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. 2024 Jan 26;9(5):5695–5704. doi: 10.1021/acsomega.3c08179

Remediation of Dyes Using Supramolecular Material Derived from Carbohydrate Based π-Gelator Using the Bottom-Up Assembly Approach

Vandana Singh †, Krishnamoorthy Lalitha †, C Uma Maheswari †, Vellaisamy Sridharan ‡, Debarchan Pradhan §, Srishti Batra §, Subbiah Nagarajan §,*
PMCID: PMC10851238  PMID: 38343926

Abstract

graphic file with name ao3c08179_0009.jpg

As a consequence of rapid population growth, the earth has faced numerous environmental sustainability issues and crises, water pollution is one of the important points of concern because of industrialization. In particular, effluents discharged from dying industries are rated top among the various industrial effluents, especially by their volume and composition. Annually >7.5 × 105 metric tons of different dyes are produced and consumed in different industries. In order to dye 1 kg of fabric, approximately 100–150 L of water is required, and after the dying process, it is discharged as an effluent either on a landfill or in water bodies. It is our responsibility to conserve environmental sustainability. In this line, we have developed a simple protocol to generate carbohydrate-based amphiphile using D-sorbitol, and pyrene-1-carboxaldehyde in good yield. This carbohydrate-based π-gelator is prone to forming a gel in various solvents and oils by the bottom-up assembly process. Morphological analysis of the self-assembled structure was identified by using optical microscopy and SEM. The viscoelastic behavior of the gel was examined by using rheology. In this paper, we explored the dye adsorption and desorption characteristics of the gel. Further, we have developed a cartridge based on cellulose using a template-assisted assembly phenomenon and demonstrated its potential in adsorbing dyes such as methylene blue, crystal violet, rhodamine B, and Congo red.

Introduction

In various industries such as textiles, cosmetics, leather, paper, paint, food, and pharmaceuticals, dyes are considered as one of the crucial necessities. Rapid industrialization to meet the demands of population growth and the subsequent discharge of the dye as waste into the environment has contributed significantly to pollution. For example, water-soluble synthetic dyes such as methylene blue (a basic dye), congo red (the anionic azo dye), rhodamine B (a cationic dye), and crystal violet (a triphenylmethane dye) are extensively used in textile and paper industries, and direct discharge of wastewater comprising these industrial dyes may cause numerous hazardous effects to the environment and human such as carcinogenic, dermatitis, mutagenic, neurotoxicity and allergic effects.1,2 To have a sustainable environment and life, the conservation of freshwater bodies is necessitated. This scenario motivated researchers to develop a new methodology and material to treat dye contamination in water. In this regard, several research has been carried out by employing various methodologies based on advanced oxidation by Fenton’s reagent, photocatalytic reactions, ozonization, solvent-extraction, electro-coagulation, adsorption, ion exchange, filtration, chemical coagulation and by biological methods.2,3 Among the various methodologies made available in the literature, adsorption is reported to be the most efficient because of its efficacy in facile removal of dyes in a cost-effective manner.3 In this context, supramolecular gels derived from low molecular weight gelators (LMWG) derived by bottom-up assembly process have received much attention among researchers.4

In the recent past, the hypothesis of using supramolecular gels as advanced materials for drug delivery, catalysis, remediation of industrial wastes, optoelectronics, wound healing, and enzyme immobilization has been clearly visualized.4−12 However, a more intense protocol encompassing sustainability has to be developed.13,14 Supramolecular assembly of various natural systems such as peptides, sugars, bile acids, steroids, amino acids, nucleobase, phenolic lipids, and long-chain fatty acids, displayed potential in the formation of gels.10,15−20 Among the various natural molecules available, carbohydrates are considered as the cheapest resource obtained from a broad range of biomass wastes, relatively in more economical pathways.21−32 The inherent chirality, biocompatibility, and rich structural diversity of sugars empower them as potent candidates for constructing advanced functional materials suitable for biological and medicinal applications.33

