CN110105947B - Synthesis and application of quaternization column [5] arene and 2' 2-biphenyl benzimidazole inclusion complex - Google Patents

Abstract

The invention provides a quaternization column [5]]The complex of arene and 2' 2-biphenyl imidazole is a quaternized column [5]]Aromatic hydrocarbon as main body, 2' 2-biphenyl imidazole as object, in DMSO-H₂The O solution is prepared by self-assembly. DMSO-H in the host-guest inclusion complex₂A series of cations were added to the O solution, only the addition of which quenches the fluorescence of the inclusion complex solution. Adding Fe to the above³⁺、Cu²⁺、Hg²⁺、Ag⁺Adding a series of anions to the CWP5-G solution, wherein CN^‑、HSO₄ ^‑、CN^‑、I^‑Can also make the corresponding CWP5-G-M (M = Fe)³⁺，Cu²⁺，Hg²⁺，Ag⁺) The fluorescence of the solution was recovered. Therefore, the inclusion compound CWP5-G can selectively and continuously identify the anion and cation pairs, which has very important significance in the technical field of ion identification.

Description

Synthesis and application of quaternization column [5] arene and 2' 2-biphenyl benzimidazole inclusion complex

Technical Field

The invention relates to a quaternization column [5] arene and 2', 2-biphenyl benzimidazole inclusion complex, which is mainly used for continuously identifying cations and anions and belongs to the technical field of ion detection.

Background

The benzimidazole compound is used as an N-containing aromatic heterocyclic compound, wherein N atoms in C = N bonds in benzimidazole can be used as hydrogen bond binding sites and can also generate coordination with metal ions; N-H units may also provide hydrogen bonding; and the existence of aromatic rings can provide pi-pi stacking interaction, and the characteristics enable the compound to have important use value in the fields of biomedicine, ionic liquid materials, flame retardants, supramolecular chemistry, coordination chemistry and the like. In recent years, benzimidazole-based fluorescent sensor molecules have been widely used for detecting picric acid, pH, ions, and the like.

Pillar arenes are receiving increasing attention as one of the new generation of supramolecular macrocyclic host compounds due to their ease of synthesis and modification, with the excellent properties of different other macrocyclic compounds. The pillared arene and the derivative thereof have very special spatial structure and physical and chemical properties, and are mainly applied to the fields of host-guest inclusion, molecular recognition, construction of self-assembly systems, intelligent materials and the like.

Disclosure of Invention

The invention aims to provide a quaternization column [5] arene and 2', 2-biphenyl benzimidazole inclusion complex and synthesis thereof;

the invention also aims to provide the application of the inclusion complex in continuously identifying anions and cations.

Mono-quaternization column [5] arene and 2' 2-biphenyl imidazole inclusion complex

The invention quaternization column [5]]The complex of arene and 2' 2-biphenyl imidazole is a quaternized column [5]]Arene (CWP 5) as host and 2' 2-biphenyl imidazole (G) as guest in DMSO-H₂The O solution is formed by self-assembly and is marked as CWP 5-G.

Wherein the structural formula of the quaternary amination column [5] arene is as follows:

see the synthesis method of CWP 5: B. shi, D, Xia and Y, Yao, A water-soluble purified by pilar [5]arene-based molecular recognition. Chem. Commun, 2014, 50, 13932-13935。

The structural formula of 2' 2-biphenylimidazole is as follows:

for the synthesis of G see: P.P. Kattimani, R.Kamble and G.Y. Meti, Expedient synthesis of benzimidazoles using amines RSC adv, 2015, 5, 29447-.

Synthesis of inclusion compound CWP 5-G: to 2' 2-Biphenylimidazoles (G) in DMSO-H₂Adding equimolar quaternization column [5] into O (v/v =1: 1-1: 2) solution]Aromatic hydrocarbons (labeled CWP 5), i.e., host-guest inclusion complexes can be formed.

