 1174, 1122, 971, 794, 742 |
Table 1 Appearance, yields, melting points, HRMS, UV-Vis and IR data for dyes C1—C6
Dye | Appearance | Yield(%) | m. p./℃ | HRMS ESI(calcd.), m/z | UV-Vis (MeOH), λmax/nm | IR(KBr), |
---|---|---|---|---|---|---|
C1 | Orange red acicular crystal | 56 | 236—237 | 305.1097 (305.1107) | 472.0 | 3067, 2926, 2854, 1599, 1571, 1499, 1445, 1304, 1217, 1162, 1127, 1071, 973, 833, 810, 749 |
C2 | Yellow solid | 65 | >300 | 302.1636 (302.1652) | 378.0 | 3019, 2987, 1616, 1506, 1452, 1371, 1251, 1182, 989, 813, 736 |
C3 | Red solid | 81 | 275—276 | 299.1532 (299.1543) | 506.0 | 3050, 2973, 1585, 1519, 1457, 1396, 1346, 1295, 1247, 1193, 1118, 993, 833, 744 |
C4 | Dark red powder | 52 | 246—247 | 333.1139 (333.1153) | 493.0 | 3097, 3035, 1589, 1509, 1457, 1305, 1220, 1182, 1114, 964, 846, 740 |
C5 | Red acicular crystal | 77 | 256—257 | 299.1540 (299.1543) | 481.0 | 3033, 3000, 1594, 1513, 1459, 1342, 1303, 1164, 1114, 966, 842, 744 |
C6 | Red solid | 82 | 245—246 | 365.2002 (365.2012) | 490.0 | 3025, 2971, 1567, 1502, 1452, 1394, 1338, 1292, 1227, 1174, 1122, 971, 794, 742 |
Dye | 1H NMR(400 MHz, DMSO-d6), δ |
---|---|
C1 | 3.94(s, 3H, NCH3), 4.25(s, 3H, N+CH3), 7.37—7.44(m, 2H, ArH), 7.46(d, 1H, J=16.0 Hz, CH=CH), 7.65—7.70(m, 2H, ArH), 7.76(t, 1H, J=8.0 Hz, ArH), 8.11(d, 1H, J=8.0 Hz, ArH), 8.30(t, 2H, J=8.0 Hz, ArH), 8.37(d, 1H, J=16.0 Hz, CH=CH), 8.42(s, 1H, pyrrole—H) |
C2 | 3.92(s, 3H, NCH3), 4.14(s, 6H, NCH3, N+CH3), 7.15(d, 1H, J=16.4 Hz, CH=CH), 7.32—7.37(m, 2H, ArH), 7.63—7.66(m, 3H, ArH), 7.99—8.04(m, 3H, ArH), 8.17—8.22(m, 2H, pyrrole—H, CH=CH) |
C3 | 3.93(s, 3H, NCH3), 4.44(s, 3H, N+CH3), 7.33—7.37(m, 2H, ArH, CH=CH), 7.62(d, 1H, J=7.6 Hz, ArH), 7.97—8.01(m, 2H, ArH), 8.19—8.23(m, 1H, ArH), 8.27(d, 1H, J=8.0 Hz, ArH), 8.30—8.37(m, 2H, ArH, pyrrole—H), 8.42(d, 1H, J=8.0 Hz, ArH), 8.52(d, 1H, J=16.0 Hz, CH=CH), 8.94(d, 1H, J=8.0 Hz, ArH), 9.09—9.10(m, 1H, ArH) |
C4 | 3.96(s, 3H, NCH3), 4.42(s, 3H, N+CH3), 7.36—7.38(m, 2H, ArH), 7.50(d, 1H, J=16.0 Hz, CH=CH), 7.64—7.65(m, 1H, ArH), 7.88(d, 1H, J=8.0 Hz, ArH), 8.24—8.25(m, 2H, ArH), 8.42(s, 1H, pyrrole—H), 8.57—8.69(m, 3H, ArH, CH=CH), 8.77(d, 1H, J=8.0 Hz, ArH) |