Recently, Sureshan and co-workers have demonstrated the use of a carbohydrate-based gel system in oil spill remediation and ion sequestration, which is considered a major environmental concern.34−39 Soft material fabricated from 1,3:2,4-dibenzyldene-D-sorbitol (DBS) displayed stimuli-responsive behavior with respect to pH and UV irradiation in the presence of diphenyl iodonium nitrate forming photo-patterned multidomain gels.40 In addition, acetal-protected D-sorbitol displays robust self-assembly behavior, which is greatly influenced by the solvent used.40−43 In continuation of our ongoing research in the field of supramolecular chemistry, we have designed a gelator from D-sorbitol, an FDA-approved molecule bearing the E number 420 displaying applications in food, cosmetics, and pharmaceutical industries, and pyrene-1-carboxaldehyde. Over the past few decades, pyrene derivatives have been considered unique in their properties because of their robustness. Owing to its tunable π–π stacking nature with respect to the environmental parameters, these classes of compounds are mostly used as chemical and biosensors.44 Further, gelators derived from pyrene displayed strong intermolecular interaction and intercalation behavior.45 In particular, an ambidextrous gelator derived from pyrene displayed excellent electronic and photophysical properties, and its interaction with carbon nanotubes (SWNT) underpins the potential of these materials in fabricating high-performance electronic devices.44,46

The fabrication of adsorbent material capable of rapid removal of dyes with good mechanical strength and regeneration is highly required for industrial applications.47 Eventhough, a broad range of methodologies have been developed for the removal of dyes from the industrial effluent,48−53 the utilization of template-assisted assembly phenomenon54,55 in dye remediation is not much studied. Herein we have constructed a supramolecular gel by judiciously combining D-sorbitol, a hydrophilic moiety generally used for commercial purposes, and pyrene-1-carboxaldehyde, a well-established molecule displaying tunable π–π stacking and capable of intercalation with various substrates by tuning its aggregation pattern. The synthesized dipyrylidene-sorbitol conjugate (DPSC) could act as an excellent gelator to construct supramolecular adsorbent gels because of its structural features, having the tendency to provide various intermolecular interactions, such as π–π interactions, and H-bonding. Even though the constructed gels display potential in absorbing the dye molecules, they display certain limitations such as moderate strength, poor water permeability, and recyclability. In order to overcome these limitations, we have adopted a cellulose as template-assisted assembly process to enhance the strength and stability of assembled DPSC. The resultant cellulose-DPSC material displayed excellent stability and efficient dye removal capacity; even after 50 cycles of adsorption and desorption, it retains the mechanical strength and efficiency. This work displays the promise of a template-assisted assembly process in dye remediation from contaminated water.

Experimental Section

Materials and Methods

All reagents and solvents needed for the synthesis of DPSC were purchased from Alfa Aesar and Sigma-Aldrich having a purity of >99% and were used as such without any distillation/purification. For the compound purification and recrystallization, LR-grade solvents were employed. AR-grade solvents were used for the gelation studies. The precoated Merck silica gel plates were used to monitor the reaction progress by thin-layer chromatography (TLC) and visualized the spots using any one or the combination of the following visualizing agents such as UV detection, KMnO4, p-anisaldehyde, H2SO4 spray, or molecular iodine.

1H and 13C NMR spectra were recorded on a Bruker Avance 300 MHz instrument in either CDCl3 or CDCl3 with a few drops of DMSO-d6 at room temperature. Chemical shifts (δ) are reported in parts per million (ppm) with reference to the internal standard TMS and coupling constants (J) are given in Hz. Proton multiplicity is assigned using the following abbreviations: singlet (s), doublet (d), triplet (t), quartet (q), and multiplet (m). High-resolution MS analysis was performed on an Agilent 6520 Q-TOF instrument by dissolving the solid sample in methanol.

To obtain the morphology of the gel, optical microscopy and scanning electron microscopy (SEM) were carried out using a Carl Zeiss AXIO ScopeA1 fluorescent/phase contrast microscope and a JEOL JSM-6701F ultrahigh resolution field emission scanning electron microscope, respectively. XRD measurements were taken by keeping a small portion of the xerogel in the X pert-PRO Diffractometer system. UV/vis spectra were recorded on a Thermo Scientific Evolution 220 UV/visible spectrophotometer. The spectra were recorded in constant mode between 200 and 700 nm, with a wavelength increment of 1 nm and a bandwidth of 1 nm. Emission spectra were measured on a JASCO spectrofluorometer FP8200. Infrared (IR) spectra were recorded from 400–4000 cm–1 using KBr in PerkinElmer spectrum 100 spectrophotometer. Agilent Q-TOF 6230 instruments were used to perform High-resolution MS analysis by dissolving the solid compound in acetonitrile or methanol.

