CN109251746B - 蒽环桥联双核钌配合物荧光探针的制备及其应用 - Google Patents
蒽环桥联双核钌配合物荧光探针的制备及其应用 Download PDFInfo
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
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- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
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Abstract
蒽环桥联双核钌配合物荧光探针的制备及其应用,该配合物以过渡金属Ru为中心离子,以蒽环桥联咪唑环的蒽环衍生物作为配体,具有pH传感的发光性能,相对于现有的pH传感器而言,本发明的双核钌配合物pH传感器分子具有较好的水溶性,pK a位于生理区范围内,可应用于生物医学体系中检测单线态氧。
Description
技术领域
本发明属于一种蒽环桥联双核钌配合物荧光探针的制备及其应用,涉及溶液中双核钌配合物对体系pH响应的荧光的测定,具体涉及一类含有蒽环衍生物配体和双核钌金属配合物pH传感荧光探针的制备及其应用。
背景技术
钌配合物具有良好的光物理性质、光化学性质、化学稳定性、氧化还原性质、可见光激发,容易被肿瘤细胞吸收,毒性较低,在生命体系中可通过改变配体的结构来调节与目标靶向分子之间的亲和力、反应速度和电子转移的方向 [(a) K. R. Weishaupt, C. J.Gomer, T. J. Dougherty. Cancer Research, 1976, 36, 2326 - 2329. (b) 吕庆銮,张苗, 岳宁宁, 王怀友. 单线态氧的检测及分析应用研究进展[J]. 化学分析计量,2008,3, 74 - 77.]。近年来,钌配合物在荧光探针、传感器方面引起了研究热潮。蒽基作为一个特殊的反应基团可以捕获单线态氧和光动力治疗中被用来破坏有害细胞或组织的一种重要的活性氧 [M. Ishizuka, F. Abe, Y. Sano, K. Takahashi, K. Inoue, M.Nakajima, T. Kohda, N. Komatsu, S. Ogura, T. Tanaka. Int. Immunopharmacol.,2011, 11, 358]。然而,蒽基能有效地猝灭某些过渡金属配合物的荧光,如Eu(III) [(a)B. Song, G.L. Wang, J.L. Yuan. Chem. Commun., 2005, 28, 3553. (b) B. Song,G.L. Wang, M.Q. Tan, J.L. Yuan. New J. Chem., 2005, 29, 1431. (c) B. Song,G.L. Wang, M.Q. Tan, J.L. Yuan. J. Am. Chem. Soc., 2006, 128, 13442. (d) Z.C.Dai, L. Tian, Y.N. Xiao, Z.Q. Ye, R. Zhang, J.L. Yuan. J. Mater. Chem. B,2013, 1, 924.]、Tb(III) [M.Q. Tan, B. Song, G.L. Wang, J.L.Yuan. Free Radical. Biol. Med., 2006, 40, 1644.]、Re(I) [Y.J. Liu, K.Z. Wang. Eur. J. Inorg. Chem., 2008, 33, 5214.]、Nd(III) [W.S. Loa, H.G. Lib, G.L. Law, W.T. Wong,K.L.Wong. J. Lumin., 2016, 169, 549.]和Ru(II) [(a) H.Y. Ding, X.S. Wang, L.Q.Song, J.R. Chen, J.H. Yu, C. Li, B.W. Zhang. J. Photochem. Photobio. A: Chem., 2006, 177, 286. (b) Z.Q. Ye, B. Song, Y.J. Yin, R. Zhang, J.L. Yuan.Dalton Trans., 2013, 42, 14380.] 配合物。然而,这些稀土荧光探针和蒽基的发射都需要紫外光激发,这对生物组织是有害的。Re(I)和Ru(Ⅱ)配合物在可见光下的激发,适合于生物***减少细胞损伤。