C5 | 3.94(s, 3H, NCH3), 4.45(s, 3H, N+CH3), 7.34—7.38(m, 2H, ArH), 7.52(d, 1H, J=16.0 Hz, CH=CH), 7.62—7.63(m, 1H, ArH), 7.83—7.86(m, 1H, ArH), 8.08—8.10(m, 1H, ArH), 8.23—8.24(m, 2H, ArH), 8.38(s, 1H, pyrrole—H), 8.42(d, 1H, J=16.0 Hz, CH=CH), 8.60—8.65(m, 2H, ArH), 8.79—8.83(m, 1H, ArH) |
C6 | 2.05[s, 6H, C(CH3)2], 4.00(s, 3H, NCH3), 4.14(s, 3H, N+CH3), 7.21(d, 1H, J=15.6 Hz, CH=CH), 7.46—7.48(m, 2H, ArH), 7.64—7.68(m, 1H, ArH), 7.72(d, 1H, J=8.0 Hz, ArH), 7.76—7.79(m, 1H, ArH), 8.03(d, 1H, J=8.0 Hz, ArH), 8.17(d, 1H, J=8.0 Hz, ArH), 8.23(d, 1H, J=8.0 Hz, ArH), 8.32(d, 1H, J=8.0 Hz, ArH), 8.39(d, 1H, J=8.0 Hz, ArH), 8.70(s, 1H, pyrrole—H), 8.74(d, 1H, J=15.6 Hz, CH=CH) |
Table 2 1H NMR data for dyes C1—C6
Dye | 1H NMR(400 MHz, DMSO-d6), δ |
---|---|
C1 | 3.94(s, 3H, NCH3), 4.25(s, 3H, N+CH3), 7.37—7.44(m, 2H, ArH), 7.46(d, 1H, J=16.0 Hz, CH=CH), 7.65—7.70(m, 2H, ArH), 7.76(t, 1H, J=8.0 Hz, ArH), 8.11(d, 1H, J=8.0 Hz, ArH), 8.30(t, 2H, J=8.0 Hz, ArH), 8.37(d, 1H, J=16.0 Hz, CH=CH), 8.42(s, 1H, pyrrole—H) |
C2 | 3.92(s, 3H, NCH3), 4.14(s, 6H, NCH3, N+CH3), 7.15(d, 1H, J=16.4 Hz, CH=CH), 7.32—7.37(m, 2H, ArH), 7.63—7.66(m, 3H, ArH), 7.99—8.04(m, 3H, ArH), 8.17—8.22(m, 2H, pyrrole—H, CH=CH) |
C3 | 3.93(s, 3H, NCH3), 4.44(s, 3H, N+CH3), 7.33—7.37(m, 2H, ArH, CH=CH), 7.62(d, 1H, J=7.6 Hz, ArH), 7.97—8.01(m, 2H, ArH), 8.19—8.23(m, 1H, ArH), 8.27(d, 1H, J=8.0 Hz, ArH), 8.30—8.37(m, 2H, ArH, pyrrole—H), 8.42(d, 1H, J=8.0 Hz, ArH), 8.52(d, 1H, J=16.0 Hz, CH=CH), 8.94(d, 1H, J=8.0 Hz, ArH), 9.09—9.10(m, 1H, ArH) |
C4 | 3.96(s, 3H, NCH3), 4.42(s, 3H, N+CH3), 7.36—7.38(m, 2H, ArH), 7.50(d, 1H, J=16.0 Hz, CH=CH), 7.64—7.65(m, 1H, ArH), 7.88(d, 1H, J=8.0 Hz, ArH), 8.24—8.25(m, 2H, ArH), 8.42(s, 1H, pyrrole—H), 8.57—8.69(m, 3H, ArH, CH=CH), 8.77(d, 1H, J=8.0 Hz, ArH) |
C5 | 3.94(s, 3H, NCH3), 4.45(s, 3H, N+CH3), 7.34—7.38(m, 2H, ArH), 7.52(d, 1H, J=16.0 Hz, CH=CH), 7.62—7.63(m, 1H, ArH), 7.83—7.86(m, 1H, ArH), 8.08—8.10(m, 1H, ArH), 8.23—8.24(m, 2H, ArH), 8.38(s, 1H, pyrrole—H), 8.42(d, 1H, J=16.0 Hz, CH=CH), 8.60—8.65(m, 2H, ArH), 8.79—8.83(m, 1H, ArH) |
