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Cellulose polymers with β-amino ester pendant group: design, synthesis, molecular docking and application in adsorption of toxic metals from wastewater

Cellulose polymers with β-amino ester pendant group: design, synthesis, molecular docking and... Background: Cellulose polymers with multidentate chelating functionalities that have high efficiency for toxic metal ions present in water were designed, synthesized, and analyzed. The synthesis was carried out by reacting microcrys- talline cellulose extracted from the solid waste of the olive industry with tert-Butyl acetoacetate (Cell-AA), produced cellulose with β-ketoester functionality was then reacted with aniline and the amino acid glycine to produce Cell- β-AN and Cell-β-GL, respectively. Results: The adsorption efficiency of the three polymers toward Pb(II) and various toxic metal ions present in sewage was evaluated as a function of adsorbent dose, time, temperature, pH value, and initial ion concentration to deter- mine optimum adsorption conditions. The three polymers showed excellent efficiency toward about 20 metal ions present in a sewage sample collected from the sewer. The adsorption process follows the Langmuir adsorption iso- therm model with a second-order of adsorption rate, the calculated qe values (2.675, 15.252, 20.856 mg/g) were close to the experimental qe values (2.133, 13.91, 18.786 mg/g) for the three polymers Cell-AA, Cell-β-AG and Cell-β-AN, respectively. Molecular Dynamic (MD) and Monte Carlo (MC) simulations were performed on the three polymers com- plexed with Pb(II). Conclusion: The waste material of the olive industry was used as a precursor for making the target cellulose polymers with β-Amino Ester Pendant Group. The polymer was characterized by SEM, proton NMR, TGA, and FT-IR spectroscopy. The efficacy of adsorption was quantitative for metal ions present in a real sample of wastewater and the efficiency didn’t drop even after 7 cycles of use. The results indicate the existence of strong complexation. The thermodynamic study results showed a spontaneous bonding between of Pb(II) and the polymers pendant groups expressed by the negative value of the Gibbs free energy. Keywords: Water treatment, Persistent pesticides, Difenoconazole, Cellulose nanocrystalline, 2-furan carbonyl chloride, Cellulose, Monte Carlo, Glycine, Molecular dynamic, Adsorption, Wastewater Introduction Water contamination has become a critical global prob- *Correspondence: ohamed@najah.edu; sjodeh@najah.edu lem and a major health issue for living organisms and Chemistry Department, Faculty of Science, An-Najah National University, P.O. ecosystems. The issue was related to [1–3] industrial Box 7, Nablus, Palestine waste, agricultural waste, and the household cleaning Full list of author information is available at the end of the article © The Author(s) 2022. 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The Creative Commons Public Domain Dedication waiver (http:// creat iveco mmons. org/ publi cdoma in/ zero/1. 0/) applies to the data made available in this article, unless otherwise stated in a credit line to the data. Nairat et al. BMC Chemistry (2022) 16:43 Page 2 of 21 items that release toxic heavy metals, organic mate- evaluated toward Pb(II) and other metal ions from real rial, dyes and other to the sewage system [4–6]. Other wastewater samples. sources of toxic contaminants include medical, agricul- tural, plumbing, body care products. Among the toxic Experimental heavy metal ions that pose a risk and required immediate Material attention are Cd(II), Cu(II), Mn(II), Mg(II) Sr(II), Al(II), All chemicals and reagents used in this work were pur- Co(II), Ni(II), Cr(III), Zn(II) and Pb(II) ions [7, 8]. Recy- chased from Sigma-Aldrich chemical company (Jeru- cling of wastewater released from industrial and human salem) and used as received. The chemicals include activities has become a necessity. Among the most effec - tert-Butyl acetoacetate (t-BAA), lithium chloride tive technologies used in wastewater purification and anhydrous (LiCl), N,N-dimethylacetamide anhydrous recycling wastewater from toxic heavy metals and other (DMAc), aniline, glycine, lead(II) nitrate, acetic acid, contaminants are precipitation, membrane filtration, methanol and nitrogen gas (purity 99.9%). All reagents electrodialysis, electrochemical treatment, coagula- used were of analytical grade. Deionized water was used tion [9], flotation [10], cementation [11], solvent-solvent to prepare all solutions. Cellulose used in this work was extraction [12], ion exchange [13], chemical oxidation extracted from olive industry solid waste (Jeft) by a [14], reverse osmosis [15], and adsorption [16]. Amon chemical process that was developed at the laboratories these methods, adsorption received the highest atten- of An-Najah National University-Nablus/Palestine. tion due to its simplicity, availability, profitability, prac - ticality, ecofriendly, recyclability, relatively low cost, less Methods sludge production, high efficiency, and high selectivity Characterization [17–19]. The adsorption method mainly focuses on acti - Nicolet 6700 Fourier Transform Infrared (FT-IR) spec- vated carbon as the