CN116376041A - Preparation and application of controllable homochiral supermolecule assembly based on hydrotalcite finite field effect - Google Patents

Preparation and application of controllable homochiral supermolecule assembly based on hydrotalcite finite field effect Download PDF

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CN116376041A
CN116376041A CN202310308555.1A CN202310308555A CN116376041A CN 116376041 A CN116376041 A CN 116376041A CN 202310308555 A CN202310308555 A CN 202310308555A CN 116376041 A CN116376041 A CN 116376041A
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史文颖
梁开香
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Beijing University of Chemical Technology
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Abstract

The invention discloses a novel technology for inducing planar achiral molecules to form and determine chiral HSA and application thereof. According to the method, planar achiral N, N-dipropionic acid-Perylene Diimide (PDI) is taken as a model molecule, and the space asymmetric structure of a PDI molecular array between layers is researched. After the LDH laminate is removed, the asymmetric structure is in a thermodynamic non-equilibrium state, and is amplified to HSA by using a finite field assisted active growth technology. The chirality of HSA is controllable and predictable. Analysis resulted in suitable candidate molecules with the following characteristics for the preparation of controllable HSA: the number of the molecular center plane rings is more than 3; these molecules can form large and ordered arrays. Therefore, the scheme breaks the bottleneck of complex molecular design and has certain universality. Thanks to the properties of HSA (amplification of the built-in electric field), HSA herein exhibits excellent photoelectric properties (HSA photoelectric signal is 5 times that of a common PDI assembly), which will provide new possibilities for applications of such materials in the fields of photoelectric devices, chiral recognition and biosensing.

Description

Preparation and application of controllable homochiral supermolecule assembly based on hydrotalcite finite field effect
Technical Field
The invention belongs to the technical field of chiral supermolecule assembly. In particular to a controllable homochiral supermolecule assembly formed by inducing planar achiral molecules by utilizing the domain-limited effect of hydrotalcite nano materials under vortex motion.
Background
The chirality is a sign of life and the origin is still a puzzle. To solve this puzzle, a strong effort is made to assemble achiral supramolecules (HSA) of achiral molecular composition, as it can provide useful insight for understanding natural achiral properties. However, artificial HSA systems remain very difficult in achiral monomer design. Some surprising findings clearly indicate that achiral monomers must be non-planar twisted pi conjugated systems or have a side chain structure with aliphatic chirality to form HSA. Obtaining these specific structures inevitably increases the complexity of the molecular design and cost. Thus, the common commercially available planar molecules appear to be the most desirable choice as HSA monomers. However, this design approach is rarely implemented, as assemblies made from such molecules typically do not have CD signals. In other words, lack of a twisted stack driving force may not induce the occurrence of symmetry breaking and the formation of HSA. To address this troublesome problem, it is a good idea to introduce non-centrosymmetric surfaces from a two-dimensional (2D) host material to induce the formation of ordered arrays of guest monomers. In particular, the synergistic interaction of molecules and interactions of molecules with surfaces may force molecules to form a staggered bilayer array. This predicts the likelihood that adjacent arrays with different spatial positions may interact to form structurally asymmetric units (chiral units). However, due to the achiral nature of the host material, such chiral units cannot grow into HSA by direct imprinting of 2D structures. Thus, the 2D host material selected needs to be easy to remove and have an alternative mechanism to facilitate the amplification of chiral units to HSA.
Chiral selection is a long standing challenge for most HSA examples based on symmetry breaking. The reason is that the left and right hand are mirror image enantiomer assemblies, with the same energy, which results in different batches of HSA being random in the thermodynamic control system. In various approaches, swirling motion (macroscopic chiral factor) has proven effective in amplifying chiral deviations in symmetry breaking systems. However, the swirling motion alone is insufficient to induce a deviation in HSA made of small molecules in the liquid phase. Because small molecules hardly feel the hydrodynamic forces beyond the shear force part of the brownian motion of the solvent. Thus, an array (aggregation) of molecules with a larger size (> 10 nm) should be formed. At the same time, an energy trap is required to stabilize the molecular array selected from vortex chirality.
Disclosure of Invention
In this work, we achieved a partial symmetry break in a planar achiral system by forming a two-dimensional intercalated Layered Double Hydroxide (LDH) nanomaterial in a swirling motion, which was amplified to chiral controllable HSA by a limited-domain assisted active growth technique.