C6 | 2.05[s, 6H, C(CH3)2], 4.00(s, 3H, NCH3), 4.14(s, 3H, N+CH3), 7.21(d, 1H, J=15.6 Hz, CH=CH), 7.46—7.48(m, 2H, ArH), 7.64—7.68(m, 1H, ArH), 7.72(d, 1H, J=8.0 Hz, ArH), 7.76—7.79(m, 1H, ArH), 8.03(d, 1H, J=8.0 Hz, ArH), 8.17(d, 1H, J=8.0 Hz, ArH), 8.23(d, 1H, J=8.0 Hz, ArH), 8.32(d, 1H, J=8.0 Hz, ArH), 8.39(d, 1H, J=8.0 Hz, ArH), 8.70(s, 1H, pyrrole—H), 8.74(d, 1H, J=15.6 Hz, CH=CH) |
Solvent | Dye | λmax/nm | λex/nm | λem/nm | Stokes shift/nm | 104ε/(L·mol-1·cm-1) | Ф |
---|---|---|---|---|---|---|---|
H2O | C1 | 461.0 | 461.0 | 522.0 | 61.0 | 2.40 | 0.0666 |
C2 | 370.0 | 370.0 | 475.4 | 105.4 | 0.94 | 0.0037 | |
C3 | 475.0 | 475.0 | 576.6 | 101.6 | 2.14 | 0.0175 | |
C4 | 468.0 | 468.0 | 561.6 | 93.6 | 3.04 | 0.0089 | |
C5 | 461.0 | 461.0 | 555.8 | 94.8 | 2.85 | 0.0117 | |
C6 | 484.0 | 484.0 | 557.6 | 73.6 | 3.64 | 0.0958 | |
DMSO | C1 | 474.0 | 474.0 | 528.8 | 54.8 | 2.40 | 0.3838 |
C2 | 381.0 | 381.0 | 469.8 | 88.8 | 0.93 | 0.0105 | |
C3 | 507.0 | 507.0 | 600.8 | 93.8 | 2.45 | 0.3267 | |
C4 | 497.0 | 497.0 | 570.8 | 73.8 | 3.11 | 0.0768 | |
C5 | 484.0 | 484.0 | 565.8 | 81.8 | 3.36 | 0.1136 | |
C6 | 492.0 | 492.0 | 560.0 | 68.0 | 3.49 | 0.2939 | |
MeOH | C1 | 472.0 | 472.0 | 529.4 | 57.4 | 2.58 | 0.1037 |
C2 | 378.0 | 378.0 | 467.4 | 89.4 | 0.99 | 0.0030 | |
C3 | 506.0 | 506.0 | 580.2 | 74.2 | 2.79 | 0.1018 | |
C4 | 493.0 | 493.0 | 563.2 | 70.2 | 3.76 | 0.0311 | |
C5 | 481.0 | 481.0 | 559.2 | 78.2 | 3.13 | 0.0453 | |
C6 | 490.0 | 490.0 | 561.6 | 91.6 | 3.70 | 0.0756 | |
EtOH | C1 | 476.0 | 476.0 | 526.0 | 50.0 | 3.15 | 0.2037 |
C2 | 380.0 | 380.0 | 466.4 | 86.4 | 1.01 | 0.0036 | |
C3 | 513.0 | 513.0 | 582.4 | 69.4 | 2.88 | 0.2464 | |
C4 | 497.0 | 497.0 | 565.8 | 68.8 | 3.92 | 0.0925 | |
C5 | 485.0 | 485.0 | 558.4 | 73.4 | 3.68 | 0.1542 | |
C6 | 492.0 | 492.0 | 562.4 | 70.4 | 3.66 | 0.1043 | |
CHCl3 | C1 | 496.0 | 496.0 | 552.6 | 56.6 | 2.11 | 0.1407 |
C2 | 387.0 | 387.0 | 496.8 | 109.8 | 0.80 | 0.0024 | |
C3 | 515.0 | 515.0 | 573.2 | 58.2 | 2.87 | 0.2037 | |
C4 | 517.0 | 517.0 | 577.2 | 60.2 | 3.03 | 0.1173 | |
C5 | 505.0 | 505.0 | 568.0 | 63.0 | 3.56 | 0.1659 | |
C6 | 521.0 | 521.0 | 574.2 | 53.2 | 3.28 | 0.0667 |
Table 3 Absorption and fluorescence spectra data of dyes C1—C6 in different solvents
Solvent | Dye | λmax/nm | λex/nm | λem/nm | Stokes shift/nm | 104ε/(L·mol-1·cm-1) | Ф |
---|---|---|---|---|---|---|---|
H2O | C1 | 461.0 | 461.0 | 522.0 | 61.0 | 2.40 | 0.0666 |