Second, subject-guest inclusion of CWP5 with G

The subject-object inclusion effect of CWP5 and G was studied by fluorescence titration and nuclear magnetic titration experiments. FIG. 1 is a graph of fluorescence titration of CWP5 against G. As can be seen from FIG. 1, the direction is 2.0X 10^-5G of M (DMSO-H)₂O, v/v =1: 1) solution is added into the CWP5 solution drop by drop, the fluorescence emission intensity of G between 400 nm and 600 nm is gradually increased and finally tends to be stable, and therefore the fact that the CWP5 and G have host-guest interaction is shown. The complexation coefficient of CWP5 with G was calculated to be 9.62X 10 according to the Bensi-Hildebrand equation³M^-1The molar ratio is 1:1 (see figure 2).

FIG. 3 is CWP5 vs G¹H-NMR titrimetric chart. FIG. 3 shows: DMSO + to G-d ₆H on G after addition of CWP5 to the solution₁The proton is split into two peaks, one of which is clearly shifted to the high field, and H₂The proton peak is slightly shifted to low field; h in CWP5_fAnd H_gThe proton peak also undergoes a slight high field shift. This is due to the displacement change caused by the penetration of G into the cavity of CWP5, further demonstrating the host-guest inclusion interaction of CWP5 with G.

Third, CWP5-G ion recognition performance

1. Recognition performance of CWP5-G on metal cations

2mL of the prepared CWP5-G in DMSO-H₂O (v/v =1: 1) solution (2.0 × 10)^-5mol/L) respectively adding Ca²⁺，Mg²⁺，Pb²⁺，Ni²⁺，Co²⁺，Hg²⁺，Zn²⁺，Cd²⁺，Ag⁺，Cu²⁺，Cr³⁺，Al³⁺，Ba²⁺，La³⁺，Eu³⁺，Fe³⁺In an aqueous solution (0.1M), Fe was found³⁺，Cu²⁺，Hg²⁺And Ag⁺Enabling its fluorescence to be quenched (FIG. 4). Gradually adding cation M (M = Fe) by accumulative sample adding method³⁺，Cu²⁺，Hg²⁺，Ag⁺) The fluorescence intensity of CWP5-G at 490 nm was found to decrease gradually until the fluorescence was quenched (FIGS. 5-8). By processing and applying fluorescence titration data 3σThe minimum detection limit range of CWP5-G to ions is calculated to be 10 by the equation of/s^-9~10^-10And mol/L, high sensitivity detection on cations is realized.

2. Continuous identification of anions by CWP5-G

2.0mL of CWP5-G-M in DMSO-H was removed₂O (v/v =1: 1) solution (2.0 × 10)^-5mol/L) to which CN was added^-，I^-，F^-，Cl^-，N₃ ^-，ClO₄ ^-，H₂PO₄ ^-，HSO₄ ^-，SCN^-，Br^-，OH^-，S^2-In an aqueous solution of (2), wherein CN^-、HSO₄ ^-、CN^-、I^-Can also make the corresponding CWP5-G-M (M = Fe)³⁺，Cu²⁺，Hg²⁺，Ag⁺) The fluorescence of the solution was recovered. By processing and applying titration data 3σThe minimum detection limit of the CWP5-G-M on the anions is calculated by the method of/s and reaches 10^-7M。

Under the same conditions, a single 2' 2-biphenyl imidazole (G) is detected after adding Fe³⁺，Cu²⁺，Hg²⁺，Ag⁺And then, the continuous identification property of anions is discovered, and the effect of identifying the anion-cation pairs in a one-to-one correspondence manner is not found.

The above experimental results show that the addition of CWP5 can regulate and control the ion recognition property of G, thereby achieving the specificity and continuity recognition of one-to-one corresponding cation and anion pairs (as shown in FIGS. 9-12, 1-13 respectively show CWP5-G-M, F^-，Cl^-，S^2-，Ac^-，H₂PO₄ ^-，Br^-，N₃ ^-，SCN^-，HSO₄ ^-，ClO₄ ^-，I^-And CN^-）。

Drawings

FIG. 1 is a graph of fluorescence titration of CWP5 against G.