adsorbents. However, some withdraw trometer equipped with the Smart Split Pea micro-ATR backs such as processing costs have led the scientist to accessory (Thermo Fisher Scientific, Waltham, MA, search for other means [20]. More desirable adsorbents USA) was used in this work. The following IR param - -1 are those made from renewable, low-cost materials, eters were used: resolution 4  cm , spectral range 400– -1 especially those derived from agricultural waste materi-4000  cm , number of scans 128. Thermo-gravimetric als [21] and biological adsorbent [22, 23]. Natural based analysis (TGA) and differential scanning calorimetry adsorbents made from cellulose [24], lignin, chitosan and (DSC) measurements were performed using a TG/DSC hemicellulose received the most attention. They are eco - Star System (Mettler-Toledo) coupled with a MS-Ther - nomically feasible, environmentally friendly, and highly mostar GSD320 (Pfeiffer Vacuum) Mass Spectrometer. efficient for removal of heavy metal ions from wastewa - TG/DSC analysis was performed with Pt crucibles, in N −1 −1 ter [25]. Cellulosic based adsorbents and related obtained flow (20  mLmin ) at a heating rate of 5 ºC min in the from waste materials such as Kenaf [26, 27], cotton lint- range 25–1100 ºC by a HT1100 oven connected to a MX5 ers [28], wheat straw [29], wood sawdust [30], rice husk microbalance (thermostatic at 22  ºC). The STARE soft - [31] were prepared and investigated for the adsorption of ware v.10.0 (Mettler Toledo) controlled the process. several metals such as those mentioned above. Nanopar- Metal ions concentrations were determined using ticle adsorbents made from natural materials such as cel- Flame Atomic Absorption Spectrometer (FAAS, ICE3500 lulose nanocrystalline (CNC) were the most promising, AA System, Thermo scientific, United Kingdom) and the especially. Despite all the rapid progress in the nanocellu- inductively coupled plasma mass spectrometry (ICP- TM lose adsorbents still many celluloses-based materials and MS) via an iCAP RQ ICP-MS (Thermo Fisher Sci - derivatives have not been explored in wastewater purifi - entific, Waltham, MA, USA). All analysis studies were cation. In this work, new cellulose-based adsorbents were performed in triplicate and the mean of the three runs prepared and used in wastewater purification. The new was reported. The error range in the experimental data adsorbents were prepared by functionalizing microcrys- was analyzed using Excel Microsoft software, a certainty talline cellulose with β-ketoester to form cellulose with interval of 95% was used. The data analysis was per - 1,3-dicarbonyl pendant group, which then converted to a formed using the t-test. All variations were considered Schiff base by reacting it with aniline and the amino acid statistically when p ˂  0.05 for the analysis of t-test. The glycine. Microcrystalline cellulose used in this work was flame type was air-C H . 2 2 extracted from olive industry solid waste (OISW) [32, 33]. The prepared polymer showed an excellent affinity Preparation of cellulose acetoacetate (Cell‑AA) for various heavy metals since the functional groups are A sample of microcrystalline cellulose (5.0  g, 0.15  mol/ considered multidentate chelating agents. The adsorp - anhydrous glucose repeat unit) was added to a 0.5  L tion efficiency of the three cellulose-based polymers was one necked round bottomed flask containing 200.0  ml Nair at et al. BMC Chemistry (2022) 16:43 Page 3 of 21 OH OH OH OH OH OH OH OH OH OH OH OH O O O O O O O O O O O O O HO OH HO HO OH HO OH HO HO HO OH HO LiCl/DMAc O O O O O O OH OH OH OH OH OH O O OH OH OH O O O O O O O O O O O HO OH O HO OH HO OH HO OH O O O O O Cell-AA O O O NH MeOH, HOAc NH NH NH O O O OH OH OH OH OH O O O OH OH OH OH O O O O O O O O O O O HO OH O HO OH HO OH HO OH O O O O O NH NH HN NH Cell- -AN Fig. 1 Preparation of cellulose acetoacetate from Cellulose and t-BAA distilled water and stirred magnetically for 2  h at room (2.697  mol) in a 500  ml round bottomed flask equipped temperature. The cellulose was collected from water by with a magnetic stir bar and condenser, the flask was con - suction filtration then suspended in 200 ml methanol for nected to a trap via the condenser and kept under nitro- one hour. This process was repeated three times to acti - gen gas. The mixture was stirred at room temperature vate the cellulose and remove water. The activated cel - until a clear solution was obtained (about two hours). lulose was collected by suction filtration then suspended Then, a 33.5  ml of a t-butyl acetoacetate (t-BAA) (9.6  g, in a 130.0 ml anhydrous DMAc two times, the first time 61.5  mmol) was added dropwise to the solution under a was done for an hour, while the second time was carried blanket of nitrogen and heated to 120  ºC using oil bath out overnight. The activated cellulose was then collected in a 2  h period and stirred overnight. The reaction was by suction filtration and transferred to was added to a transferred to a 1 L beaker, then 500 ml of distilled water solution of LiCl in DMAc (8.0%, 150  mL) prepared by was added dropwise to the reaction and then placed in dissolving a 9.75 g of anhydrous LiCl in a 150 ml DMAc the refrigerator overnight. Nairat et al. BMC Chemistry (2022) 16:43 