C2 | 370.0 | 370.0 | 475.4 | 105.4 | 0.94 | 0.0037 | |
C3 | 475.0 | 475.0 | 576.6 | 101.6 | 2.14 | 0.0175 | |
C4 | 468.0 | 468.0 | 561.6 | 93.6 | 3.04 | 0.0089 | |
C5 | 461.0 | 461.0 | 555.8 | 94.8 | 2.85 | 0.0117 | |
C6 | 484.0 | 484.0 | 557.6 | 73.6 | 3.64 | 0.0958 | |
DMSO | C1 | 474.0 | 474.0 | 528.8 | 54.8 | 2.40 | 0.3838 |
C2 | 381.0 | 381.0 | 469.8 | 88.8 | 0.93 | 0.0105 | |
C3 | 507.0 | 507.0 | 600.8 | 93.8 | 2.45 | 0.3267 | |
C4 | 497.0 | 497.0 | 570.8 | 73.8 | 3.11 | 0.0768 | |
C5 | 484.0 | 484.0 | 565.8 | 81.8 | 3.36 | 0.1136 | |
C6 | 492.0 | 492.0 | 560.0 | 68.0 | 3.49 | 0.2939 | |
MeOH | C1 | 472.0 | 472.0 | 529.4 | 57.4 | 2.58 | 0.1037 |
C2 | 378.0 | 378.0 | 467.4 | 89.4 | 0.99 | 0.0030 | |
C3 | 506.0 | 506.0 | 580.2 | 74.2 | 2.79 | 0.1018 | |
C4 | 493.0 | 493.0 | 563.2 | 70.2 | 3.76 | 0.0311 | |
C5 | 481.0 | 481.0 | 559.2 | 78.2 | 3.13 | 0.0453 | |
C6 | 490.0 | 490.0 | 561.6 | 91.6 | 3.70 | 0.0756 | |
EtOH | C1 | 476.0 | 476.0 | 526.0 | 50.0 | 3.15 | 0.2037 |
C2 | 380.0 | 380.0 | 466.4 | 86.4 | 1.01 | 0.0036 | |
C3 | 513.0 | 513.0 | 582.4 | 69.4 | 2.88 | 0.2464 | |
C4 | 497.0 | 497.0 | 565.8 | 68.8 | 3.92 | 0.0925 | |
C5 | 485.0 | 485.0 | 558.4 | 73.4 | 3.68 | 0.1542 | |
C6 | 492.0 | 492.0 | 562.4 | 70.4 | 3.66 | 0.1043 | |
CHCl3 | C1 | 496.0 | 496.0 | 552.6 | 56.6 | 2.11 | 0.1407 |
C2 | 387.0 | 387.0 | 496.8 | 109.8 | 0.80 | 0.0024 | |
C3 | 515.0 | 515.0 | 573.2 | 58.2 | 2.87 | 0.2037 | |
C4 | 517.0 | 517.0 | 577.2 | 60.2 | 3.03 | 0.1173 | |
C5 | 505.0 | 505.0 | 568.0 | 63.0 | 3.56 | 0.1659 | |
C6 | 521.0 | 521.0 | 574.2 | 53.2 | 3.28 | 0.0667 |
Dye | c(Dye)/ (mol·L-1) | c(Biomolecules)/ (μg·mL-1) | ΦDNA/ ΦFree | ΦBSA/ ΦFree | ΦMurmidase/ ΦFree | ΦAmylase/ ΦFree | ΦChmotrypsin/ ΦFree | ΦBovine hemoglobin/ ΦFree |
---|---|---|---|---|---|---|---|---|
C1 | 1×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
4 | 2.23 | 1.10 | 1.26 | 1.16 | 1.10 | 1.24 | ||
10 | 4.23 | 1.21 | 1.13 | 1.07 | 1.32 | 1.20 | ||
5×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
4 | 1.26 | 0.91 | 0.86 | 0.87 | 0.92 | 0.68 | ||
10 | 1.77 | 1.01 | 1.00 | 1.10 | 1.00 | 0.74 | ||
C2 | 1×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
4 | 0.20 | 0.56 | 0.36 | 0.12 | 0.13 | 0.29 | ||
