阅读说明：本技术 用于e-ab传感器中具有抗污染特性分子的合成方法 (Synthesis method of molecules with anti-pollution property for E-AB sensor ) 是由 李辉 王园园 张子硕 梅子吟 李少光 夏帆 于 2020-12-29 设计创作，主要内容包括：本发明公开了一种用于E-AB传感器中具有抗污染特性分子的合成方法,包括以下步骤：取棕色试剂瓶,加入如式(1)所示的化合物,再加入去除氧气的氯仿溶液,橡胶塞密封,磁力搅拌,补加去除氧气的氯仿溶液继续搅拌0.5h,再向棕色试剂瓶中加入1,6-己二硫醇和2,6-二异丙基苯胺,搅拌8～12h后,倒入装有第一体积丙酮的离心管中,析出,混匀,离心,去除丙酮,干燥离心管中的物质,得有机硫醇类物质。本发明用于E-AB传感器中的分子合成路线较为简单,并且产量较高,且修饰的E-AB传感器在血液中具有较好的稳定性。(The invention discloses a method for synthesizing a molecule with an anti-pollution characteristic used in an E-AB sensor, which comprises the following steps: adding a compound shown as a formula (1) into a brown reagent bottle, adding an oxygen-removed chloroform solution, sealing a rubber plug, carrying out magnetic stirring, adding the oxygen-removed chloroform solution, continuously stirring for 0.5h, adding 1, 6-hexanedithiol and 2, 6-diisopropylaniline into the brown reagent bottle, stirring for 8-12 h, pouring into a centrifugal tube filled with a first volume of acetone, separating out, mixing uniformly, centrifuging, removing acetone, and drying substances in the centrifugal tube to obtain the organic thiol substance. The molecular synthesis route of the invention used in the E-AB sensor is simpler, the yield is higher, and the modified E-AB sensor has better stability in blood.)

1. The method for synthesizing the molecules with the anti-pollution property for the E-AB sensor is characterized by comprising the following steps of: adding a compound shown as a formula (1) into a brown reagent bottle, adding an oxygen-removed chloroform solution, sealing a rubber plug, carrying out magnetic stirring, adding the oxygen-removed chloroform solution, continuously stirring for 0.5h, adding 1, 6-hexanedithiol and 2, 6-diisopropylaniline into the brown reagent bottle, stirring for 8-12 h, pouring into a centrifugal tube filled with a first volume of acetone, separating out, mixing uniformly, centrifuging, removing acetone, and drying substances in the centrifugal tube to obtain an organic mercaptan substance; represented by formula (1)The structural formula of the compound is shown as follows:

2. the method of claim 1, wherein the molar ratio of the compound of formula (1) to the 1, 6-hexanedithiol is 2: 3.

3. A method of synthesising a molecule having anti-fouling properties for use in an E-AB sensor as claimed in claim 1 wherein the chloroform solution depleted of oxygen is obtained by: filling the chloroform solution into a container, sealing the container by using a rubber plug, penetrating a long needle through the rubber plug to stretch into the chloroform solution below the liquid level for air blowing, and balancing the internal and external pressures of the container while air blowing.

4. The method of claim 1, wherein the volume ratio of the chloroform solution with oxygen removed to the acetone in the centrifuge tube is 1: 6.

5. A method of synthesising a molecule having anti-fouling properties for use in an E-AB sensor as claimed in claim 1 wherein the centrifugation is carried out at 8000 rpm for a period of 15min and at a temperature of 4 ℃.

6. The method of claim 1, wherein the centrifugation is performed in three steps, wherein after the first centrifugation step, acetone is removed, one third of the acetone in the centrifuge tube is added to the first volume of acetone for a second centrifugation step, after the second centrifugation step, acetone is removed, and one third of the acetone in the centrifuge tube is added to the first volume of acetone for a third centrifugation step.

7. A method for synthesizing molecules with anti-pollution property for use in an E-AB sensor as claimed in any one of claims 1 to 6, wherein a brown reagent bottle is sleeved with a balloon for pressure equalization during magnetic stirring.