Page 4 of 21 Fig. 2 FT-IR spectrum for Cell-AA Fig. 3 FT-IR spectrum for Cell-β-AN Nair at et al. BMC Chemistry (2022) 16:43 Page 5 of 21 O O O O O OH OH OH OH OH O O O OH OH OH OH O O O O O O O O O O HO OH O HO OH HO OH HO OH O O O O O O O O OH H N OH OH O O H NH NH N OH O O O OH OH OH OH OH O O O OH OH OH OH O O O O O O O O O O O O HO OH O HO OH HO OH HO OH O O O O O NH NH HN NH O O HO HO HO HO Fig. 4 Preparation of cellulose β-aminoacetonate using glycine Fig. 5 FT-IR spectrum for Cell-β-GL The resulted gel was filtered by suction filtration then first stirring was done for 15  min, while the second one transferred to a 1000  ml beaker containing 500  ml of was carried out for 30 min. Product was collected by suc- methanol for washing. This step was repeated twice, the tion filtration and dried at 100 ºC, yield was about 86.7%. Nairat et al. BMC Chemistry (2022) 16:43 Page 6 of 21 Preparation of cellulose β‑glycine ester (Cell‑β‑GL) OH A 2.0 g of cell-AA polymer was suspended in acetic acid (40  ml), then 2.0  g (1.587  ml, 26.6  mmol) of glycine was Pb(II) added at once. Reflux was done for 6  h at 70  ºC. The Pb(II) O resulting polymer was washed two times with water, diluted solution of sodium bicarbonate (1.0%), water and O O finally two times with methanol, and dried at 90 ºC. HO OH HO OH Fig. 6 Representative structures show the interaction between Adsorption study Cell-β-GL and Cell-β-AN and the metal ion Pb(II) All experiments were performed in plastic vials (50  ml each) that were held in a shaker and placed in a water bath equipped with a thermostat. The effect of various variable such as metal ion concentration (C ), adsorp- tion time, pH value, adsorbent dosage, and temperature on adsorption efficiency was evaluated. The adsorption study was performed on the Pb(II) metal ion. A sample of each mixture was withdrawn using a 5.0  ml plastic syringe, then filtered through a 0.45 µm syringe filter. The collected filtrate was analyzed by FAAS at 217.0  nm for determining the residual metal ion concentration and thus to determine the adsorption efficiency according to Eq. 1 and 2, respectively. C − C o e R (% ) = 100 (1) C − C o e Q = V (2) C and C are the initial and equilibrium concentration in 0 e ppm of metal ion in solution respectively, Q (ppm) is the equilibrium adsorption capacity of the adsorbent (mg/g), m is the weight of the adsorbent (g), and V is the volume of the solution (L). Wastewater purification A sample of sewage water collected from the Beit Dajan wastewater purification planet (Nablus-Palestine) was Fig. 7 The SEM images of a Cell-β-AN and b Cell-β-GL at a used in this study. The sample was first analyzed by ICP- magnification of 250x 500x, respectively AES (Water Center, An-Najah National University, Nab- lus, Palestine) to determine the metals content and their concentrations. Then three 10  ml samples of the waste - Preparation of cellulose β‑aniline ester (Cell‑βAN) ‑ water were placed in two Erlenmeyer flasks, a 100  mg A 2.0  g sample of cell-AA polymer was suspending in a of each cellulose-based polymer (Cell-AA, Cell-β-AN, 100 ml methanol, then 2.0 ml (2.04 g, 21.9 mmol) of ani- Cell-β-GL) was added to each flask. The pH of the solu - line was added in one portion, followed with a 2.0  ml tion was adjusted to 8.0. The mixtures were shaken at (2.1  g, 34.96  mmol) of acetic acid, added at once as a room temperature for 30 min using a thermostat shaker. catalyst. The mixture was refluxed for 8  h. The resulting A 5.0 mL sample of each mixture was withdrawn and fil - polymer was filtered, washed with water (3 x 20 mL) and tered through a 0.45  µm syringe filter and analyzed by dried in an oven at 110 ºC. ICP-AES for residual metal ions concentrations. Nair at et al. BMC Chemistry (2022) 16:43 Page 7 of 21 110 10 TGA for Cell-β-AN TGA for Cell-AA 90 8 DTG for Cell-β-AN DTG for Cell-AA 70 6 50 10 50 4 40 40 30 30 2 20 20 10 0 -10 -2 -10 0200 400600 800 -100 0 100 200 300 400 500 600 700 800 900 Temperature Temprature ( C) TGA for Cell-β-GL DTG for Cell-β-GL 80 C -5 0100 200 300 400 500 600 700 800 900 Temperature ( C) Fig. 8 TGA and DTG analysis results of A Cell-AA, B Cell-β-AN C Cell-β-GL polymers DFT calculations scheme (D30) [40]. The adsorption energy is evaluated DFT was performed using the Dmol3 software. Geom- using the well-known method [41–44]. The non-covalent etry optimization (spin unrestricted) using the double interaction (NCI) was calculated using Multiwfn soft- numerical plus polarization basis set (DNP) along with ware [45]. The NCI surface is plotted using software the the PBE functional within the m-GGA approximation is Visual Molecular Dynamics [46]. used. Grimee DFT-D was used to provide dispersion cor- Molecular Dynamic simulations were with the universal rection effects. The COSMO method is used to include force field [47] to obtain detailed molecular details to eluci - water as a solvent [34–37]. For the ELF—analysis, a sin- date the adsorption process of the between lead ions and the gle point geometry calculation (using geometry coordi- Cell-β-AN or Cell-β-GL surface. The adsorption is modelled nates generated by the Dmol software in the previous using an 8 monomeric cellulose unit with a side chain modi- step) was performed