pH传感器在测量生物和环境***中的单线态氧、pH和二氧化碳时尤为重要。许多具有pH敏感功能的发光染料,如萘、荧光素和香豆素衍生物,已被用作测定pH值的指示剂[(a) C. Zhou, Y. Li, Y. Zhao, J. Zhang, W. Yang, Y. Li. Org. Lett., 2011, 13,292; (b) N. Saleh, Y.A. Al-Soud, W.M. Nau. Spectrochim. Acta. A, 2008, 71,818.]。然而,这些发光有机分子的Stokes’位移较小,光稳定性差。而Ru(Ⅱ)配合物有质子/可脱质子的位点,可见光激发和激发态电离常数可能使配合物被用于生物***,因此Ru(II)配合物作为pH传感器对生物分子的影响方面具有重要意义 [(a) C.S. Allardyce,P.J. Dyson, D.J. Ellis, S.L. Heath. Chem. Commun., 2001, 15, 1396. (b) M.Haga, T. Takasugi, A. Tomie, M. Ishizuya, T. Yamada. J. Chem. Soc. Dalton Trans., 2003, 10, 2069. (c) F.X. Cheng, N. Tang, J.S. Chen, F. Wang, L.H.Chen. Inorg. Chem. Commun., 2011, 14, 852.]。含有咪唑基的Ru(II)配合物是较好的π供体和较差的π受体,在可逆酸碱相互转化过程中可能引起较大的能量扰动 [(a) S.D.Jiang, K.Z. Wang, F.R. Liu, Y.A. Zhang, Acta. Chim. Sinica, 2005, 63, 783-786. (b) Y.P. Ou, G. Chen, J. Yin, G.A. Yu, S.H. Liu. J. Coord. Chem., 2011,64, 3062. (c) F.X. Cheng, C.X. He, L.F. Yao, F. Wang, N. Tang. J. Coord. Chem., 2015, 68, 704.],因此,设计金属钌配合物pH传感器的研究中,最重要的因素是设计含有咪唑环的有机配体,然后与钌配合物配位,形成金属配合物。据文献报道,只有少数含咪唑环的Ru(Ⅱ)多联吡啶配合物被报道[(a) S.H. Fan, K.Z. Wang, W.C. Yang. Eur. J. Inorg. Chem., 2009, 2009, 508 ; (b) .Z. Ma, H.J. Yin, K.Z. Wang. J. Phys. Chem. B, 2009, 113, 11039; (c) X.L. Zhao, Z.S. Li, Z.B. Zheng, A.G. Zhang,K.Z. Wang. Dalton Trans., 2013, 42, 5764; (d)Z.B. Zheng, S.Y. Kang, X. Yi, N.Zhang, K.Z. Wang. J. Inorg. Biochem., 2014, 141, 70.],其中有些钌配合物具有晶体结构。近几年来,王克志课题组报告了一个含有咪唑环与蒽环的铼(I)配合物的荧光探针[Y. J. Liu, K. Z. Wang,Eur. J. Inorg. Chem., 2008, 5214.]、一个蒽环桥联咪唑基双核钌配合物荧光探针 [H.J. Yin, Y.J. Liu, J. Gao, K.Z. Wang. Dalton Trans.,2017, 46, 3325–3331.] 