A second object of the present invention is to provide the use of HSA materials prepared using said method in the photovoltaic field.
The method for realizing the partial symmetry breaking of a planar achiral system and determining the formation of chiral HSA by utilizing the formation of two-dimensional host-guest nano materials (intercalation layered double hydroxide, LDH) in vortex motion comprises the following steps:
a. preparation of intercalation molecule PDI: PDI is a planar achiral monomer that possesses a perylene ring with hydrogen bonds (carboxyl groups). This structure provides the possibility of pi-pi stacking and hydrogen bonding assembly through the perylene plane.
b. Synthesis of intercalated hydrotalcite (PDI-LDH): the co-precipitation process for preparing PDI-LDH is in fact a vortex-guided self-assembly process. The space asymmetric structure is formed by multistage assembly of LDHs, while the laminate and the two-dimensional constrained space serve as energy traps to stabilize the existence of the asymmetric structure.
Preparation of HSA: propionic acid/CH is added into prepared PDI-LDHs (3.00-3.50 mg) by utilizing two-dimensional domain-limited space of LDHs 3 The release of ordered PDI units is defined as active units by the mixture solvent of OH (1:3 v/v). The active units (4.00-4.50 mM) were then sonicated to expose more active sites. After a period of standing of the active units (4.00-4.50 mM), the corresponding energy favorable state of stable HSA is achieved. During the ultrasonic treatment, a mixture of ice and water was used to maintain the temperature at 0 ℃.
After removal of LDH by addition of propionic acid solvent, the active units are amplified to HSA by active growth techniques.
d. Preparation of seed-induced active supramolecular assemblies (SSP): SSP is prepared by mixing active seed (4.00-4.50 mM) with PDI agg (2.50-3.00 mM) in equal volumes (1:1 v/v) followed by sonication for a period of time. Here, the active seed is a freshly released active unit that is sonicated. PDI (PDI) agg Is PDI molecule in propionic acid/CH 3 Fresh stock solution in OH (1:3 v/v). During the sonication, the temperature was maintained at 0 ℃ using a mixture of ice and water.
By mixing equal volumes of active units (4.00-4.50 mM) and PDI agg (2.50-3.00 mM) ultrasonic mixing for a period of time to produce cycle1 product, the resulting product is referred to as SSPcycle1. The products in cycle2 and cycle3 are obtained by reacting PDI agg (2.50-3.00 mM) was further added to the product of the previous cycle (1:1 v/v) to repeat SSP to give the product, which was in turn called SSPcycle2, SSAcycle3. During the sonication, the temperature was maintained at 0 ℃ using a mixture of ice and water.
To demonstrate that HSA is "live", HSA growth from the active end should be demonstrated by a multicycle experiment.
The invention also provides an application of the HSA material prepared by the method in the photoelectric field, and the method comprises the following steps:
treatment of ITO
Firstly, washing the ITO glass three times by using a detergent, water and ethanol respectively, and carrying out ultrasonic treatment for 15-20min each time. Then at N 2 Blow-drying in atmosphere for subsequent electrochemical working electrode testing.
Preparation of HSA modified ITO electrode
Before using the ITO electrode, the conductive surface of the ITO electrode needs to be tested with a universal meter.
4.0-4.5mM metastable HSA was coated onto a clean ITO conductive surface by spin coating at 4000-5000rpm, which was continued for 60-70 seconds, followed by standing for a period of time to obtain a supramolecular assembly that grew on the electrode.
c. Electrolyte solution Na 2 SO 4 Preparation of the solution
Configuration of 0.500M Na 2 SO 4 A solution. 3.551g of Na is weighed 2 SO 4 Adding 50mL deionized water into the powder, and completely dissolving by ultrasonic treatment to obtain Na 2 SO 4 A solution.
d. Electrochemical testing
Photoelectrochemical testing on a CHI660E electrochemical workstation using platinum with working electrode (HSA modified ITO electrode)Standard three electrode system of wire counter electrode and saturated calomel reference electrode. The electrolyte solution was 0.500M Na 2 SO 4 A solution. The photoelectric test was carried out using a xenon lamp > 420nm under no bias.