using the Orca software [38] at the fied by 8 GL or AN moiety, containing an upper layer com - density functional theory level with the M06 exchange- posed of 400 water molecules and 3 Pb(II) ions. The MD is correlation functional and the def2-TZVP basis set [39]. performed under NVT ensemble at 298.15 K, with 1 fs time The van der Waals interactions were accounted for by an step and a total simulation time of 2500  ps [37, 48–57]. A atom-pair dispersion correction using the zero-damping Nose thermostat is used for temperature control [58]. mass% mass% DTG (%/min) mass% DTG (%/min) DTG (%/min) Nairat et al. BMC Chemistry (2022) 16:43 Page 8 of 21 60 B Cell-AA Cell-AA Cell-β-AN Cell-β-AN Cell-β-GL Cell-β-GL Polymer dosage (mg) time (min) 70 70 Cell-AA Cell-β-AN 60 Cell-AA 60 C Cell-β-GL Cell-β-AN Cell-β-GL 10 20 30 40 50 60 10 20 30 40 50 60 70 o Lead solution concentration (ppm) Temperature ( C) Cell-β-GL Cell-β-AN Cell-AA 246 81012 PH value Fig. 9 The effect of a: adsorbent dose, b adsorption time, c temperature, d pH, and e initial ion concentration on the metal removal by the three adsorbents The prepared Cell-AA was characterized by FT-IR, Result and discussion obtained spectrum is shown in Fig.  2. The most sig - Synthesis of cellulose‑acetoacetate polymers (Cell‑AA) nificant peaks for Cell-AA were observed at 1742 and Cellulose functionalized with acetoacetate group was -1 1709  cm assigned to the carbonyls of ester and ketone, prepared according to a procedure reported in the lit- respectively. The IR spectrum also shows three bands at erature with major modification [59]. Cellulose was -1 about 1152, 1057 and 1033  cm corresponding to the dissolved in 8.0 wt% LiCl/DMAc solution at room tem- vibration of C–O–C of ester, pyranose ring skeletal and perature then reacted with tert-butyl β-ketoester at about to β-glycosidic linkage respectively. The broad peak at 110 °C for 6 h (Fig. 1). The yield after product purification -1 3439  cm attributed to the O-H bond stretching. was about 86.7%. Metal removal (%) Percent removal of lead ions % Adsorption % removal Percent removal of lead ions Nair at et al. BMC Chemistry (2022) 16:43 Page 9 of 21 is not sharp, because it overlaps with the OH group peak 100.2 which has almost the same wavenumber. The carbonyl of Cell-AA 100.0 -1 the ester group appears at 1740  cm , IR spectrum shows Cell-β-AN -1 99.8 Cell-β-GL two bands at about 1157 and 1033  cm  of C–O–C ring of pyranose ring skeletal and to β-glycosidic linkage vibra- 99.6 −1 tion, respectively. The adsorption peak at 2922  cm   is 99.4 corresponding to symmetric and asymmetric stretching 99.2 vibration of the C–H bond. The two peaks at about 3010 -1 99.0 and 1582  cm could be attributed to =C-H and C=C stretching vibrations in an aromatic part of Cell-β-AN as 98.8 shown in Fig. 3. 98.6 The cellulose β-glycinocetoester (Cell-β-GL) was pro - 98.4 duced from reacting cellulose acetoacetate with the 01234567 8 amino acid glycine, acetic acid was used as a solvent and Recycle nubber a catalyst as proposed in Fig.  4. The FT-IR spectrum of the Cell-β-GL is shown in Fig.  5. The broad strong peak Fig. 10 Adsorption efficiency, effect of adsorbent recycling -1 at 1713  cm composed of several overlapped peaks that could be attributed to C=O of ester and carboxyl groups. -1 The broad peak at about 3300  cm is attributed to the stretching hydrogen bonded hydroxyl group of alcohol and carboxyl. Table 1 Percent removal of metal ions present in sewer using The IR spectrum also shows three bands at about 1152, the three adsorbents. -1 1050 and 1030  cm for C-O–C of ester, pyranose ring Metal Ions Initial conc. (ppm) % Removal skeletal and to β-glycosidic linkage vibration respectively. −1 The adsorption peak at 2963  cm is corresponding to Cell‑ AA Cell‑β ‑ AN Cell‑β ‑ GL symmetric and asymmetric stretching vibration of the Al(III) 12.936 84.539 95.371 82.195 C-H bond. Ba(II) 34.307 94.753 95.737 92.316 The cellulose-based Schiff bases were designed to have B(III) 97.531 98.052 97.575 97.947 a high affinity for various metals. As shown in Fig.  6, the Cr(IV ) 27.844 89.585 85.270 84.789 coordination sites bi and tridentate ligand with binding Cu(II) 3.773 52.293 90.125 45.593 sites contain amines, carbonyl and hydroxyl. Fe(III) 205.49 98.686 99.745 98.201 Pb(II) 7.473 87.957 61.165 89.476 SEM analysis Mn(II) 19.822 87.388 90.582 84.893 The SEM images of the two polymers Cell-β-GL and Ni(II) 4.139 85.504 59.839 72.363 Cell-β-AN are shown in Fig.  7, the images show the sur- V(III) 1.973 8.768 59.253 64.587 face morphology that appears as a spongy. This explains Zn(II) 13.07 68.631 95.371 82.195 the high affinity of the polymers for the metal ions. Polymer solubility in water The solubilities of the three polymers in water was deter - mined by suspending 0.5  g of each of the polymers in 50  ml water and stirring for about 6  h. Then collected Cell-AA was reacted with aniline, which undergoes a by suction filtration, dried in an oven at 100  °C, and condensation reaction with the Ketone carbonyl to form weighed. Negligible reduction in the weight was noticed. Cell-β-AN functionality. The reaction is summarized in Fig 1. The FT-IR spectrum of the Schiff base Cell-β-AN TGA analysis and thermal