和3个专利 [(a) 王克志,刘艳菊,陈春辉,钌和铱金属配合物单线态氧荧光探针的制备及其应用,中国发明专利,申请号 2008102405914, 公布号CN101475597A; (b) 王克志,尹红菊,李奇,刘艳菊,水溶性钌金属配合物单线态氧荧光探针的制备及应用,中国发明专利,专利号CN102344464A;(c) 王克志,李奇,刘艳菊,尹红菊,Hdppz配体的钌配合物作为单线态氧荧光探针的应用,中国发明专利,专利号CN.]。这些配合物在可见光激发,可用于生物体系中检测单线态氧,作为荧光探针具有较大的优势,单线态氧探针在细胞中的应用,也跟溶液的酸碱性息息相关,单线态氧探针在生理环境下的应用要求探针在生理条件下的pH下具有某些性质,因此,探针分子酸碱性之的研究显得尤为重要。因此进一步研究具有水溶性好、灵敏度高、选择性好,适用范围广,可见光激发的pH传感钌配合物荧光探针具有重要的现实意义。
发明内容
本发明的目的是提供一种蒽环桥联双核钌配合物荧光探针的制备及其应用,开发可见光激发、荧光背景低、水溶性好、灵敏度高的新型双核金属钌配合物荧光探针。
为实现上述目的,本发明的技术方案如下:
一种蒽环桥联双核钌配合物荧光探针的制备及其应用,其特征在于所述蒽环桥联的双核钌配合物,其结构通式为[RuoAmLn]Xk,其中:X为抗衡离子;L为蒽环桥联衍生物配体,A为辅助配体;其结构式如式I所示;
I
R1为氢或C1-C10的直链或支链烷基;R2为氢或C1-C10的直链或支链烷基;辅助配体A为联吡啶(bpy)、邻菲罗啉(phen)或4,4’二甲基联吡啶(mbpy);所选的抗衡离子X为Cl-,PF6 -,ClO4 -,NO3 -,BF4 - 和CF3SO3 -中的一种;
所述钌配合物,将配体L与Ru(bpy)2·Cl2在溶剂中加热至120~140°左右进行配位反应,当X不是Cl-时,反应结束冷却后,需要加入抗衡阴离子X搅拌反应一段时间,过滤得相应粗产品,然后通过重结晶或柱层析分离纯化,获得所述双核钌配合物。
式I中R1为氢或C1-C6的直链或支链烷基;R2为氢或C1-C6的直链或支链烷基。
式I中 R1为氢;R2为氢。
按照下述方法制备配体L:氮气保护下,将式(1)或(2)中的1,10-邻菲啰啉-5,6-二酮与蒽醛进行醛酮缩合反应,反应液冷却后,用蒸馏水稀释,调节pH得粗产品,通过重结晶提纯,可得到配体L;
(1)
按上述方法得到的任何一个钌配合物作为pH传感荧光探针应用。
利用所述的双核钌配合物在BR缓冲体系中,测试对缓冲体系中pH的响应及光谱性质,包括以下步骤:
1)在BR缓冲溶液中,加入所述双核钌配合物,通过加入浓硫酸或者饱和氢氧化钠溶液进行调节体系中的pH,通过可见光激发测定体系的荧光强度和吸光度,得到相对应的荧光量子效率,获得双核钌配合物在BR缓冲溶液中的酸碱性质图谱。
2)根据步骤1)获得双核钌配合物在BR体系中的质子化和去质子化的过程分段性质,并对某一波长下的吸光度进行Sigmoidal拟合,获得基态下的pK a *。
3)根据2)中测得的pK a *和荧光性质图谱,利用如下公式计算得出激发态的电离常数pK a *:
pK a * = pK a + (0.625/T) (ν B-ν HB)
其中,ν B 为化合物以去质子化形式存在时发射峰的波数,而ν HB为化合物以质子化形式存在时发射峰的波数。
以下作进一步说明:
所述蒽环桥联双咪唑环衍生物配体,其结构通式为 [RuoAmLn]Xk,其中:X为抗衡离子;L为蒽环桥联衍生物配体,其结构式如式I所示;
I
式中R1为C1-C10的直链或支链烷基;R2为C1-C10的直链或支链烷基。上述配体L中R1优先选择为氢或C1-C6的直链或支链烷基,更优先选为氢,R2优先选择为氢或C1-C6的直链或支链烷基,更优先选为氢。所述烷基主要是甲基、乙基、丙基、丁基、戊基、己基。
上述A为辅助配体,常用联吡啶(bpy),邻菲咯啉(phen),4,4’二甲基联吡啶(mbpy),结构参加式Ⅱ,但是不限于这三种配体。
Ⅱ
上述抗衡离子X多为负一价的阴离子,例如Cl-,PF6 -,ClO4 -,NO3 -,BF4 -,CF3SO3 -。