FIG. 2 is a linear plot fitted according to the Bensi-Hildebrand equation.

FIG. 3 is CWP5 vs G¹H-NMR titrimetric chart.

FIG. 4 is a graph of the fluorescence response of CWP5-G to cations.

FIG. 5 is CWP5-G vs Fe³⁺Fluorescence titration graph of (a).

FIG. 6 is a CWP5-G vs Cu²⁺Fluorescence titration graph of (a).

FIG. 7 shows CWP5-G vs Hg²⁺Fluorescence titration graph of (a).

FIG. 8 is CWP5-G vs Ag⁺Fluorescence titration graph of (a).

FIG. 9 shows CWP5-G-Fe³⁺And G-Fe³⁺Fluorescence response plot for anion.

FIG. 10 shows CWP5-G-Cu²⁺And G-Cu²⁺Fluorescence response plot for anion.

FIG. 11 shows CWP5-G-Hg²⁺And G-Hg²⁺Fluorescence response plot for anion.

FIG. 12 shows CWP5-G-Ag⁺And G-Ag⁺Fluorescence response plot for anion.

Detailed Description

The following will further explain the application of the synthesis of the subject-guest inclusion complex CWP5-G in the continuous ion identification of anions and cations by specific examples.

Example 1

Weighing equal molar amounts of CWP5 and G, adding DMSO-H₂Adding O (v/v =1: 1) solution, shaking thoroughly, mixing well to obtain the solution with concentration of 2.0 × 10^-5mol/L CWP5-G solution.

2.0mL of CWP5-G in DMSO-H were removed separately₂O solution (2.0X 10)^-5mol/L) in a series of test tubes, Ca is added respectively²⁺，Mg²⁺，Pb²⁺，Ni²⁺，Co²⁺，Hg²⁺，Zn²⁺，Cd²⁺，Ag⁺，Cu²⁺，Cr³⁺，Al³⁺，Ba²⁺，La³⁺，Eu³⁺，Fe³⁺Aqueous solution (0.1M); if the fluorescence of the CWP5-G solution is quenched, it indicates that Fe is added³⁺、Cu²⁺、Hg²⁺Or Ag⁺。

Example 2

2.0mL of CWP5-G in DMSO-H were removed separately₂O (v/v =1: 1) solution (2.0 × 10)^-5mol/L) in a series of test tubes, Fe is added respectively³⁺The fluorescence of the CWP5-G solution was quenched in an aqueous solution (0.1M); respectively adding CN into the solution^-，I^-，F^-，Cl^-，N₃ ^-，ClO₄ ^-，H₂PO₄ ^-，HSO₄ ^-，SCN^-，Br^-，OH^-，S^2-An aqueous solution of (a); if CWP5-G-Fe³⁺The fluorescence emission of the solution is recovered, indicating that CN was added^-. Thus, CWP5-G vs Fe is realized³⁺- CN^-Specific and continuous identification.

Example 3

2.0mL of CWP5-G in DMSO-H were removed separately₂O (v/v =1: 1) solution (2.0 × 10)^-5mol/L) in a series of test tubes, Cu is added respectively²⁺The fluorescence of the CWP5-G solution was quenched in an aqueous solution (0.1M); respectively adding CN into the solution^-，I^-，F^-，Cl^-，N₃ ^-，ClO₄ ^-，H₂PO₄ ^-，HSO₄ ^-，SCN^-，Br^-，OH^-，S^2-An aqueous solution of (a); if CWP5-G-Cu²⁺The fluorescence emission of the solution is recovered, indicating that HSO is added₄ ^-。