Technical Field

The invention relates to the technical field of molecular synthesis. More particularly, the invention relates to a method for synthesizing a molecule with anti-pollution property for an E-AB sensor.

Background

In recent years, self-assembled monolayers (SAMs) have been widely used, and have achieved certain achievements mainly in the fields of metal protection, nano-films, surface modification, biomedicine, pH measurement, electrochemical analysis, molecular immobilization, catalysts, and drug delivery. SAMs provide a simple approach to electrode surface functionalization. The characteristics of uniformity, high order and flexible change of the terminal group functional group enable the monomolecular film to provide a good microenvironment for biomolecule immobilization, and have great significance for development and application of biosensors.

Depending on the head group functionality of the self-assembled molecule, these self-assembled film systems can be broadly classified as: organosilanes SAMs, organophosphorous SAMs, organosulfur alcohols SAMs, fatty acids SAMs and other SAMs. At present, the synthesis of organic sulfur alcohol substances can be mainly divided into a method for synthesizing mercaptan by alcohol, a method for synthesizing mercaptan by halogenated hydrocarbon and a novel method for synthesizing mercaptan. Lihua and the like improve the mercaptan technology, the mode reduces the energy consumption of salt forming reaction, reduces the treatment amount of hydrolysis reaction, does not need organic solvent, is simpler and more convenient to separate and purify, but does not improve the defects of more three wastes, long route, corrosivity and the like obviously existing in the technology, and the yield of mercaptan is low.

Disclosure of Invention

An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.

It is a further object of the present invention to provide a method for synthesizing molecules with anti-fouling properties for use in E-AB sensors, which has a short route, high yield, and good electrochemical stability.

To achieve these objects and other advantages in accordance with the purpose of the invention, there is provided a method for synthesizing a molecule having anti-contamination property for use in an E-AB sensor, comprising the steps of: taking a brown reagent bottle, adding a compound shown as a formula (1), and then addingRemoving the chloroform solution of oxygen, sealing the rubber plug, magnetically stirring, supplementing the chloroform solution of oxygen, continuously stirring for 0.5h, adding 1, 6-hexanedithiol and 2, 6-diisopropylaniline into the brown reagent bottle, stirring for 8-12 h, pouring into a centrifuge tube filled with a first volume of acetone, separating out, uniformly mixing, centrifuging, removing acetone, and drying substances in the centrifuge tube to obtain the organic mercaptan substances; the structural formula of the compound represented by the formula (1) is as follows:

preferably, the molar ratio of the compound represented by the formula (1) to the 1, 6-hexanedithiol is 2: 3.

Preferably, the chloroform solution from which oxygen is removed is obtained by the following method: filling the chloroform solution into a container, sealing the container by using a rubber plug, penetrating a long needle through the rubber plug to stretch into the chloroform solution below the liquid level for air blowing, and balancing the internal and external pressures of the container while air blowing.

Preferably, the volume ratio of the oxygen-depleted chloroform solution to acetone in the centrifuge tube is 1: 6.

Preferably, the rotation speed of the centrifugation is 8000r/min, the time is 15min and the temperature is 4 ℃.

Preferably, the centrifugation is performed in three steps, after the first centrifugation is completed, acetone is removed, acetone of one third of the volume of the first centrifugation is added into the centrifuge tube for the second centrifugation, after the second centrifugation is completed, acetone is removed, and acetone of one third of the volume of the first centrifugation is added into the centrifuge tube for the third centrifugation.

Preferably, during magnetic stirring, a balloon is placed over the brown reagent bottle to equalize pressure.

The invention at least comprises the following beneficial effects: the molecular synthesis route of the self-assembled membrane is simple, the yield is high, and the modified E-AB sensor has good stability in blood.

Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.

Drawings

FIG. 1 is a mass spectrum of an organosulfur alcohol substance according to embodiment 2 of the invention;

FIG. 2 is a mass spectrum of an organosulfur alcohol substance according to embodiment 3 of the invention;

FIG. 3 is a mass spectrum of an organosulfur alcohol substance according to embodiment 4 of the invention;

FIG. 4 is a mass spectrum of an organosulfur alcohol substance according to embodiment 5 of the invention;

FIG. 5 shows the stability test of the electrochemical performance of the modified E-AB sensor in embodiments 2-5 of the present invention.