stability (Fig.  3). The disappearance of the ketone domain at TGA was performed on the three polymers, results are 1709 and the presence of an amine group C-N at about -1 shown in Fig. 8. All polymers show about the same trend, 1271  cm is an indication that the amine linkage is -1 a major drop in the mass appears at 200  °C that could formed. The peak at 3473  cm is due to N-H vibration of -1 be related to the loss of the pendant group. Complete the secondary amine groups. The peak at 1740  cm  could decomposition started at about 400 °C. The polymers are be attributed to C=O of the ester group. The broad peak -1 considered thermally stable since it synthesized mainly at 3430  cm   could be attributed to the stretching of the for wastewater purification. hydrogen bonded hydroxyl group (O–H). The amine peak adsorption effeciency Nairat et al. BMC Chemistry (2022) 16:43 Page 10 of 21 0.36 0.32 0.28 0.24 0.20 0.16 Cell-AA 0.12 Cell-AA Cell-β-AG Cell-β-AN 0.08 Cell-β-AN Cell-β-AG 0.04 0.00 5 678 91011121314151617 1.61.8 2.02.2 2.42.6 2.83.0 Ce (mg/L) LnCe Fig. 11 A Langmuir adsorption model and B Freundlich adsorption model of Pb(II) ions on three adsorbents Table 2 Langmuir and Freundlich parameters for the adsorption the aqueous solution. So, the optimum pH value was of Pb(II) ions by cellulose-based polymers selected to be 9.0. Pb(II) Concentration effect on adsorption Cell‑ AA Cell‑β ‑ AG Cell‑β ‑ AN The effect of the initial lead ions concentration on adsorption efficiency was also investigated, the other Langmuir isotherm variables being kept constant (pH 4.3, time 30 min, solu- Q (mg/g) 2.4587 2.1256 2.1254 tion volume 10 mL and temperature at 30 °C). The maxi - K (L/mg) 0.1524 0.1202 0.1965 mum percentage of lead ions removal was about 44.4% by R 0.9625 0.8958 0.8548 cell-AA, 57.29% by Cell-β-AN and 63.7 % by Cell-β-GL Freundlich isotherm at 10 ppm initial concentration of Pb(II) (Fig. 9e). At con- 1/n 1.2154 0.9587 1.2548 centration higher than 10 ppm the rate of adsorption K (L/mg) 16.325 23.3254 17.325 decreases with increasing the concentration of lead ions. R 0.8536 0.9621 0.93254 The results show that, at a concentration of 10.0 ppm or lower, there are sufficient binding sites, and the adsorp - tion process is controlled by ion diffusion [60]. As the Adsorption of Pb(II) concentration increases, the availability of the binding pH effect on adsorption sites decreases until the binding site are almost saturated, The effect of the pH value on adsorption efficiency for and the adsorption process is controlled by the adsorbent the three polymers was studied, the other parameters dosage. were kept constant (adsorbent dose 40.0  mg, time 30 min, solution volume 10  mL and temperature at 30  °C). The results are shown in Fig 9d. At low pH value (about Contact time effect on adsorption 3.0) the amine presents in ammonium form (-NR H ), The effect of the contact time on %removal was evalu - 2 2 also the carboxyl and hydroxyl groups are in protonated ated under conditions of pH 4.3, initial ion concentration form (COOH and OH), so the adsorption efficiency was 10  ppm, volume of adsorbate 10  ml, adsorption tem- low. As the pH value increased the amines, carbonyl and perature 30 °C and adsorbent dose 50.0  mg. Results are hydroxyl groups start to shift to the Lewis base form, shown in Fig. 9b, the figure shows a sharp increase in the causing the hydroxyl, carbonyl and amine to behave as adsorption of Pb(II) after 30  min for all three polymers, a stronger chelating agent due to the availability of O which could have related to the availability of plenty of and N lone pairs of electrons. The highest efficiency was binding sites on the outer surface of the adsorbent. Then observed at pH 9. At pH value higher than 9, the adsorp- a slow increase was observed, the adsorption rate reached tion efficiency started to decline, this decrease could equilibrium after about 120 min, so at this period almost be related to formation of soluble metal oxide complex all adsorption sites are occupied [60]. A contact time of which reduced the adsorption efficiency of Pb(II) from Ce/Qe (g/l) LnQe Nair at et al. BMC Chemistry (2022) 16:43 Page 11 of 21 Table 3 The pseudo-second-order model for adsorption of Pb(II) ions onto cell-AA, cell-β-AN, and cell-β-AG Cell AA Cellβ AN Cellβ AG 2 2 2 K (g/ Q (mg/g) R K (g/mg.min) Q (mg/g) R K (g/ Q (mg/g) R 2 cal 2 cal 2 cal mg.min) mg.min) Pb(II) 0.3356 427.3254 0.9885 0.4325 548.3224 0.9750 0.465 632.2134 0.9887 Cell AA Cellβ AN Cellβ AG 2 2 2 K Z R K Z R K Z R id id id Pb(II) 0.1625 5.9021 0.9402 0.1503 5.8507 0.9514 0.1844 5.6977 0.9465 Parameters explain the intra-particle diffusion of Pb(II) ions onto cell-AA, cell-β-AN, and cell-β-AG. Nairat et al. BMC Chemistry (2022) 16:43 Page 12 of 21 2.0 A B 1.5 1.0 Cell-β-AN Cell-β-AN 0.5 Cell-β-AG Cell-β-AG Cell-AA Cell-AA 0.0 020406080100 120140 020406080100 120140 t (min) t (min) Cell-β-AN Cell-β-AG Cell-AA 345678 9101112 1/2 1/2 t (min ) Fig. 12 A Pseudo first-order model B Pseudo-second order model and C Intra-particle diffusion model for the adsorption of Pb(II) ions onto cell-AA, cell-β-AN, and cell-β-AG at various concentrations Table 4 Thermodynamic parameters for the adsorption of Pb(II) 2.50 ions onto cell-AA, cell-β-AN, and cell-β-AG 2.25 Pb(II) 2.00 ∆G° (KJ/mol) ∆H° (KJ/mol) ∆S° (J/K.mol) 1.75 1.50 Cell-AG − 17.2525 13.20211 74.92155 1.25 Cell-β-AG − 18.2314 Cell-β-AG − 18.8021 1.00 Cell-β-AN 0.75 Cell-β-AG Cell-AA 0.50 30  min was chosen as an equilibrium time for the three 0.25 polymers. 