本发明的配合物的具体例子如下:
当o = 2,m = 4,k = 4,L是配体L1(bippa,其中R1 = H),A是辅助配体联吡啶(bpy),X = PF6 -,该配合物的结构如下式1所示:
当o = 2,m = 4,k = 4,L是配体L2(m-bippa,其中R1 = H),A是辅助配体联吡啶(bpy),X = PF6 -,该配合物的结构如下式2所示:
上述蒽环桥联的配体L1和L2的制备方法如下:
1,10-邻菲啰啉-5,6-二酮与蒽醛 [Suspene, Clement, Simonato, JeanPierre.PCT Int. Appl., 2010142864 (2010).] 进行醛酮缩合反应,反应液冷却后,用蒸馏水稀释,调节pH得粗产品,通过重结晶提纯,可得到配体L。反应方程式如下:
(1)
(2)
上述钌配合物 [Ru2AmLn]Xk的制备方法如下:
将配体L与Ru(bpy)2·Cl2在溶剂中加热至120~140°左右进行配位反应,当X不是Cl-时,反应结束冷却后,需要加入抗衡阴离子X搅拌反应一段时间,过滤得相应粗产品,然后通过重结晶或柱层析分离纯化,获得所述双核钌配合物。
本发明的双核钌配合物pH传感探针,以过渡金属钌为中心离子,用蒽环桥联两个咪唑环的衍生物作为配体,具有pH传感的发光性能,通过研究其酸碱性质,发现磁探针pK a位于生理区范围内,可应用于生物医学体系中检测单线态氧。
该双核钌配合物的pH传感探针的应用过程为:在BR缓冲溶液中,利用所述的配合物作为pH响应的荧光探针,使体系的荧光强度随着体系的pH的变化而发生变化,通过可见光激发的荧光测定上述钌配合物的荧光与体系酸碱度的关系。具体步骤是:
1.Britton-Robinson缓冲液中0.04 M H3BO3, 0.04 M H3PO3, 0.04 M CH3COOH)加入本发明的配合物,取浓硫酸和饱和氢氧化钠溶液调节体系pH值,每隔约0.2个pH值测定一个点,测定pH范围为0-14。实验通过测定不同pH下溶液的紫外-可见吸收光谱和荧光发射光谱,从而进一步研究其质子化和去质子化过程。根据酸碱质子理论,任何一种弱酸(HB)在水溶液中存在解离平衡,经过公式推导可得到酸碱解离常数pK a,如式1所示:
配合物基态去质子化的pK a *可由式2式计算得到 [A. M. Bond, M. Haga. Inorg. Chem. 1986,25, 4507.]。
其中A 0,A f分别是指初始和终态的吸光度。用Origin软件进行Sigmoidal拟合,拐点即pK a *。激发态的电离常数pK a *可根据公式 (3) 计算而得,其中ν B 和ν HB为化合物以去质子化和质子化形式存在时发射峰的波数 [K. Kalyanasundaram. Coord. Chem. Rev. 1982,46, 159 - 244.]。
pK a * = pK a + (0.625/T) (ν B-ν HB) (3)
本发明在已经报道的pH传感器和钌配合物荧光探针的基础上设计合成了可见光激发,含有单线态氧响应单元的蒽基的双核钌配合物pH荧光传感器。本发明的pH传感器具有以下优点:
1. Cl-作为抗衡离子时,该钌配合物的水溶性较好,可在各种缓冲溶液中使用,干扰小,比较适合于生物体系中作为pH传感探针分子。
2. 本发明是双核钌配合物,可作为单线态氧检测探针,检测1O2。
附图说明:
图1为配体L1(bippa)及配合物 [Ru2(bpy)4(bippa)](PF6)4的合成路线。
图2为配体L2(m-bippa)及配合物[Ru2(bpy)4(m-bippa)](PF6)4的合成路线。
图3为在BR缓冲体系中pH对配合物 [Ru2(bpy)4(bippa)](PF6)4 (3.3×10-6 M) 紫外-吸收光谱的影响。
图4为在BR缓冲体系中pH对配合物 [Ru2(bpy)4(bippa)](PF6)4 (3.3×10-6 M)荧光光谱的影响。
图5为BR缓冲体系中配合物 [Ru2(bpy)4(bippa)](PF6)4质子化和去质子化的过程。