The beneficial effects are that: the invention realizes the partial symmetry break in a plane achiral system by forming two-dimensional intercalated Layered Double Hydroxide (LDH) nano material in vortex motion, and can be amplified into chiral controllable HSA [25] by the prior domain-limited auxiliary activity growth technology. From the formation mechanism, the synthesis process of intercalated LDHs is a layered assembly with swirling motion. In primary assembly, positive charges uniformly distributed on the LDH layer can induce the formation of ordered arrays of negatively charged monomers (PDI, N-dipropionic acid-perylene diimide). The size of the LDH can be tuned on the nano-micrometer scale, which means that the size of the PDI array is sufficient to imprint the vortex trajectories, which is a key factor for vortex guided HSA. In secondary assembly, strong pi-pi and hydrogen bond interactions between ordered PDI arrays drive the formation of 2D intercalation structures in which alternating PDI bilayers are immobilized on the upper and lower surfaces of the LDH, respectively. Thus, upon removal of the LDH template, adjacent arrays form a spatially asymmetric structure (chiral unit) which can be amplified to HSA by active growth (tertiary assembly). Since LDH overcomes a huge obstacle as an energy trap, the chiral unit is kept in a thermodynamically non-equilibrium state. The handedness of HSA is controllable and predictable. For example, the percentage of left-handed helix HSA under CW rotation is 90% (n=30), and the percentage of right-handed helix HSA under ACW rotation is 87% (n=30). As the Internal Electric Field (IEF) of the PDI molecule gradually amplifies, the photocurrent of PDI HSA is 5 times that of the common PDI assembly.
Description of the drawings:
fig. 1 is a schematic diagram of the process of intercalated LDH formation, i.e. the primary and secondary assembly, under the conditions of example 1 of the present invention. The co-precipitation process for preparing PDI-LDH is in fact a vortex-guided self-assembly process.
FIG. 2 shows fluorescence anisotropy spectra of PDI powder and PDI-LDH under the condition of example 1 of the present invention. Fluorescence (FL) polarization spectra confirmed that the anisotropy value of PDI-LDH (r=1.012) was higher than that of PDI powder (r=0.018).
FIG. 3 is a graph showing Mg under the condition of example 1 of the present invention 3 XRD structures of Al-LDH and PDI-LDH. Hydrotalcite was a typical two-dimensional (2D) layered structure, confirmed by powder X-ray diffraction (XRD). The PDI-LDH and the Mg3Al-LDH are consistent, namely, the intervals between the (003) crystal faces and the (006) crystal faces have good multiple relation, the intensity of diffraction peaks is gradually reduced, and the characteristic diffraction peaks of the (110) crystal faces are clearly visible, so that the formation of a PDI-LDH lamellar structure is well illustrated. XRD results also demonstrate that the interlayer spacing d (2.602 nm) is greater than the long axis of the molecule (2.359 nm). Thus, adjacent molecules tend to form spatially asymmetric structures, which provides a prerequisite for the formation of HSA by chiral stacking.
FIG. 4 shows the UV spectra of (a) PDI and PDI-LDH and (b) PDI and PDI-LDH under the conditions of example 1 of the present invention. With PDI solution (. Lambda. abs ＝525nm，λ em =580 nm), PDI-LDH shows blue-shifted uv (λ abs =460 nm) and red-shifted fluorescence (λ em =650 nm). Such a significant wavelength shift suggests that the energy traps greatly enhance pi-pi stacking interactions between the PDI arrays in the PDI-LDH. The oriented PDI molecular array in PDI-LDH is in a thermodynamically non-equilibrium state (metastable state) and stably exists between hydrotalcite layers.
FIG. 5 is a CD spectrum of PDI and PDI HSA under the conditions of example 1 of the present invention. Chiral units can continue to grow to HSA, as evidenced by an increase in time-dependent CD spectral intensity at 550nm over time. In contrast, because PDI is achiral at the molecular level, PDI solutions show a loss of CD signal.
FIG. 6 shows the temperature dependent absorption of active units prepared with PDI-LDHs at different concentrations under the conditions of example 1 of the present invention. The PDI-LDHs with different concentrations are utilized to prepare active units with different concentrations. They observe their self-replicating properties through a nonlinear "S" shaped increase in temperature-varying uv absorption.