Synthesis

To a stirred solution of D-sorbitol (0.5 mmol) in 0.3 mL of methanol were added pyrene-1-carboxaldehyde (3.0 mmol) and p-toluenesulfonic acid (1.0 mmol), and the mixture was stirred at room temperature for 12 h. After the completion of the reaction was confirmed, a yellow precipitate separated out is filtered and washed very well with cold methanol. The yellow precipitate thus obtained is suspended in DCM to remove the excess pyrene-1-carboxaldehyde and again filtered in a vacuum pump and dried.

Isolated as a pale yellow solid. Purity: > 98%; Yield = 88%; 1H NMR (300 MHz, DMSO-d6) δ = 8.67 (d, J = 9.3 Hz, 1H), 8.47 (d, J = 9.3 Hz, 1H), 8.34–8.20 (m, 6H), 8.12–8.07 (m, 1H), 6.45 (s, 1H), 4.81- 4.65 (m, 3H), 4.50–4.46 (m, 1H), 4.10–4.06 (m, 1H), 3.97 (d, J = 8.4 Hz, 1H), 3.87 (d, J = 6.9 Hz, 1H), 3.78–3.57 (m, 3H); 13C NMR (75 MHz, DMSO-d6) δ = 132.5, 131.6, 131.2, 130.7, 128.6, 128.2, 127.9, 127.8, 126.8, 125.9, 125.8, 125.4, 125.0, 124.8, 124.4, 124.3, 99.9, 81.7, 80.2, 69.9, 63.3, 62.3, 61.6. HRMS (ESI, m/z): [M + H]+ calcd. for C40H31O6: 607.2121; found: 607.2097.

Gelation Studies

The gelation ability of DPSC was investigated by the “stable to inversion method”39 in a diverse range of organic solvents such as cyclohexane, DMSO, DMSO + H2O, ethylene glycol, DMF, 1,2-dichlorobenzene, ethyl acetate, acetonitrile, xylene, glycerol, lauryl alcohol, polyethylene glycol, etc., and oils like castor, olive, paraffin, jojoba, hazelnut, soybean, sesame, linseed oil. To check gelation ability, the appropriate amount of solvent/oil was added to the calculated quantity of gelator, which was taken in a vial and sealed. On heating the vial is heated, complete dissolution of the gelator occurs and the gelation is observed upon subsequent cooling to room temperature. At the end of the gelation test, the stage in which there is no gravitational flow in the inverted vial denotes the gelation, “G”. Instead, it remains in solution and is referred to as “S”; if it remains as precipitate, it is indicated as precipitation, “P” and if the gelator did not get dissolved upon heating, it is referred to as insoluble (I).

Characterization of Gel Using Rheology

The viscoelastic characteristics of the DPSC gel are investigated by carrying out the rheological measurements at 23 °C using a stress-controlled rheometer (Anton Paar Modular Compact Rheometer 302) furnished with a 25 mm diameter sized steel-coated parallel-plate geometry. Rheological measurements for the gel were recorded by placing the gel sample over a parallel plate with a 1 mm gap between the plates and subsequently trimming the excess gel.

Results and Discussion

The fabrication of smart soft materials is considered as an attractive research area for developing multifunctional materials due to the involvement of self-complementary noncovalent interactions, which can form a three-dimensional network structure.56,57 However, in the earliest stages of supramolecular gels, molecular design and details behind the assembly were not well established. Indeed, the significance of soft materials in various sectors further motivated researchers to investigate these fascinating materials. In this context, our research group has reported the design, synthesis, and potential applications of pyrene-based amphiphiles.8,58−68 In an attempt to understand the bottom-up assembly of DPSC, initially, we have synthesized DPSC from D-sorbitol and pyrene-1-carboxaldehyde using relatively a simple procedure given in Scheme 1.40,69−75 In 1H NMR spectra, the presence of a singlet at δ = 6.45 ppm and a peak at δ = 99 ppm in the 13C NMR spectrum confirms the formation of acetal in DPSC. After the product formation was confirmed by various spectral techniques, the supramolecular assembly of DPSC is studied. At this juncture, molecules in certain solvents under suitable environmental factors such as concentration, temperature, and pressure in the presence or absence of additives are considered more crucial to induce the supramolecular assembly process. Even though Hansen solubility and molecular packing are considered as key parameters, in a real scenario this tends to deviate and the variable that contributes to gel formation is very hard to predict. However, the gelation propensity of DPSC is tested in various solvents like dimethyl sulfoxide (DMSO), dimethylformamide (DMF), water, ethyl acetate, cyclohexane, xylene, acetonitrile, 1,2-dichlorobenzene, methanol, ethylene glycol, glycerol, polyethylene glycol, lauryl alcohol, DMSO:H2O and oils such as heavy paraffin, light paraffin, olive, linseed, sesame, jojoba, soybean, hazelnut, eucalyptus oil (Table 1).