Example 4

2.0mL of CWP5-G in DMSO-H were removed separately₂O (v/v =1: 1) solution (2.0 × 10)^-5mol/L) in a series of test tubes, adding into each tubeHg²⁺The fluorescence of the CWP5-G solution was quenched in an aqueous solution (0.1M); respectively adding CN into the solution^-，I^-，F^-，Cl^-，N₃ ^-，ClO₄ ^-，H₂PO₄ ^-，HSO₄ ^-，SCN^-，Br^-，OH^-，S^2-An aqueous solution of (a); if CWP5-G-Hg²⁺The fluorescence emission of the solution is recovered, indicating that CN was added^-. Therefore, CWP5-G is realized to Hg²⁺- CN^-Specific and continuous identification.

Example 5

2.0mL of CWP5-G in DMSO-H were removed separately₂O (v/v =1: 1) solution (2.0 × 10)^-5mol/L) in a series of test tubes, adding Ag respectively⁺The fluorescence of the CWP5-G solution was quenched in an aqueous solution (0.1M); respectively adding CN into the solution^-，I^-，F^-，Cl^-，N₃ ^-，ClO₄ ^-，H₂PO₄ ^-，HSO₄ ^-，SCN^-，Br^-，OH^-，S^2-An aqueous solution of (a); if CWP5-G-Ag⁺The fluorescence emission of the solution is recovered, indicating that I is added^-. Thus, CWP5-G vs Ag is realized⁺- I^-Specific and continuous identification.

Claims (5)

1. Quaternary amination column [5]The application of the inclusion complex of aromatic hydrocarbon and 2' 2-biphenyl benzimidazole in identifying cations is characterized in that: in a series of quaternization columns [5]]DMSO-H of inclusion complex of aromatic hydrocarbon and 2' 2-biphenyl benzimidazole₂Adding Ca into O solution²⁺，Mg²⁺，Pb²⁺，Ni²⁺，Co²⁺，Hg²⁺，Zn²⁺，Cd²⁺，Ag⁺，Cu²⁺，Cr³⁺，Al³⁺，Ba²⁺，La³⁺，Eu³⁺，Fe³⁺In an aqueous solution of (2), Fe was found³⁺，Cu²⁺，Hg²⁺And Ag⁺Quenching the fluorescence;

the quaternization column [5]]The complex of arene and 2' 2-biphenyl imidazole is a quaternized column [5]]Aromatic hydrocarbon as main body, 2' 2-biphenyl imidazole as object, in DMSO-H₂An inclusion complex formed by self-assembly in an equimolar amount in O solution, wherein the column [5] is quaternized]The structural formula of the aromatic hydrocarbon is as follows:

the structural formula of 2' 2-biphenylimidazole is as follows:

DMSO-H₂in O, DMSO and H₂The volume ratio of O is 1: 1-1: 2.

2. Quaternary amination column [5]The application of the inclusion complex of aromatic hydrocarbon and 2' 2-biphenyl benzimidazole in identifying anions is characterized in that: in a series of quaternization columns [5]]DMSO-H of inclusion complex of aromatic hydrocarbon and 2' 2-biphenyl benzimidazole₂Adding Fe into O solution³⁺The fluorescence of the solution is quenched; respectively adding CN into the solution^-，I^-，F^-，Cl^-，N₃ ^-，ClO₄ ^-，H₂PO₄ ^-，HSO₄ ^-，SCN^-，Br^-，OH^-，S^2-An aqueous solution of (a); if the fluorescence emission of the solution is recovered, this indicates that CN was added^-；

The quaternization column [5]]The complex of arene and 2' 2-biphenyl imidazole is a quaternized column [5]]Aromatic hydrocarbon as main body, 2' 2-biphenyl imidazole as object, in DMSO-H₂An inclusion complex formed by self-assembly in an equimolar amount in O solution, wherein the column [5] is quaternized]The structural formula of the aromatic hydrocarbon is as follows:

the structural formula of 2' 2-biphenylimidazole is as follows:

DMSO-H₂in O, DMSO and H₂The volume ratio of O is 1: 1-1: 2.