Fig. 7 is a FL spectrum of reversible disassembly and reassembly of HSA under the conditions of example 1 of the present invention. The reversibility of HSA can be demonstrated by increasing the good solvent for disassembly and by increasing the poor solvent for reassembly into HSA. This process can be performed byThe FL spectrum was used for verification (FIG. 7). By increasing the content of acrylic acid, HSA (lambda em =660 nm) into active units (λ em =647 nm), as evidenced by the shift in FL wavelength from 660 to 647 nm; by adding CH 3 OH to propionic acid/CH 3 The OH ratio again reached (1:3 v/v) and the active units could be rapidly reassembled into HSA, as evidenced by the shift in FL wavelength from 647 to 661 nm.
FIG. 8 shows the passage of PDI under the conditions of example 1 of the present invention agg The corresponding fresh SSP: SEM images of (a) cycle1, (b) cycle2, and (c) cycle3. The activity properties were monitored by SEM (fig. 8), where the helical length of SSP was continuously increased from 1.0 μm (cycle 1) to 5.28 μm (cycle 3). Thus, chiral amplification is achieved by active elongation.
Fig. 9 is a CD spectrum under the conditions of example 1 of the present invention showing the opposite chirality of PDI HSA in the CW and ACW states. When magnetic stirring is concurrent with LDH, the synergistic effect of two-dimensional confinement and vortexing of LDH enables chiral control of HSA. For example, in Clockwise (CW) vortex agitation, HSA shows a positive CD signal at 536nm and a negative CD signal at 330 nm. In contrast, in counter-clockwise (ACW) vortex agitation, HSA showed positive CD signals at 364nm and negative CD signals at 532 nm.
Fig. 10 shows the chiral control of PDI HSA by CW and ACW for the CD signals of 30 independent experiments under the conditions of example 1 of the present invention. The chiral sign of HSA in 30 different batches remained almost unchanged. The percentage of left-handed helical twist in CW-rotated HSA is 90% (n=30) and the percentage of right-handed helical twist in ACW-rotated HSA is 87% (n=30)
Fig. 11 shows photocurrents of HSA and normal self-assemblies under the conditions of example 1 of the present invention. The photoelectric value of HSA is about 10 μa, whereas the photoelectric value of a normal PDI assembly is only 2 μa, and the photoelectric value of HSA is 5 times that of a normal self-assembly. The presence of a large and ordered array of molecules facilitates electron transfer along the pi-pi stacking direction, an important condition for obtaining high photoelectric signals.
FIG. 12 is an SEM image of (a) PMDI HSA under the conditions of example 2 of the present invention; (b) CD spectra of PMDI HSA under CW rotation and ACW rotation. Scanning electron microscopy confirmed that PMDI can form HSA with detectable chirality in the CD spectrum.
FIG. 13 is an SEM image of DABSASA under the conditions of example 1 (a) of the present invention; (b) CD spectra of DABSA CSA. The DABSA system can observe CD signals, but only macroscopic chirality can be observed in the SEM.
FIG. 14 is an SEM image of (a) BPDI LSA under the conditions of example 1 of the present invention; (b) CD spectra of BPDI LSAs. BPDI fails to form HSA, which can be demonstrated by the absence of CD signaling and the absence of macroscopic chirality in SEM images.
The specific embodiment is as follows:
example 1
a.N preparation of N-dipropionic acid-Perylene Diimide (PDI): 1.38g of perylene-3, 4,9, 10-tetracarboxylic dianhydride (PTCDA), 18.0g of imidazole and 2.50g of 3-aminopropionic acid were weighed into a round bottom flask and heated at 100 ℃. At the same time the mixture is under N 2 Stirring and heating for 4h under the atmosphere. After the reaction was completed, the reaction product was cooled to room temperature and dispersed in 100mL of ethanol (CH 3 CH 2 OH), 300mL of diluted hydrochloric acid was added thereto, and the mixture was stirred for 24 hours. The final product was vacuum filtered through a 0.45 μm membrane and the red solid was collected. Washing with distilled water until the pH of the solution became neutral. The resulting solid product was dried in a vacuum oven at 60 ℃ to give pure PDI powder.
