Metal complexes of bicalix[4]arene derivatives and their synthesis methods and applications

A technology of aromatic hydrocarbon derivatives and metal complexes, which is applied in the field of medical biological detection, can solve the problems of unsuitable labeling of biomolecules and low sensitivity, and achieve the effect of simple synthesis process, improved yield and high yield

CN108314690BActive Publication Date: 2019-06-07SUZHOU INST OF BIOMEDICAL ENG & TECH CHINESE ACADEMY OF SCI +1
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Publication Date
2019-06-07

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Abstract

The present invention discloses a metal complex of a biscalix[4]arene derivative, having a chemical structure represented by formula II. The complex has a small toxicity and a high biocompatibility, is suitable for being covalently combined with nucleic acids, peptides, proteins or other biological molecules to form a fluorescent probe molecule having a high fluorescence quantum ratio, a long fluorescence lifetime and a low detection limit, is suitable for biomolecule detection in cells, tissues or living organisms, and has a broad application prospect in the field of biomedicines. The invention discloses a synthesis method of the complex. The method provides multiple selection routes for the synthesis of the complex, and has the advantages of simplicity and easiness in the synthesis routes, high yield in the obtained complex, and suitableness for large-scale production preparation of the complex.
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Description

technical field

[0001] The invention belongs to the technical field of medical biological detection, and specifically relates to a biscalix[4]arene derivative and a metal complex thereof, a synthesis method and an application thereof. Background technique

[0002] Molecular recognition is the process in which the subject (receptor) selectively binds to the guest (substrate) and produces a specific function. The recognition process may cause changes in the magnetic, electrical, optical properties and conformation of the system, resulting in the storage, transmission and processing of chemical information. Therefore, molecular recognition plays an important role in information processing and transmission, and in the fabrication of molecular and supramolecular devices.

[0003] Molecular recognition using the change of magnetic or fluorescent properties caused by the combination of host and guest molecules is the main research direction at present, and has a wide range of appl...

Examples

Embodiment 1

[0067] This embodiment provides a metal complex of a biscalix[4]arene derivative and a preparation method thereof. The biscalix[4]arene derivative has a molecular structure as shown in Formula I-1; the biscalix[4]arene derivative and rare earth metal ions Tb 3+ Coordinate to obtain complex, its molecular structure is as shown in formula II-1:

[0068]

[0069] Intermediate I'-1 was synthesized from intermediate E-1 and intermediate F-1, and intermediate I'-1 was oxidized to obtain biscalix[4]arene derivative I-1, biscalix[4]arene derivative I -1 complex rare earth metal ion Tb 3+ , to obtain biscalix [4] arene derivatives I-1 and Tb 3+ The complex II-1, the synthetic route is:

[0070]

[0071] (1) Preparation of Intermediate E-1

[0072] Step 1: Taking calix[4]arene as reaction raw material, get calix[4]arene (30.0g / 70.7mmol), anhydrous potassium carbonate (10.7g / 77.4mmol) and methyl p-toluenesulfonate (26.3g / 141.4mmol), dissolved in 500mL of CH 3 CN was refluxed...

Embodiment 2

[0100] This example provides a method for synthesizing the metal complex II-1 of biscalix[4]arene derivatives:

[0101] With Intermediate E-1, Intermediate E'-1 (equal to Intermediate E-1) and TsO-CH 2 -CH 2 -OsT synthesizes intermediate I'-1, intermediate I'-1 is oxidized to obtain biscalix[4]arene derivative I-1, biscalix[4]arene derivative I-1 is complexed with rare earth metal ion Tb 3+ , to obtain biscalix [4] arene derivatives I-1 and Tb 3+ The complex II-1, the synthetic route is:

[0102]

[0103] (1) Preparation of Intermediate E-1

[0104] Synthetic process is with the synthesis of the intermediate E-1 of embodiment 1, and intermediate E'-1 and intermediate E-1 are identical compound.

[0105] (2) Preparation of intermediate I'-1

[0106] Intermediate E-1 (0.8mmol), Intermediate E'-1 (1mmol) and K 2 CO 3 (7mmol) was dissolved in toluene, then added TsO-CH 2 -CH 2 -OsT (1.1mmol), under the protection of nitrogen, reflux at a temperature of 110°C for 2h, th...

Embodiment 3

[0112] This embodiment provides a metal complex of a biscalix[4]arene derivative and a preparation method thereof. The biscalix[4]arene derivative has a molecular structure as shown in Formula I-2; the biscalix[4]arene derivative and rare earth metal ions Eu 3+ Cooperate to obtain complex, its molecular structure is as shown in formula II-2:

[0113]

[0114] Synthesize intermediate I'-2 with intermediate E-2 and intermediate F-2 (the intermediate shown in formula F-2 is equivalent to the intermediate shown in formula F-1), after intermediate I'-2 is oxidized Two calix[4] arene derivatives I-2 are obtained, and two calix[4] arene derivatives I-2 are complexed with rare earth metal ions Eu 3+ , to obtain biscalix[4]arene derivative I-2 and Eu 3+ The complex II-2, the synthetic route is:

[0115]

[0116] (1) Preparation of Intermediate E-2

[0117] Step 1: Taking calix[4]arene as the reaction raw material, take calix[4]arene (30.0g / 70.7mmol), anhydrous potassium carbo...