Scheme 1. Synthesis of DPSC, 3.

Scheme 1

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Table 1. Gelation Studies of DPSC in Various Solventsa.

s.no. solvent/oil observation CGC (wt/v%)
1. olive oil S  
2. heavy paraffin oil S  
3. light paraffin oil S  
4. sesame oil S  
5. linseed oil S  
6. H2O I  
7. dimethyl sulfoxide S  
8. dimethylformamide S  
9. ethyl acetate I  
10. cyclohexane I  
11. jojoba oil S  
12. castor oil G 1.0
13. xylene S  
14. glycerol P  
15. ethylene glycol S  
16. soybean oil S  
17. eucalyptus oil S  
18. hazelnut oil S  
19. polyethylene glycol S  
20. acetonitrile I  
21. methanol I  
22. 1,2-dichlorobenzene G 1.0
23. DMSO: water (1:1) G 1.5
24. lauryl alcohol G 1.5
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a

CGC is calculated by performing the experiment triplicate.

Gelation studies revealed that DPSC could form Oleogel in castor oil and organogels in solvents like 1,2-dichlorobenzene (CGC = 1.0 wt %/v), lauryl alcohol (CGC = 1.5 wt %/v), and hydrogel in DMSO:H2O (1:1) (CGC = 1.5 wt %/v). At this point, gelation studies revealed that DPSC could form Oleogel, organogel, and hydrogel as a result of intermolecular interactions such as π–π stacking and hydrogen bonding. It is very important to document that the gelation process results in 3-dimensional network formation should be balanced by solvent, and the parameters stabilizing the gel system cannot be broadly generalized. A complete dissolution of water-insoluble DPSC can be achieved by DMSO, followed by the addition of H2O resulting in the formation of hybrid hydrogel. A similar trend was not observed in any of the other polar aprotic solvents. Hence water is considered as an additive to promote gelation in DMSO solvent. It also provided an interesting clue that the seeding of H2O facilitates the intermolecular hydrogen bonding, in addition to the existing π–π stacking.

In order to understand the overall aggregation pattern of DPSC in various solvents, we performed morphological analysis using optical and scanning electron microscopy (SEM). An optical micrograph of the gel formed by DPSC in DMSO–H2O and lauryl alcohol is shown in Figure 1a–c. Interestingly, the gel formed by DPSC in DMSO-H2O displayed lamellar architecture with green fluorescence under fluorescent light, whereas in lauryl alcohol, a bundle of flower petal-like morphology is observed. SEM analysis of xerogel of DPSC in DMSO-H2O, lauryl alcohol, and 1,2-dichlorobenzene displayed the formation of lamellar bundles, flower petals, and fibrillar architectures respectively (Figure 1d–i). The SEM micrographs of the xerogels formed from DPSC in DMSO:H2O revealed the formation of a well-defined densely packed lamellar structure having a width of ∼1.0 μm, whereas in 1,2-dichlorobenzene the structure displayed a width of ∼500 nm. Based on the results of morphological analysis, it is worth mentioning that the aggregation pattern of DPSC is solvent-dependent.

Figure 1.

Figure 1

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Morphology of DPSC gels. (a–c) Optical micrograph of the gel formed by DPSC (a) in DMSO:H2O under day light (b) in DMSO:H2O under fluorescent light; (c) in lauryl alcohol. (d–i) SEM images of xerogel of DPSC (d, e) DMSO:H2O; (f, g) lauryl alcohol; and (h, i) 1,2-dichlorobenzene.