10 | 0.50 | 0.76 | 0.27 | 0.43 | 0.14 | 0.21 | ||
5×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
4 | 1.20 | 0.85 | 0.85 | 0.35 | 0.98 | 0.57 | ||
10 | 1.41 | 1.11 | 0.66 | 0.58 | 0.34 | 0.37 | ||
C3 | 1×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
4 | 3.50 | 0.91 | 0.91 | 0.85 | 0.97 | 0.85 | ||
10 | 10.04 | 0.99 | 0.78 | 0.79 | 0.89 | 0.81 | ||
5×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
4 | 2.14 | 1.20 | 1.62 | 1.71 | 1.31 | 1.30 | ||
10 | 3.45 | 1.63 | 1.07 | 1.26 | 1.19 | 1.60 | ||
C4 | 1×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
4 | 2.82 | 1.14 | 1.48 | 1.07 | 1.16 | 1.14 | ||
10 | 17.41 | 1.09 | 1.23 | 0.98 | 1.14 | 1.13 | ||
3×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
4 | 0.55 | 1.00 | 1.01 | 1.04 | 0.94 | 1.04 | ||
10 | 5.36 | 0.97 | 0.93 | 1.01 | 0.94 | 1.00 | ||
C5 | 1×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
4 | 5.55 | 0.89 | 0.94 | 0.92 | 0.92 | 0.92 | ||
10 | 12.27 | 0.96 | 0.88 | 0.92 | 0.90 | 0.94 | ||
3×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
4 | 1.37 | 1.02 | 1.00 | 1.10 | 1.00 | 1.07 | ||
10 | 1.15 | 1.03 | 0.99 | 1.11 | 0.93 | 0.98 | ||
C6 | 5×10-6 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
4 | 2.22 | 1.22 | 1.14 | 1.08 | 1.14 | 1.09 | ||
10 | 4.04 | 1.40 | 1.18 | 1.13 | 1.16 | 1.08 | ||
1×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
4 | 1.85 | 1.15 | 1.12 | 1.07 | 1.06 | 1.09 | ||
10 | 2.80 | 1.18 | 1.11 | 1.27 | 1.08 | 1.05 |
Table 4 Fluorescence quantum yield of dyes C1—C6 with different biomolecules*
Dye | c(Dye)/ (mol·L-1) | c(Biomolecules)/ (μg·mL-1) | ΦDNA/ ΦFree | ΦBSA/ ΦFree | ΦMurmidase/ ΦFree | ΦAmylase/ ΦFree | ΦChmotrypsin/ ΦFree | ΦBovine hemoglobin/ ΦFree |
---|---|---|---|---|---|---|---|---|
C1 | 1×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
4 | 2.23 | 1.10 | 1.26 | 1.16 | 1.10 | 1.24 | ||
10 | 4.23 | 1.21 | 1.13 | 1.07 | 1.32 | 1.20 | ||
5×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
4 | 1.26 | 0.91 | 0.86 | 0.87 | 0.92 | 0.68 | ||
10 | 1.77 | 1.01 | 1.00 | 1.10 | 1.00 | 0.74 | ||
C2 | 1×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
4 | 0.20 | 0.56 | 0.36 | 0.12 | 0.13 | 0.29 | ||
10 | 0.50 | 0.76 | 0.27 | 0.43 | 0.14 | 0.21 | ||