Detailed Description

The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.

It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.

< example 1>

The method for obtaining the chloroform solution for removing the oxygen comprises the following steps: the method comprises the steps of filling 25mL of chloroform solution into a 50mL round-bottom flask, sealing the container by using a rubber plug, then penetrating a long needle through the rubber plug to be blown below the liquid level of the chloroform solution for 10min, wherein the blown gas is argon, and inserting a short needle head which does not extend below the liquid level of the chloroform solution while blowing the gas to balance the internal pressure and the external pressure of the container.

< example 2>

Synthesis method of molecules with anti-pollution property for E-AB sensor

Taking a brown reagent bottle, putting a magneton, adding 2.5mmol of a compound shown as a formula (1) into the brown reagent bottle, adding 5mL of chloroform solution without oxygen, sealing the brown reagent bottle by using a rubber plug, magnetically stirring, installing a balloon for balancing pressure during stirring, supplementing 2-3 mL of chloroform solution without oxygen, continuously stirring for 0.5h, adding 0.6mL of 1, 6-hexanedithiol and 50mL of 2, 6-diisopropylaniline into the brown reagent bottle, stirring for 8-12 h, pouring into a 50mL centrifuge tube filled with 30mL of acetone, separating out flocculent white precipitate, uniformly mixing, centrifuging by using a centrifuge again for three times, removing the acetone after the first centrifugation is finished, adding 10mL of acetone into the centrifuge tube for second centrifugation, removing the acetone after the second centrifugation is finished, adding 10mL of acetone into the centrifuge tube for third centrifugation, removing acetone, transferring into 14mL centrifuge tube, sealing the tube opening with sealing film, plugging hole with needle, drying the substance in the centrifuge tube with freeze dryer to obtain organic thiols substance, and storing in-20 deg.C refrigerator; the rotation speed of centrifugation is 8000r/min, the time is 15min, and the temperature is 4 ℃; the synthetic substance is AP for short, and the yield of the main component is 34 percent; the calculated molecular weight of the principal component is 381, the mass spectrum of the synthesized material is shown in FIG. 1, and the molecular weight of the principal component is 380.12.

The structural formula of the compound shown as the formula (1) is

The main component of the synthetic substance is

< example 3>

Synthesis method of molecules with anti-pollution property for E-AB sensor

Taking a brown reagent bottle, placing a magneton, adding 2.5mmol of a compound shown as a formula (1) into the brown reagent bottle, adding 5mL of chloroform solution without oxygen, sealing the brown reagent bottle by using a rubber plug, magnetically stirring, installing a balloon for balancing pressure during stirring, supplementing 2-3 mL of chloroform solution without oxygen, continuously stirring for 0.5h, adding 0.6mL of 1, 6-hexanedithiol and 50mL of 2, 6-diisopropylaniline into the brown reagent bottle, stirring for 8-12 h, pouring into a 50mL centrifuge tube filled with 30mL of acetone, layering liquid, uniformly mixing, centrifuging by using a centrifuge, wherein the lower layer is a product layer, centrifuging for three times, removing acetone after the first centrifugation is finished, adding 10mL of acetone into the centrifuge tube for second centrifugation, removing acetone after the second centrifugation is finished, adding 10mL of acetone into the centrifuge tube for third centrifugation, removing acetone, transferring into 14mL centrifuge tube, sealing the tube opening with sealing film, plugging hole with needle, drying the substance in the centrifuge tube with freeze dryer to obtain organic thiols substance, and storing in-20 deg.C refrigerator; the rotation speed of centrifugation is 8000r/min, the time is 15min, and the temperature is 4 ℃; the synthetic substance is abbreviated as PC, and the yield of the main component is 80 percent; as the product is viscous liquid, the mass spectrum comprises other miscellaneous peaks, the mass spectrum is shown in figure 2, and the molecular weight of the main component is 446.18.