Having established the morphology of DPSC gels, further, ATR-FTIR is recorded to obtain the intermolecular interactions existing in the bottom-up assembled gel. ATR-FTIR spectra of DPSC in amorphous and xerogel states are displayed in Figure 2a. Irrespective of the amorphous or xerogel state, the stretching frequency of the −OH bond displayed absorption at ∼3400 cm–1, which indicates that a random intermolecular H-bonding is observed even in the amorphous state; however, it does not induce gelation. Stretching frequencies of aromatic −C–H, −C=C–, and −C–O in an amorphous state displayed absorption at 3043, 1640, 1585, and 1097 cm–1 respectively. Upon aggregation, −C–H, −C=C–, and −C–O stretching frequencies have shifted to 3032, 1676, 1590, and 1038 cm–1 respectively, which suggest the involvement of π–π stacking and hydrogen bonding during the bottom-up assembly process (Figure 2a). The existence of distinct morphologies of DPSC gels in different solvents motivated us to further probe the responsible noncovalent interactions. UV–vis spectral studies are one of the straightforward techniques to understand the prevailing solvent-gelator interaction during the bottom-up assembly process. UV–vis spectra of DPSC in gelling solvents such as DMSO, lauryl alcohol, and 1,2-dichlorobenzene displayed three absorption peaks each at λmax = 313, 327, and 344 nm, 312, 326, and 342 nm, and 315, 330, 346 nm, respectively (Figure 2b). The varying absorbance of DPSC in DMSO, lauryl alcohol, and 1,2-dichlorobenzene is due to the gelator–solvent interactions, which directly reflected on the morphology.

Figure 2.

Figure 2

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(a) ATR-FTIR spectra of DPSC in amorphous and xerogel state; (b) UV–vis spectra of DPSC in different gelling solvents (1 × 10–5 M).

Even though UV–vis studies support the existence of various types of aggregation patterns in different solvents, the same trend has been further confirmed by fluorescence characteristics. Emission spectra of DPSC in DMSO displayed emission at 379, 391, and 418 nm, whereas other gelling solvents such as lauryl alcohol and 1,2-dichlorobenzene displayed a marginal shift in the emission wavelength (Figures S6 and S7), which support the existence of molecular aggregation during bottom-up assembly.76 Further dilution of these solutions by the sequential addition of the corresponding gelling solvents displayed hypsochromic shift accompanied by the broadening of emission peaks, suggesting the formation of aggregates (Figures S6 and S7).

In order to ascertain the molecular packing mechanism during the gelation process, small-angle X-ray diffraction (SAXD) of xerogel of DPSC in DMSO–water was recorded (Figure 3). The xerogel of DPSC displayed sharp peaks at 2θ = 10.32, 11.98, 14.56, 15.88, 20.96, 21.92, 22.80, 24.27, 25.11, 26.34, 27.85, and 28.79° corresponding to the d-spacing of 0.86, 0.74, 0.61, 0.56, 0.42, 0.41, 0.39, 0.35, 0.34, 0.32, 0.31 nm respectively, which follows a well-defined periodic pattern indicating the lamellar organization.77 Furthermore, the appearance of sharp and highly intense peaks between 20 and 30° confirms the existence of π–π stacking in the pyrene moiety.

Figure 3.

Figure 3

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(a) SAXRD of the xerogel formed from DPSC in DMSO-H2O and (b) probable packing of DPSC during bottom-up assembly.

After ensuring the existence of noncovalent interactions like H-bonding, π–π stacking in self-assembly, and exploring the possible packing mechanism, we were curious to examine the mechanical strength of the DPSC gels and identify their prospective for potential practical usage in the field of medicine, sensor, environmental remediation, etc. For this purpose, the viscoelastic property of the gel formed from DPSC in the DMSO-H2O system was examined using a rheometer.78,79Figure 4 depicts the rheological measurement of the gel formed from DPSC in DMSO-H2O. In the frequency sweep experiment, the response of storage modulus, G′, and loss modulus, G″ were measured as a function of applied frequency at the constant strain whereas, in the amplitude sweep experiment, the variation of G′ and G″ was measured as a function of applied strain (Figure 4). The results of the amplitude sweep experiment reveal that G′ is greater than G″ until it reaches the critical strain (γc = 0.005%), which reveals the strength of the gel. Upon increasing the strain beyond critical strain, G′ and G″ begin to decline because of the gel-to-sol transition, which occurs at 0.27% (G′ = G″ = 662.6 Pa) (Figure 4a). Furthermore, it is observed that throughout the entire executed range of frequency sweep at room temperature, the value of G′ was about 5 times greater than G″ revealing its potential to withstand external forces (Figure 4b).