5×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
4 | 1.20 | 0.85 | 0.85 | 0.35 | 0.98 | 0.57 | ||
10 | 1.41 | 1.11 | 0.66 | 0.58 | 0.34 | 0.37 | ||
C3 | 1×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
4 | 3.50 | 0.91 | 0.91 | 0.85 | 0.97 | 0.85 | ||
10 | 10.04 | 0.99 | 0.78 | 0.79 | 0.89 | 0.81 | ||
5×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
4 | 2.14 | 1.20 | 1.62 | 1.71 | 1.31 | 1.30 | ||
10 | 3.45 | 1.63 | 1.07 | 1.26 | 1.19 | 1.60 | ||
C4 | 1×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
4 | 2.82 | 1.14 | 1.48 | 1.07 | 1.16 | 1.14 | ||
10 | 17.41 | 1.09 | 1.23 | 0.98 | 1.14 | 1.13 | ||
3×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
4 | 0.55 | 1.00 | 1.01 | 1.04 | 0.94 | 1.04 | ||
10 | 5.36 | 0.97 | 0.93 | 1.01 | 0.94 | 1.00 | ||
C5 | 1×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
4 | 5.55 | 0.89 | 0.94 | 0.92 | 0.92 | 0.92 | ||
10 | 12.27 | 0.96 | 0.88 | 0.92 | 0.90 | 0.94 | ||
3×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
4 | 1.37 | 1.02 | 1.00 | 1.10 | 1.00 | 1.07 | ||
10 | 1.15 | 1.03 | 0.99 | 1.11 | 0.93 | 0.98 | ||
C6 | 5×10-6 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
4 | 2.22 | 1.22 | 1.14 | 1.08 | 1.14 | 1.09 | ||
10 | 4.04 | 1.40 | 1.18 | 1.13 | 1.16 | 1.08 | ||
1×10-5 | 0 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
4 | 1.85 | 1.15 | 1.12 | 1.07 | 1.06 | 1.09 | ||
10 | 2.80 | 1.18 | 1.11 | 1.27 | 1.08 | 1.05 |
Dye | c(DNA)/ (μg·mL-1) | Absorption | Fluorescence | |||||
---|---|---|---|---|---|---|---|---|
λmax/nm | Hypochromic effect(%) | 104ε/ (L·mol-1·cm-1) | λex/nm | λem/nm | Stokes shift/nm | ΦDNA/ΦFree | ||
C3 | 0 | 477.0 | 0.0 | 2.09 | 475.0 | 572.4 | 97.4 | 1.00 |
2 | 445.0 | 13.8 | 1.8 | 475.0 | 574.4 | 99.4 | 1.84 | |
4 | 448.0 | 24.9 | 1.57 | 475.0 | 592.8 | 117.8 | 3.50 | |
6 | 484.0 | 29.1 | 1.48 | 475.0 | 592.6 | 117.6 | 7.79 | |
8 | 478.0 | 15.7 | 1.76 | 475.0 | 593.4 | 118.4 | 8.02 | |
10 | 488.0 | 9.5 | 1.9 | 475.0 | 595.4 | 120.4 | 10.04 | |
12 | 489.0 | 5.3 | 1.98 | 475.0 | 592.6 | 117.6 | 12.22 | |
C4 | 0 | 473.0 | 0.0 | 1.57 | 468.0 | 559.4 | 91.4 | 1.00 |
2 | 465.0 | 2.7 | 1.14 | 468.0 | 565.2 | 97.2 | 2.14 | |
4 | 465.0 | 5.3 | 1.94 | 468.0 | 567.2 | 99.2 | 2.82 | |