0.00 0.00300 0.00315 0.00330 0.00345 -1 1/T (K ) Temperature effect on adsorption Fig. 13 Adsorption thermodynamics of Pb(II) ions onto cell-AA, The effect of temperature on the adsorption rate of Pb(II) cell-β-AN, and cell-β-AG ions was studied under the conditions shown above at 15, 22, 30, 40 and 60  C. The highest adsorption rate was Ln(Qe-Qt) linKd Qt(mg/g) t/Qt (min,g/mg) Nair at et al. BMC Chemistry (2022) 16:43 Page 13 of 21 Fig. 14 A Different energy terms during the exploration of random MC configurations (3 000 000) and B Probability of the adsorption energy distributions during MC for the adsorbate ions onto modified cellulose surface found to be at 30  °C. At temperature higher than 30  °C, concentration of 10.0  ppm and a pH value of 4.3. The the percentage of removal tends to decrease as the tem- adsorption time was performed for 30  min at room perature rises as shown in Fig.  9c. This result is an indi - temperature. The results show that the amount of metal cation that the adsorption process is spontaneous at low extracted increased by increasing the polymer dosage. temperature. At high temperature values, over 30 °C, the The highest removal of about 60.5% was achieved using a percentage of metal removal decrease could be related to 40.0 mg of Cell-β-GL polymers. the kinetic energy of the adsorbed particle on the adsor- bent surface increase, which leads to an increase in the Desorption studies possibility of de-complexing from the adsorbent surface. The regeneration experiment was repeated seven times using the same adsorbent to determine the efficiency of Adsorbent dose effect on adsorption the polymers and the result are shown in Fig.  10. The The effect of adsorbent dosage on %removal is sum - adsorption efficiency decreases slightly as the number marized in Fig.  9a. The experiment was performed of regeneration cycles increases. In the seventh time, the using various amounts of adsorbents ranging from Cell-AA, Cell-β-GL and Cell-β-AN polymers absorption 5.0 mg to 50.0  mg and 10  ml solutions of Pb(II) with a of lead metals were 99%, 98.5% and 98.7% respectively. Nairat et al. BMC Chemistry (2022) 16:43 Page 14 of 21 2+ Fig. 15 Lowest energy configurations of Pb Pb ions onto the corresponding modified cellulose surfaces as obtained from MD Wastewater purification from metals unfavorable. However, when the R value is between Samples of sewage water were taken from the Beit Dajan 1 and 0, this indicates favorable adsorption, whereas wastewater treatment plant in Palestine. Three samples of when R = 1 indicates the presence of linear adsorp- this water were prepared to be treated with the prepared tion [20]. polymers according to the optimum conditions. The C 1 1 concentrations of the metal ions in each of the sewage = C + e (3) Q q q K e max max L samples prior and after using the polymers are summa- rized in Table  1. Metal ions concentrations were meas- Where C represents the equilibrium concentration of ured using ICP-MS. Excellent efficiency was achieved the adsorbate (mg/L), Qe is the amount of the adsorbate against some metal ions present in the wastewater sam- adsorbed per unit mass of cellulose-based polymers at ples because polymers contain several coordination sites equilibrium (mg/g), q is the adsorption capacity equi- max including hydroxyl, amine, and aromatics groups. librium (mg/g), and K is usually, the Langmuir affinity constant (L/mg). R = (4) Adsorption analysis 1 + K LC Isotherm C is the initial adsorbate concentration. Langmuir (Eq.  3) and Freundlich isotherm (Eq.  5) o models were applied to investigate the adsorption In (q ) = In k + In C (5) equilibrium between Pb(II) ion solution and the three e F e adsorbents [20]. Both models were used to assess the metal ion dispersion on the adsorbent surface at the K is the Freundlich constant that deals with adsorption equilibrium stage. The value of the correlation coef- capacity (mg/g) and n is the heterogeneity coefficient ficients, R (Eq.  4) can lead to the type of isotherm which leads to how favorable the adsorption process model of the adsorption process. The R ratio was (g/L). defined as a dimensionless quantity indicating that Figure  11 summarizes all adjustment parameters. sorption is favorable or not, since if the value of R The correlation coefficients of the Freundlich iso- is higher than 1, this indicates that the adsorption is therm model is lower for Cell-AA while it is higher for Nair at et al. BMC Chemistry (2022) 16:43 Page 15 of 21 1/2 Cell-β-AG and Cell-β-AN than those of the Langmuir From (Fig.  12C) (Qt vs. t) K and Z were calculated id isotherm model (Table  2), reflecting that the adsorp- and reported in Table  3. All graphs plotted in Fig.  16 tion of Pb(II) ions obey the Freundlich isotherm model didn’t cross the origin, indicating the occurrence of more for Cell-β-AG and Cell-β-AN and Langmuir isother- than one rate-limiting process. mal model for Cell-AA. The results indicate a single- Based