The structural formula of the compound shown as the formula (1) is

The main component of the synthetic substance is

< example 4>

Synthesis method of molecules with anti-pollution property for E-AB sensor

Taking a brown reagent bottle, placing a magneton, adding 2.5mmol of a compound shown as a formula (1) into the brown reagent bottle, adding 5mL of chloroform solution without oxygen, sealing the brown reagent bottle by using a rubber plug, magnetically stirring, installing a balloon for balancing pressure during stirring, supplementing 2-3 mL of chloroform solution without oxygen, continuously stirring for 0.5h, adding 0.6mL of 1, 6-hexanedithiol and 50mL of 2, 6-diisopropylaniline into the brown reagent bottle, stirring for 8-12 h, pouring into a 50mL centrifuge tube filled with 30mL of acetone, separating out oily precipitate, uniformly mixing, centrifuging for three times by using a centrifuge, placing the centrifuged product at the lower layer, removing the acetone after the first centrifugation, adding 10mL of acetone into the centrifuge tube for the second centrifugation, removing the acetone after the second centrifugation, adding 10mL of acetone into the centrifuge tube for the third centrifugation, removing acetone, transferring into 14mL centrifuge tube, sealing the tube opening with sealing film, plugging hole with needle, drying the substance in the centrifuge tube with freeze dryer to obtain organic thiols substance, and storing in-20 deg.C refrigerator; the rotation speed of centrifugation is 8000r/min, the time is 15min, and the temperature is 4 ℃; the yield of the main component of the synthetic substance is 69.4 percent, the mass spectrum of the synthetic substance is shown in figure 3, and the molecular weight of the main component is 322.18;

the structural formula of the compound shown as the formula (1) is

The main component of the synthetic substance is

< example 5>

Synthesis method of molecules with anti-pollution property for E-AB sensor

Taking a brown reagent bottle, putting a magneton, adding 2.5mmol of a compound shown as a formula (1) into the brown reagent bottle, adding 5mL of chloroform solution without oxygen, sealing the brown reagent bottle by using a rubber plug, magnetically stirring, installing a balloon for balancing pressure during stirring, supplementing 2-3 mL of chloroform solution without oxygen, continuously stirring for 0.5h, adding 0.6mL of 1, 6-hexanedithiol and 50mL of 2, 6-diisopropylaniline into the brown reagent bottle, stirring for 8-12 h, pouring into a 50mL centrifuge tube filled with 30mL of acetone, separating out flocculent white precipitate, uniformly mixing, centrifuging by using a centrifuge again for three times, removing the acetone after the first centrifugation is finished, adding 10mL of acetone into the centrifuge tube for second centrifugation, removing the acetone after the second centrifugation is finished, adding 10mL of acetone into the centrifuge tube for third centrifugation, removing acetone, transferring into 14mL centrifuge tube, sealing the tube opening with sealing film, plugging hole with needle, drying the substance in the centrifuge tube with freeze dryer to obtain organic thiols substance, and storing in-20 deg.C refrigerator; the rotation speed of centrifugation is 8000r/min, the time is 15min, and the temperature is 4 ℃; the yield of the main component of the synthetic substance is 58.81% in SP for short, the mass spectrum of the synthetic substance is shown in FIG. 4, and the molecular weight of the main component is 357.09;

the structural formula of the compound shown as the formula (1) is

The main component of the synthetic substance is

< electrochemical stability test >

Selecting the product of the embodiment 2-5 to modify the E-AB sensor, carrying out electrochemical stability test on the modified E-AB sensor, after testing for 1h by using 1 XPBS buffer solution, replacing the 1 XPPBS buffer solution with blood with the same amount, and continuously carrying out stability test for more than 12 h; the results are shown in figure 5 and it can be seen that the products of examples 2, 3, 5 are reproducible in the blood test and have remained substantially stable at 5h, the product of example 4 is reproducible in the blood test and has remained substantially stable at 8 h.

While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the embodiments shown and described without departing from the generic concept as defined by the claims and their equivalents.