6 | 473.0 | 19.5 | 1.15 | 468.0 | 567.8 | 99.8 | 11.55 | |
8 | 479.0 | 19.1 | 1.46 | 468.0 | 567.4 | 99.4 | 12.19 | |
10 | 479.0 | 17.8 | 1.33 | 468.0 | 566.6 | 98.6 | 17.41 | |
12 | 483.0 | 18.8 | 1.40 | 468.0 | 566.4 | 98.4 | 20.03 | |
C5 | 0 | 462.0 | 0.0 | 3.98 | 461.0 | 553.8 | 92.8 | 1.00 |
2 | 459.0 | 19.0 | 3.22 | 461.0 | 559.4 | 98.4 | 1.20 | |
4 | 461.0 | 23.3 | 3.05 | 461.0 | 564.0 | 103.0 | 5.55 | |
6 | 462.0 | 16.8 | 3.31 | 461.0 | 563.6 | 102.6 | 7.29 | |
8 | 462.0 | 16.6 | 3.32 | 461.0 | 564.4 | 103.4 | 10.17 | |
10 | 464.0 | 15.2 | 3.37 | 461.0 | 564.0 | 103.0 | 12.27 | |
12 | 465.0 | 15.4 | 3.36 | 461.0 | 563.8 | 102.8 | 15.30 |
Table 5 Spectroscopic data of dyes C3—C5(1×10-5 mol/L) in presence of DNA
Dye | c(DNA)/ (μg·mL-1) | Absorption | Fluorescence | |||||
---|---|---|---|---|---|---|---|---|
λmax/nm | Hypochromic effect(%) | 104ε/ (L·mol-1·cm-1) | λex/nm | λem/nm | Stokes shift/nm | ΦDNA/ΦFree | ||
C3 | 0 | 477.0 | 0.0 | 2.09 | 475.0 | 572.4 | 97.4 | 1.00 |
2 | 445.0 | 13.8 | 1.8 | 475.0 | 574.4 | 99.4 | 1.84 | |
4 | 448.0 | 24.9 | 1.57 | 475.0 | 592.8 | 117.8 | 3.50 | |
6 | 484.0 | 29.1 | 1.48 | 475.0 | 592.6 | 117.6 | 7.79 | |
8 | 478.0 | 15.7 | 1.76 | 475.0 | 593.4 | 118.4 | 8.02 | |
10 | 488.0 | 9.5 | 1.9 | 475.0 | 595.4 | 120.4 | 10.04 | |
12 | 489.0 | 5.3 | 1.98 | 475.0 | 592.6 | 117.6 | 12.22 | |
C4 | 0 | 473.0 | 0.0 | 1.57 | 468.0 | 559.4 | 91.4 | 1.00 |
2 | 465.0 | 2.7 | 1.14 | 468.0 | 565.2 | 97.2 | 2.14 | |
4 | 465.0 | 5.3 | 1.94 | 468.0 | 567.2 | 99.2 | 2.82 | |
6 | 473.0 | 19.5 | 1.15 | 468.0 | 567.8 | 99.8 | 11.55 | |
8 | 479.0 | 19.1 | 1.46 | 468.0 | 567.4 | 99.4 | 12.19 | |
10 | 479.0 | 17.8 | 1.33 | 468.0 | 566.6 | 98.6 | 17.41 | |
12 | 483.0 | 18.8 | 1.40 | 468.0 | 566.4 | 98.4 | 20.03 | |
C5 | 0 | 462.0 | 0.0 | 3.98 | 461.0 | 553.8 | 92.8 | 1.00 |
2 | 459.0 | 19.0 | 3.22 | 461.0 | 559.4 | 98.4 | 1.20 | |
4 | 461.0 | 23.3 | 3.05 | 461.0 | 564.0 | 103.0 | 5.55 | |
6 | 462.0 | 16.8 | 3.31 | 461.0 | 563.6 | 102.6 | 7.29 | |
8 | 462.0 | 16.6 | 3.32 | 461.0 | 564.4 | 103.4 | 10.17 | |
10 | 464.0 | 15.2 | 3.37 | 461.0 | 564.0 | 103.0 | 12.27 | |
12 | 465.0 | 15.4 | 3.36 | 461.0 | 563.8 | 102.8 | 15.30 |
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