Figure 4.

Figure 4

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Rheological measurements of DPSC gel. (a) Amplitude sweep and (b) Frequency sweep experiments.

Remediation of Dyes

The discharge of water-soluble toxic dyes without prior treatment led to shrinking water quality and environmental concerns in the current scenario. This has triggered much interest among researchers to discover a suitable method for the removal of toxic dye effectively from water. Based on the molecular design and structure, we were curious to investigate the possibility of using the DPSC gel formed in the DMSO-H2O system as an absorbent material for the removal of water-soluble organic dyes. Among the various dyes present in industrial effluent, we have selected four common dyes such as rhodamine B, Congo red, methylene blue, and crystal violet (Figure 5) for our studies.

Figure 5.

Figure 5

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Chemical structure of dyes selected for the present adsorption studies.

To check the dye adsorption capacity of DPSC gel, initially, we added 5 mL of 20 μM rhodamine B dye solution carefully onto the 1 mL of freshly prepared DPSC gel in DMSO-H2O at CGC of 1.5% wt/v and observed the dye adsorption capability. Immediately after addition, slow penetration of the rhodamine B dye into the gel network was observed. Based on the preliminary results, we are further interested in examining the practical utility of DPSC gel as a filter bed to remove dye from wastewater. The direct use of DPSC gel formed in DMSO:H2O, lauryl alcohol, 1,2-dichlorobenzene in the form of beads packed in a column furnished satisfactory results in removing dyes, however, during the process of recovery of dyes and regeneration of gel beads, an attritional loss of beads were observed because of lack of exceptional strength. In order to overcome this issue, a template-assisted assembly process has been followed. A cotton ball of about 750 mg is dipped in a hot solution of DPSC (2.5 wt %/v) in DMSO:H2O and kept undisturbed for about 1 h. During this process, free hydroxyl groups in DPSC form a stable H-bonding with the hydroxyl group of cellulose of cotton. DPSC-treated cotton is washed thoroughly in water to remove free DPSC and dried. This material is referred to as “cellulose as a template-assisted assembly of DPSC” (CTDPSC). A completely dried CTDPSC is packed in a mini column and used as a cartridge for dye remediation studies.

To probe the dye adsorption behavior of the cartridge, a dye solution of 10 ppm was introduced, and the treated water was analyzed using UV–vis spectroscopy to identify the traces of the dye. Surprisingly, the cartridge developed is capable of rapidly adsorbing various dyes such as congo red, rhodamine B, crystal violet, and methylene blue from aqueous solution, leaving behind pure transparent water at room temperature, which was collected in test tubes. The removal of dye was witnessed by the naked eye as well as by recording the UV–vis absorption spectrum of each collected fraction. Additionally, the efficiency of the cartridge to adsorb dye is determined by comparing the absorption spectral changes for each fraction collected after the treatment and compared with the effluent (Figure 6). The dye removal efficiency of the cartridge is calculated using the formulas

graphic file with name ao3c08179_m001.jpg

where Co and Ce are the initial and final concentrations.

Figure 6.

Figure 6

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UV–vis spectra of each fraction collected before and after treatment with a cartridge. (a) Congo red, (b) crystal violet, (c) methylene blue, and (d) rhodamine B. Numbers represented in the figure denote the various fractions collected in continuous adsorption and desorption mode.

Our optimization studies revealed that 100 mg of cartridge material (2.5% w/v) can effectively remove 500 mL of effluent containing 10 ppm of dye concentration. After complete exhaustion of the cartridge, the inside material is taken off and soaked in an isopropyl alcohol/water mixture (1:1 ratio) for the desorption of dyes. After desorption, the cartridge material is dried and packed again for reuse.

Regeneration of the cartridge is established by carrying out each experiment in continuous adsorption and desorption mode, and encouraging results were obtained (Figures S8 and S9). The continuous ad/desorption studies revealed that the developed cartridge can effectively absorb up to 500 mL of effluent containing 10 ppm of Congo red; 200 mL of effluent containing 10 ppm of rhodamine B; 400 mL of effluent containing 10 ppm of crystal violet and 350 mL of effluent containing 10 ppm of methylene blue.