on initial graphs linearity presented in Fig.  12B layer adsorption behavior with a heterogeneous energy it can be conclude that, at the outset of the adsorption distribution of the active sites along with the interac- process, the adsorption of Pb(II) on the three polymers tions between adsorbent and adsorbate. However, in takes place initially by an instantaneous adsorption step the case of Cell-AA polymer the Pb(II) cation are dis- (on the external surface), which caused a chemical com- tributed equally and homogeneously across the porous plexation between the metal ions and functional groups, surfaces of the cellulose based polymers [61].COOH, NR and the OH [21, 24, 63–70]. The other steps The separation factor R , which has been calculated were also linear, showing a progressive adsorption of for different quantities of adsorbent, ranges from 0< Pb(II) ions and the step of limiting intraparticle diffusion R <1 (Table 2). This reflects the high degree of affinity rate. of the three adsorbents for the studied metal ions. The results presented in Table  3 reveal that the Z values reflect an expansion in the upper layer of the adsorbent and Adsorption kinetics a decrease in the outer mass transfer although the inner The kinetic of the adsorption of metal ion Pb(II) by the mass transfer potential was increasing. The energy of acti - three adsorbents was evaluated using the kinetic mod- vation of the adsorption process was computed at 298 and els: pseudo-first order (Eq.  6) and pseudo-second order 323 K according to Eq. 8. models (Eq.  7) [62]. Weber and Morris developed Eq.  8 These findings are important for understanding how describing the intraparticle diffusion [62]. temperature influences adsorption performance of three polymers. The activation energy computed was nearly zero, ln(q − q ) = ln q − K t e t e 1 (6) suggesting a spontaneous adsorption process. 1 1 t Thermodynamics study = + (7) q K 2 q The thermodynamic parameters free energy, standard t 2q e enthalpy, and standard entropy for adsorption of Pb(II) by the three polymers were calculated using the following 1/2 Q = K t + Z (8) id equations [52]. The aim of this study is to understand the -1 spontaneity and the nature of adsorption. where Q (mg g ) is adsorption capacity at any time t, k t id 1/2 (mg/g min ) is the intraparticle diffusion rate constant, K = C /C c ads e (9) and Z (mg/g) is a constant proportional to the thickness of the boundary layer. G =−RTlnK (10) Table 3 and Fig. 12 summarize the values of all param- eters obtained using the above equations. The plots of S H Ln (q -q ) versus t (Fig.  12A) provide the value of K , e t 1 In K − (11) whereas the values of K and the adsorption capacity q R RT 2 e were derived from the slope and intercept of the plot of where K is an apparent constant of the thermodynamics; t/Qt versus t (Fig. 12B), while K and Z were deduced by id and C and C are respectively the amount adsorbed at 1/2 ads e tracing Qt vs t (Fig. 12C). equilibrium (mg/L) and concentration of metal ion in the The experimental results show that the correlation solution (mg/L), R is the universal gas constant (8.314 J/ coefficient (R ) for the pseudo-second order kinetics mol K); T is the solution temperature [54]. The (ΔG ) (J model (0.91 to 0.973) was greater than the value obtained -1 mol ) value was determined according to Eq.  10. The ln by pseudo-first order (0.891). Also, the qe values (2.675, K vs. 1/T was mapped as illustrated in Fig. 13, the slopes 15.252, 20.856  mg/g) which are close to the experimen- and crossings were utilized to determine various thermo- tal qe values (2.133, 13.91, 18.786  mg/g) for the three dynamics parameters as shown in Table 4. polymers Cell-AA, Cell-β-AG and Cell-β-AN, respec- 0 0 The value obtained for ΔS and ΔH are positive, tively, indicating that the adsorption process follows the whereas the entropy raised at the solid/solution interface pseudo-second order model for adsorption of Pb on the induced as a result of the adsorption process. The find - surfaces of the three polymers obey the pseudo-second ings further indicate that, the free energies for the three order (Table 3 and Fig. 12B). Nairat et al. BMC Chemistry (2022) 16:43 Page 16 of 21 2+ Fig. 16 The change of the adsorption energy (and corresponding energy terms) for the P b ions onto the modified cellulose surfaces obtained during the MD polymers were negative reflecting a spontaneous process intra-particle diffusion and adsorption of ions across the of adsorption at various temperatures. adsorbent particles. The results indicate that the metal removal occurs at various stages. In the first stage, metal ions migrate from Monte Carlo and molecular dynamic simulations the solution to the outer surface of the adsorbent, then Recognizing the adsorbate molecules’ preferred adsorp- diffuse across the boundary-layer to the outer surface of tion arrangement on the Cell-β-AN or GL surface is cru- the adsorbents, followed by coordination of metals ions cial for determining the various energy outputs. at the binding sites on the adsorbent surface, and lastly, Nair at et al. BMC Chemistry (2022) 16:43 Page 17 of 21 2+ Fig. 17 Noncovalent interaction surfaces and the plot of RDG vs sign(λ)ρ for the van der