b. PDI-LDHs (LDH) is prepared by adopting a coprecipitation method. First, 50.0mL of PDI solution (10.0 mM) was added to a 500mL four-necked flask. 50.0mL of a solution containing 3.75mM Mg (NO 3 ) 2 ·6H 2 O and 1.25mM AlCl 3 ·6H 2 O was designated as solution A and 50.0mL of NaOH solution (1.00M) was designated as solution B. They were simultaneously added dropwise to the flask with vigorous stirring. The pH of the suspension was maintained at 9.00 throughout the process. The mixture was kept under stirring and under N 2 The reaction was carried out under an atmosphere while aging at 80℃for 48 hours. After the reaction, the product was treated with decarbonated water and deionized water and methanol (CH) 3 OH) 3 times and redispersed in CH 3 In OH as a stock solution (30.0 g L -1 ) Further use. All solutions were treated with de-carbonated water and de-ionizedAnd (5) preparing water.
Preparation of HSA: using the two-dimensional domain-limited space of LDHs, 800. Mu.L of propionic acid/CH was added to the prepared PDI-LDHs (3.00 mg) 3 The release of ordered PDI units is defined as active units by the mixture solvent of OH (1:3 v/v). The active units (4.00 mM) were then sonicated for 1h to expose more active sites. After 12h of standing of the active unit (4.00 mM), the corresponding energy favorable state of stabilization of HSA was achieved. During the ultrasonic treatment, a mixture of ice and water was used to maintain the temperature at 0 ℃.
d. Preparation of seed-induced active supramolecular assemblies (SSP): SSP was prepared by mixing active seed (4.00 mM) with PDI agg (2.50 mM) was mixed in an equal volume (1:1 v/v) and then sonicated for 1h. Here, the active seed is a freshly released active unit that is sonicated. PDI (PDI) agg Is PDI molecule in propionic acid/CH 3 Fresh stock solution in OH (1:3 v/v). During the sonication, the temperature was maintained at 0 ℃ using a mixture of ice and water.
By mixing equal volumes of active units (4.00 mM) and PDI agg (2.50 mM) ultrasonic mixing for 1h to prepare cycle1 product, the resulting product was called SSPcycle1. The products in cycle2 and cycle3 are obtained by reacting PDI agg (2.50 mM) was further added to the product of the previous cycle (1:1 v/v) to repeat SSP to give the product, which was in turn called SSPcycle2, SSAcycle3. During the sonication, the temperature was maintained at 0 ℃ using a mixture of ice and water.
Preparation of HSA modified ITO electrode Prior to use of the ITO electrode, the conductive surface of the ITO electrode needs to be tested with a Universal meter.
4.0mM metastable HSA was coated on a clean ITO conductive surface by spin coating at 4000rpm, which was continued for 60 seconds, followed by standing for 24 hours to obtain a supramolecular assembly grown on an electrode.
Comparative example
Preparation of PDI Assembly: selecting concentrated sulfuric acid and water to form H 2 SO 4 /H 2 Mixed solvent system of O. Typically, 0.1g of PDI is dissolved in 10mL of H under sonication 2 SO 4 In (good solvent), 100mL of deionized water was then usedWater (poor solvent) was added to the above solution at a time. The solid insoluble precipitate appeared immediately and the suspensions were kept stationary for 0.5h and the resulting dark red solids (PDI assemblies) were collected by filtration through a 0.45 μm membrane filter. Finally, the mixture was washed with deionized water several times and then dried in an oven at 60 ℃ for subsequent use.

Claims (8)

1. The preparation method of the controllable homochiral supermolecule assembly based on hydrotalcite finite field effect and the application thereof comprises the following specific steps:
preparation of HSA: propionic acid/CH is added into the prepared PDI-LDHs by utilizing the two-dimensional domain-limited space of the LDHs 3 The OH mixture solvent defines the ordered PDI units released as active units. The active units are then sonicated to expose more active sites. After a period of standing of the active unit, the advantageous state of corresponding energy for stabilizing HSA is achieved. During the ultrasonic treatment, the temperature was maintained at 0 ℃ using a mixture of ice and water;
b. preparation of seed-induced active supramolecular assemblies (SSP): preparation of SSP by combining active seed with PDI agg Mix at equal volume (1:1 v/v) and then sonicate for a period of time. Here, the active seed is a freshly released active unit that is sonicated. PDI (PDI) agg Is PDI molecule in propionic acid/CH 3 Fresh stock solution in OH (1:3 v/v). During the sonication, the temperature was maintained at 0 ℃ using a mixture of ice and water. By combining equal volumes of active units and PDI agg Ultrasonic mixing for a period of time produces cycle1 product, the resulting product being referred to as SSPcycle1. The products in cycle2 and cycle3 are obtained by reacting PDI agg Further addition to the product of the previous cycle (1:1 v/v) to repeat SSP gave the product, which was in turn called SSPcycle2, SSAcycle3. During the sonication, the temperature was maintained at 0 ℃ using a mixture of ice and water;
treatment of ITO: firstly, washing the ITO glass three times by using a detergent, water and ethanol respectively, and carrying out ultrasonic treatment for 15-20min each time. Then at N 2 Blow-drying in atmosphere for subsequent electrochemical working electrode testing.