具体实施方式
下面通过实施例对本发明进一步说明。
实施例一、配体bippa及配合物 [Ru2(bpy)4(bippa)](PF6)4的合成。
合成路线如图1所示,基本操作过程如下:
4,4’(蒽-9,10-二)苯甲醛是按照文献 [Suspene, Clement, Simonato,JeanPierre. PCT Int. Appl., 2010142864 (2010).] 合成的。
1. 配体9,10-二-(4-(咪唑[4,5-f]1,10-邻菲咯啉)苯基)蒽(bippa)的合成
称取1,10-邻菲啰啉-5,6-二酮353 mg,蒽醛216 mg,乙酸铵2.6 g,放入圆底烧瓶中,加入50 mL冰醋酸,氮气保护下加热回流8小时。冷却至室温后过滤,滤液中加入200 mL蒸馏水稀释,用浓氨水调pH至7,出现大量黄色沉淀。过滤之后将沉淀收集起来用水洗涤而后用CH2Cl2洗涤,最后真空干燥。粗产品用三氯甲烷和甲醇混合溶液(v/v=4:1) 重结晶。重结晶后抽滤得配体,真空干燥,得产品300 mg,产品配体为红色。产率为:23%。ESI - MS:m/z= 383.8([M+2H+]2+),m/z = 766.8([M + H+]+)。
2. 配合物[Ru2(bpy)4(bippa)](PF6)4的合成
称取配体bippa 76.6 mg和Ru(bpy)2Cl2·2H2O 130 mg,在氮气保护下回流反应24h。冷却至室温后,减压蒸馏除去乙二醇,用柱层析(中性氧化铝,乙腈/乙醇=10:1)提纯,得到橘黄色色带,加入饱和的六氟磷酸铵水溶液产生红色沉淀,抽滤,得产物100 mg。1H NMR(400 MHz,DMSO-d 6) δ: 7.25 (s,2 H),7.39 (t,6 H),7.55 (m,3 H),7.62 (t,4 H),7.67(m,4 H),7.76 (m,3 H),7.87 (m,7 H),8.00 (m,6 H),8.13 (m,8 H),8.25 (t,4 H),8.65(m,4 H),8.91 (dd,8 H),9.17 (d,3 H)。ESI - MS:m/z = 398([M-4PF6]4+)。
实施例二、配体m-bippa及配合物 [Ru2(bpy)4(m-bippa)](PF6)4的合成。
合成路线如图2所示,基本操作过程如下:
1. 3,3’(蒽-9,10-二)苯甲醛的合成
合成方法与4,4’(蒽-9,10-二)苯甲醛的制备方法一致。1H NMR (400 MHz,CDCl3)δ: 7.40(dd, 4 H) , 7.64(dd, 4 H), 7.83 (m, 4 H), 8.04(d, 2 H), 8.14(dd, 2 H),10.18(d, 2 H)。
2. 配体9,10-二-(3-(咪唑[4,5-f]1,10-邻菲咯啉)苯基)蒽(m-bippa)的合成
方法与制备配体L1一致。1 H NMR (δ H,ppm,400 MHz,CDCl3-d 6):7.55(dd, 4 H),7.71(t, 2 H), 7.70(dd, 4 H), 7.84(m, 4 H), 7.98(d, 2 H), 8.44(d, 2 H), 8.61(t, 2 H), 8.90(m, 4 H), 9.05(d, 4 H).
3. 配合物[Ru2(bpy)4(m-bippa)](PF6)4的合成
方法与制备配合物[Ru2(bpy)4(bippa)](PF6)4的方法一致。1H NMR (δ H,ppm,400MHz,DMSO-d 6):14.55(s, 2 H), 9.13(dd, 4 H), 8.87(dd, 8 H), 8.69(s, 2 H), 8.61(d, 2 H), 8.23(t, 4 H), 8.10(m, 8 H), 7.93(m, 2 H), 7.86(m, 4 H), 7.85(d, 4H), 7.60(m, 8 H), 7.35(t, 8 H),7.21(s, 2 H), 7.08(s, 2 H), 6.96(s, 2 H). ESI- MS:m/z = 406(1/4[M-4PF6+2H2O]4+).
