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A chiral lactate reporter based on total and circularly polarized Tb(iii) luminescence†
New Journal of Chemistry ( IF 2.7 ) Pub Date : 2018-01-16 00:00:00 , DOI: 10.1039/c7nj04640e Marco Leonzio 1, 2, 3, 4, 5 , Andrea Melchior 6, 7, 8, 9, 10 , Georgina Faura 6, 7, 8, 9, 10 , Marilena Tolazzi 6, 7, 8, 9, 10 , Marco Bettinelli 1, 2, 3, 4, 5 , Francesco Zinna 10, 11, 12 , Lorenzo Arrico 10, 11, 12 , Lorenzo Di Bari 10, 11, 12 , Fabio Piccinelli 1, 2, 3, 4, 5
New Journal of Chemistry ( IF 2.7 ) Pub Date : 2018-01-16 00:00:00 , DOI: 10.1039/c7nj04640e Marco Leonzio 1, 2, 3, 4, 5 , Andrea Melchior 6, 7, 8, 9, 10 , Georgina Faura 6, 7, 8, 9, 10 , Marilena Tolazzi 6, 7, 8, 9, 10 , Marco Bettinelli 1, 2, 3, 4, 5 , Francesco Zinna 10, 11, 12 , Lorenzo Arrico 10, 11, 12 , Lorenzo Di Bari 10, 11, 12 , Fabio Piccinelli 1, 2, 3, 4, 5
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The coordination features and signaling of a L-lactate ion by a [Tb(bpcd)]+ (bpcd = N,N′-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N′-diacetate) complex have been investigated by means of a combination of techniques, including total luminescence, calorimetry and circularly polarized luminescence. The L-lactate/[Tb(bpcd)]+ association constant, determined by both luminescence titration and isothermal titration calorimetry, indicates a weak interaction (log K = 1.3–1.45) between the analyte and both enantiomers of the complex. The theoretical DFT calculations suggest that the most likely coordination of L-lactate to the possible stereoisomers of the [Tb(S,S-bpcd)]+ complex (trans-O,O or trans-Npy,Npy) is one involving a hydroxyl group. The results of [Tb(rac-bpcd)]+ as a chiroptical luminescent probe of L-lactate underline the peculiar role of the chiral 1,2-diaminocyclohexane (DACH) backbone. Indeed, the target anion is capable of inducing CPL activity in the racemic mixture of Tb complexes containing DACH-based ligands. The same is not observed for the achiral analogue [Tb(bped)]+ (bped = N,N′-bis(2-pyridylmethyl)ethylenediamine-N,N′-diacetate) complex, likely because of the flexibility of the ethylenic group which allows an interconversion between different isomers which produces a null net CPL activity. Thanks to the differential quantum yield of the two diastereomeric species (R,R)-L and (S,S)-L, one can use the racemic complex to reveal L-lactate by measuring the induced CPL spectrum. Interestingly, this has been demonstrated in a commercial complex solution for medical use, containing several electrolytes, namely Ringer's lactate.
中文翻译：
基于总和圆极化的Tb（iii）发光的手性乳酸盐报告剂†
协调功能和信令大号由乳酸盐离子[TB（bpcd的）] +（bpcd的= Ñ，Ñ ' -双（2-吡啶基甲基） -反式-1,2- diaminocyclohexane- Ñ，Ñ ' -二乙酸根）已经通过包括总发光，量热法和圆偏振发光在内的多种技术对复合物进行了研究。由发光滴定法和等温滴定量热法测定的L-乳酸/ [Tb（bpcd）] +缔合常数表明相互作用弱（log K= 1.3–1.45）在分析物与复合物的两个对映体之间。DFT理论计算表明，L-乳酸与[Tb（S，S -bpcd）] +复合物（反式-O，O或反式-N py，N py）的可能立体异构体最可能的配位是羟基。[Tb（rac -bpcd）] +作为L的手性发光探针的结果-乳酸强调了手性1,2-二氨基环己烷（DACH）骨架的特殊作用。实际上，目标阴离子能够在含有基于DACH的配体的Tb络合物的外消旋混合物中诱导CPL活性。对于非手性类似物[Tb（bped）] +（bped = N，N'-双（2-吡啶基甲基）乙二胺-N，N'-二乙酸酯）络合物，未观察到相同的结果，可能是由于烯键的柔性允许不同异构体之间的相互转化，从而产生无效的净CPL活性。由于两种非对映异构物质（R，R）-L和（S，S）-L，可以通过测量诱导的CPL光谱，使用消旋复合物揭示L-乳酸。有趣的是，这已在包含多种电解质（即林格氏乳酸）的医用医疗复杂解决方案中得到证明。
更新日期：2018-01-16
中文翻译：
基于总和圆极化的Tb（iii）发光的手性乳酸盐报告剂†
协调功能和信令大号由乳酸盐离子[TB（bpcd的）] +（bpcd的= Ñ，Ñ ' -双（2-吡啶基甲基） -反式-1,2- diaminocyclohexane- Ñ，Ñ ' -二乙酸根）已经通过包括总发光，量热法和圆偏振发光在内的多种技术对复合物进行了研究。由发光滴定法和等温滴定量热法测定的L-乳酸/ [Tb（bpcd）] +缔合常数表明相互作用弱（log K= 1.3–1.45）在分析物与复合物的两个对映体之间。DFT理论计算表明，L-乳酸与[Tb（S，S -bpcd）] +复合物（反式-O，O或反式-N py，N py）的可能立体异构体最可能的配位是羟基。[Tb（rac -bpcd）] +作为L的手性发光探针的结果-乳酸强调了手性1,2-二氨基环己烷（DACH）骨架的特殊作用。实际上，目标阴离子能够在含有基于DACH的配体的Tb络合物的外消旋混合物中诱导CPL活性。对于非手性类似物[Tb（bped）] +（bped = N，N'-双（2-吡啶基甲基）乙二胺-N，N'-二乙酸酯）络合物，未观察到相同的结果，可能是由于烯键的柔性允许不同异构体之间的相互转化，从而产生无效的净CPL活性。由于两种非对映异构物质（R，R）-L和（S，S）-L，可以通过测量诱导的CPL光谱，使用消旋复合物揭示L-乳酸。有趣的是，这已在包含多种电解质（即林格氏乳酸）的医用医疗复杂解决方案中得到证明。
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