Having established the adsorption potential of the cartridge developed by the template-assisted assembly process, it is necessary to establish the adsorption mechanism. In order to establish the mechanism, we have used SEM, ATR-FTIR, and XRD techniques. For SEM analysis, we have prepared a xerogel of rhodamine B adsorbed DPSC gel. The morphology of dye-absorbed gel reveals the lamellar sheet-like morphology, which is slightly different than the native DPSC gel. The intercalation of dye molecules in the assembled network structure induced an in situ change in the morphology of fibers. Suppose the adsorption phenomenon is based on the intermolecular ionic or H-bonding interactions, then the surface morphology of the gel would have changed (Figure 7a). Nevertheless, the adsorption in the cartridge is due to the intercalation of dyes with the pyrene unit of the DPSC, where the backbone is stabilized by the intermolecular H-bonding with cellulose. The well-established methods for the identification of intermolecular interactions are FTIR and XRD. ATR-FTIR spectra of xerogel of rhodamine-adsorbed DPSC revealed the existence of intercalation of rhodamine in between the π–π stacked pyrene units. The stretching frequency of C–H (aromatic) and C–C (aromatic) observed at 3032 and 1638 cm–1 in the xerogel of DPSC got shifted to 3045 and 1654 cm–1 (Figure 7b). Further investigation of the dye-adsorbed gel with SAXRD revealed the presence of a diffraction pattern corresponding to 2θ = 3.97, 7.95, 10.34, 11.99, 14.58, 15.93, 20.95, 21.87, 22.80, 24.30, 25.14, 25.58, 26.33, 27.91, and 28.78° corresponding to the d-spacings 2.22, 1.11, 0.85, 0.74, 0.61, 0.56, 0.42, 0.39, 0.37, 0.36, 0.35, 0.34, 0.32, 0.31 nm, respectively (Figure 7c). The existence of peak corresponding to 2θ = 20.95, 21.87, 25.14, 25.58, 26.33, 27.91, and 28.78° supports the intercalation of dye with π–π stacking pyrene unit (Figure 7c).80

Figure 7.

Figure 7

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(a) Morphology of rhodamine B adsorbed DPSC gel, (b) ATR-FTIR spectra of dye adsorbed DPSC gel, (c) SAXRD of dye adsorbed xerogel, and (d) probable interaction of the dye with the xerogel filter bed.

Conclusions

In summary, we have developed a simple protocol for the generation of dipyrylidene-sorbitol conjugate (DPSC) from sorbitol, commercially used sugar alcohol, and pyrene-1-carboxaldehyde in good yield. Molecular self-assembly of the synthesized sugar-based amphiphile in a broad range of solvents utilizing noncovalent interactions such as H-bonding and π–π stacking furnished lamellar, flower-petal-like, and fibrillar architecture in various solvents. Bottom-up assembly mechanisms of gelators involving various types of intermolecular interactions were identified by ATR-FTIR, XRD, UV–vis, and fluorescence studies, and a suitable assembly mechanism has been proposed. Rheological measurements revealed the viscoelastic characteristics and processability of gels. Dye adsorption and desorption properties displayed by assembled material expanded the scope of utilizing this gel material in dye remediation. For probable commercial applications, we have developed a cartridge based on cellulose using template-assisted assembly of the DPSC phenomenon. The reported cartridge displayed potential in adsorbing dyes such as methylene blue, crystal violet, rhodamine B, and Congo red efficiently by following the intercalation mechanism. A simple adsorption, desorption, regeneration, and material stability displayed by the cartridge enable the developed protocol as a user-friendly and commercially viable technique.

Acknowledgments

Financial support from the Science and Engineering Research Board, Department of Science and Technology, India (sanction order no: CRG/2018/001386, CRG/2023/002466) and SPARC, Ministry of Human Resource Development, India (SPARC/2018–2019/P263/SL) are gratefully acknowledged. The authors thank the Department of Science and Technology-FIST program, India (SR/FST/CS-II/2018/65) for providing funds for the improvement of S&T infrastructure at the Department of Chemistry, National Institute of Technology Warangal.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.3c08179.

  • NMR spectra; mass spectra; UV–vis spectra; and dye remediation details (PDF)

Author Contributions

The manuscript was written through the contributions of all authors. All authors have given approval for the final version of the manuscript.

The authors declare no competing financial interest.

Supplementary Material

ao3c08179_si_001.pdf (996.6KB, pdf)

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