实施例三、双核钌配合物探针随pH变化的光谱性质
以[Ru2(bpy)4(bippa)](PF6)4为例,介绍本发明配合物作为pH传感探针在BR体系中的酸碱性质。
在BR缓冲溶液中,随着pH的改变,钌配合物中含有咪唑环,能发生质子化合去质子化过程,因此,钌配合物体现出来不同的紫外可见吸收峰强度。
配合物[Ru2(bpy)4(bippa)](PF6)4在水溶液中的紫外-可见吸收光谱,参看图3。285 nm的高能带是由配体内部的π-π*跃迁引起的,353 ~ 393 nm是蒽环的特征吸 收峰[B. Song, G. L. Wang, M. Q. Tan, J. L. Yuan,J. Am. Chem. Soc. 2006,128,13442- 13450.],460 nm是由金属到配体的电荷跃迁引起的。随着溶液的pH的变化,钌配合物的紫外可见光谱呈现2个过程分别是 (1) pH = 1.81 - 4.10, (2) pH = 5.02 - 9.37。
第一个阶段,在pH值从1.81上升到4.10的过程中,285 nm处的吸收峰呈现下降的趋势。460 nm和蒽环的特征吸收峰没有明显的变化。第二阶段,在pH值从5.02上升到9.37的过程中,285 nm处的吸收峰明显下降。对285 nm处的吸光度随pH的变化分段进行Sigmoidal非线性拟合,得到配合物探针处于基态的两个电离常数:pK a1 = 1.12 ± 0.15,pK a2 =6.90 ± 0.24。
配合物[Ru2(bpy)4(bippa)](PF6)4的荧光光谱随溶液pH值的变化,参看图4。在460nm激发下,在615 nm附近产生了荧光发射峰,这是钌配合物的特征MLCT荧光。随着pH的增大,在整个范围内,双核钌配合物的荧光发射峰强度呈现下降的趋势,蓝移了8 nm,荧光强度减弱了2.8倍。根据公式(3),可求出配合物探针激发态的电离常数pK a1 * = 1.09,pK a2 * =6.92。其质子化和去质子化参见图5。配合物探针[Ru2(bpy)4(bippa)](PF6)4配体中含有两个相同的咪唑环,理论上去质子化过程应该分两个过程,相应的pH内紫外可见吸收光谱和荧光光谱的变化趋势都是一样的。
由此可见,双核钌配合物[Ru2(bpy)4(bippa)](PF6)4是一个“on-off”型荧光pH传感分子,而且pK a2是在生理区内,可用于生理环境下检测单线态氧及其他性质检测。
Claims (6)
1.一种蒽环桥联双核钌配合物荧光探针的制备方法,其特征在于所述蒽环桥联双核钌配合物,其结构通式为[RuoAmLn]Xk,其中:o为2,m为4,n为1,k为4;X为抗衡阴离子;L为蒽环桥联衍生物配体,A为辅助配体;L的结构式如式I所示,为L1或L2;
R1为氢或C1-C10 的直链或支链烷基;R2为氢或C1-C10 的直链或支链烷基;辅助配体A为联吡啶(bpy)、邻菲罗啉(phen)或4,4’二甲基联吡啶;所选的抗衡离子X为Cl-,PF6 -,ClO4 -,NO3 -,BF4 -和CF3SO3 -中的一种;所述双核钌配合物的制备方法,包括以下步骤,将配体L与Ru(A)2•Cl2在溶剂中加热至120~140℃进行配位反应,当X不是Cl-时,反应结束冷却后,需要加入抗衡阴离子X搅拌反应一段时间,过滤得相应粗产品,然后通过重结晶或柱层析分离纯化,获得所述双核钌配合物。
2.如权利要求1所述的一种蒽环桥联双核钌配合物荧光探针的制备方法 ,式I中R1为氢或C1-C6的直链或支链烷基;R2为氢或C1-C6的直链或支链烷基。
3.如权利要求1所述的一种蒽环桥联双核钌配合物荧光探针的制备方法 ,式I中R1为氢;R2为氢。
5.如权利要求1所述制备方法制备的蒽环桥联双核钌配合物荧光探针的应用,其特征在于利用所述制备方法得到的任何一个钌配合物作为pH传感荧光探针应用。
6.如权利要求5所述的蒽环桥联双核钌配合物荧光探针的应用,其特征在于利用所述的双核钌配合物在BR缓冲体系中,测试对缓冲体系中pH的响应及光谱性质,包括以下步骤:
1)在BR缓冲溶液中,加入所述双核钌配合物,通过加入浓硫酸或者饱和氢氧化钠溶液进行调节体系中的pH,通过可见光激发测定体系的荧光强度和吸光度,得到相对应的荧光量子效率,获得双核钌配合物在BR缓冲溶液中的酸碱性质图谱;
2)根据步骤1)获得双核钌配合物在BR体系中的质子化和去质子化的过程分段性质,并对某一波长下的吸光度进行Sigmoidal拟合,获得基态下的电离常数pKa;
3)根据2)中测得的pKa和荧光性质图谱,利用如下公式计算得出激发态的电离常数pKa *:
pKa *=pKa+(0.625/T) (νB-νHB)
其中,T为绝对温度,νB为化合物以去质子化形式存在时发射峰的波数,而νHB为化合物以质子化形式存在时发射峰的波数。
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