Preparation of HSA modified ITO electrode: before using the ITO electrode, the conductive surface of the ITO electrode needs to be tested with a universal meter. Coating metastable HSA onto the clean ITO conductive surface by spin coating, which is continued for 60-70s, followed by standing for a period of time to obtain a supramolecular assembly grown on the electrode;
e. electrolyte solution Na 2 SO 4 Preparation of the solution: configuration of 0.500M Na 2 SO 4 A solution. 3.551g of Na is weighed 2 SO 4 Adding 50mL deionized water into the powder, and completely dissolving by ultrasonic treatment to obtain Na 2 SO 4 A solution;
f. electrochemical testing: photoelectrochemical testing was performed on a CHI660E electrochemical workstation using a standard three electrode system with a working electrode (HSA modified ITO electrode), a platinum wire counter electrode and a saturated calomel reference electrode. The electrolyte solution was 0.500M Na 2 SO 4 A solution. The photoelectric test was carried out using a xenon lamp > 420nm under no bias.
2. The process according to claim 1, wherein the PDI-LDH is present in a concentration of 0.3-0.4M.
3. The method of claim 1, wherein the concentration of the active units is 4.00mM-4.50mM.
4. The method of claim 1, wherein the PDI is agg The concentration of (2.50 mM-3.00 mM).
5. The method according to claim 1, wherein the propionic acid/CH 3 The OH ratio was 1:3.
6. The method of claim 1, wherein the metastable HSA is applied by spin coating to a clean ITO conductive surface.
7. Root of Chinese characterThe method of claim 1, wherein the method of preparing the intercalation molecule PDI comprises: 1.38g of perylene-3, 4,9, 10-tetracarboxylic dianhydride (PTCDA), 18.0g of imidazole and 2.50g of 3-aminopropionic acid were weighed into a round bottom flask and heated at 100 ℃. At the same time the mixture is under N 2 Stirring and heating for 4h under the atmosphere. After the reaction was completed, the reaction product was cooled to room temperature and dispersed in 100mL of ethanol (CH 3 CH 2 OH), 300mL of diluted hydrochloric acid was added thereto, and the mixture was stirred for 24 hours. The final product was vacuum filtered through a 0.45 μm membrane and the red solid was collected. Washing with distilled water until the pH of the solution became neutral. The resulting solid product was dried in a vacuum oven at 60 ℃ to give pure PDI powder.
8. The method of preparation of claim 1, wherein the method of preparation of PDI-LDH comprises: PDI-LDHs (LDH) is prepared by adopting a coprecipitation method. First, 50.0mL of PDI solution (10.0 mM) was added to a 500mL four-necked flask. 50.0mL of a solution containing 3.75mM Mg (NO 3 ) 2 ·6H 2 O and 1.25mM AlCl 3 ·6H 2 O was designated as solution A and 50.0mL of NaOH solution (1.00M) was designated as solution B. They were simultaneously added dropwise to the flask with vigorous stirring. The pH of the suspension was maintained at 9.00 throughout the process. The mixture was kept under stirring and under N 2 The reaction was carried out under an atmosphere while aging at 80℃for 48 hours. After the reaction, the product was treated with decarbonated water and deionized water and methanol (CH) 3 OH) 3 times and redispersed in CH 3 In OH as a stock solution (30.0 g L -1 ) Further use. All solutions were prepared with decarbonated water and deionized water.
CN202310308555.1A 2023-03-27 2023-03-27 Preparation and application of controllable homochiral supermolecule assembly based on hydrotalcite finite field effect Pending CN116376041A (en)

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