3. Quaternary amination column [5]The application of the inclusion complex of aromatic hydrocarbon and 2' 2-biphenyl benzimidazole in identifying anions is characterized in that: in a series of quaternization columns [5]]DMSO-H of inclusion complex of aromatic hydrocarbon and 2' 2-biphenyl benzimidazole₂Adding Cu into O solution respectively²⁺The fluorescence of the solution is quenched; respectively adding CN into the solution^-，I^-，F^-，Cl^-，N₃ ^-，ClO₄ ^-，H₂PO₄ ^-，HSO₄ ^-，SCN^-，Br^-，OH^-，S^2-An aqueous solution of (a); if the fluorescence emission of the solution is recovered, it indicates that HSO is added₄ ^-；

The quaternization column [5]]The complex of arene and 2' 2-biphenyl imidazole is a quaternized column [5]]Aromatic hydrocarbon as main body, 2' 2-biphenyl imidazole as object, in DMSO-H₂An inclusion complex formed by self-assembly in an equimolar amount in O solution, wherein the column [5] is quaternized]The structural formula of the aromatic hydrocarbon is as follows:

the structural formula of 2' 2-biphenylimidazole is as follows:

DMSO-H₂in O, DMSO and H₂The volume ratio of O is 1: 1-1: 2.

4. Quaternary amination column [5]The application of the inclusion complex of aromatic hydrocarbon and 2' 2-biphenyl benzimidazole in continuously identifying anions is characterized in that: in a series of quaternization columns [5]]DMSO-H of inclusion complex of aromatic hydrocarbon and 2' 2-biphenyl benzimidazole₂Adding Hg into O solution²⁺The fluorescence of the solution is quenched; respectively adding CN into the solution^-，I^-，F^-，Cl^-，N₃ ^-，ClO₄ ^-，H₂PO₄ ^-，HSO₄ ^-，SCN^-，Br^-，OH^-，S^2-An aqueous solution of (a); if the fluorescence emission of the solution is recovered, this indicates that CN was added^-；

The quaternization column [5]]The complex of arene and 2' 2-biphenyl imidazole is a quaternized column [5]]Aromatic hydrocarbon as main body, 2' 2-biphenyl imidazole as object, in DMSO-H₂An inclusion complex formed by self-assembly in an equimolar amount in O solution, wherein the column [5] is quaternized]The structural formula of the aromatic hydrocarbon is as follows:

the structural formula of 2' 2-biphenylimidazole is as follows:

DMSO-H₂in O, DMSO and H₂The volume ratio of O is 1: 1-1: 2.

5. Quaternary amination column [5]The application of the inclusion complex of aromatic hydrocarbon and 2' 2-biphenyl benzimidazole in continuously identifying anions is characterized in that: in a series of quaternization columns [5]]DMSO-H of inclusion complex of aromatic hydrocarbon and 2' 2-biphenyl benzimidazole₂Adding Ag into the O solution respectively⁺Aqueous solution of (1), solutionQuenching the fluorescence of (a); respectively adding CN into the solution^-，I^-，F^-，Cl^-，N₃ ^-，ClO₄ ^-，H₂PO₄ ^-，HSO₄ ^-，SCN^-，Br^-，OH^-，S^2-An aqueous solution of (a); if the fluorescence emission of the solution is recovered, it is indicated that I is added^-；

The quaternization column [5]]The complex of arene and 2' 2-biphenyl imidazole is a quaternized column [5]]Aromatic hydrocarbon as main body, 2' 2-biphenyl imidazole as object, in DMSO-H₂An inclusion complex formed by self-assembly in an equimolar amount in O solution, wherein the column [5] is quaternized]The structural formula of the aromatic hydrocarbon is as follows:

the structural formula of 2' 2-biphenylimidazole is as follows:

DMSO-H₂in O, DMSO and H₂The volume ratio of O is 1: 1-1: 2.

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