Waals interactions among the P b ions and the modified cellulose moieties 2+ Fig. 18 Electron localization function (ELF) analysis of the “bonding” between Pb ions and the side groups of the modified cellulose Nairat et al. BMC Chemistry (2022) 16:43 Page 18 of 21 Table 5 Mayer bond order for selected bonding atoms in the The assessment of the interaction nature amid the 2+ 2+ Pb / modified cellulose structures. Pb ions and the modified cellulose structures is per - formed via the NCI surface plot and the reduced density System Bonding atoms Mayer bond gradient (RDG) vs. sign (λ) (Fig.  17) [79, 80]. The green - order ish-blueish colored surface and the spikes with nega- tive sign (λ) values in the 2D NCI plot support that the Pb(II)|| GL Pb-O 0.313 van der Waals interactions are presented in the formed Pb-O 0.412 structures. Pb-N 0.197 The ‘bonding’ interaction among the Pb(II) ions and Pb(II)|| AN Pb-O 0.339 the side groups of the modified cellulose is discernible Pb-N 0.507 via the ELF analysis, where the low values of ELF indicate the low degree of covalence of these formed bonds [79]. This "binding" is also evident when Mayer’s binding order 2+ The interaction of the adsorbate ions Pb with the analysis is applied as shown in Fig. 18 and Table 5. modified cellulose surface enables the calculation of this The Mayer bond order ruptures the electron density method’s adsorption energetics. This is performed quan - in such a mode that the degree of bonding is calculated titatively by use the equation below to determine the in a modest way, where a perfectly fulfilled double bond adsorption energy (Eads) [71–77] : has a value of 2, a triple bond has a value of 3, and so on as shown in Table 5 [80]. The bond order values point to E = E adsorption Pb(II)/Cell−β−GLorAN 2+ (12) that the interaction of the P b ions is moderately strong − (Cell − β − GLorAL + Pb(II)) paralleled to other types of coordinative binding [81]. where E is the total energy of the sim- Pb(II)/Cell−β−GLorAL ulated adsorption system, Cell − β − GLorAN and Pb(II) Conclusion is the total energy of the adsorbate ions. Cellulose used in this study was extracted from olive Figure 14 shows the energy terms and the energy evolu- industry solid waste, it was successfully functional- tion during MC for the most sable or low energy adsorp- ized with the pendant group β-amino ester by first tion sites of adsorbates in the vicinity of the modified introducing 1,3-dicarbonyl to the cellulose repeat unit cellulose surface obtained through an excessive number then reacting it with aniline and the amino acid gly- of randomly generated Monte Carlo calculations. cine. The structures of the target polymers were identi - The experimental findings are supported by a strikingly fied by FT-IR spectroscopy and other techniques. The superior negative value of Eads of the adsorbate ions onto prepared three polymers showed excellent efficiency the both modified cellulose surface. toward removal of toxic metal ions from wastewater. The method for measuring and imaging the dynamics The optimum value of various parameters (contact of inhibitor adsorption on the materials surface is used time, pH value, adsorbent dose, temperature, and initial in MD simulation. Fig.  15 shows the adsorbate ions final concentration of lead ion) that lead to highest adsorp- structure on the modified cellulose surfaces. tion efficiency were determined. The adsorption mech - As can be seen in Fig. 16, where the adsorption energy anism follows the Langmuir isotherm model. Kinetic of the lead ions is calculated over the course of the entire data revealed that the adsorption of Pb(II) obeys the trajectory, the adsorption of the lead ions occurs spon pseudo second order. Thermodynamic study showed taneously (as indicated by the relatively high adsorp- negative Gibbs free energies, indicating a spontane- tion energy values), and the results are consistent with ous adsorption process of Pb(II) by the three polymers. those obtained experimentally [77, 78]. The mean of the Theoretical calculation using Monte Carlo (MC) and adsorption energy is calculated after the system equi- Molecular Dynamic (MD) simulation models were con- libration (last 2000 ps of the MD trajectory). The inter - ducted to confirm the experimental results of strong action is based mostly on the electrostatic one with a interaction and spontaneous adsorption between Pb(II) contribution through van der Waals forces. and the functional groups on the cellulose polymers. The relatively small changes of the adsorption energy The polymers quantitatively removed metal ions pre - (black line) energy as observed in Fig.  16, indicate that sent in a real sample of sewage and showed good des- the system has reached the lowest energy. orption properties. To better understand this interaction DFT calculations Acknowledgments involving a monomeric system of modified cellulose were The authors would like to thank the Palestinian Water Authority and the Midle performed. East Desalination Research Center (MEDRC) for the financial support of this work. Nair at et al. BMC Chemistry (2022) 16:43 Page 19 of 21 Author contributions 8. Abdel-Ghani NT, Hefny M, El-Chaghaby GA. Removal of lead from aque- Conceptualization, OH and SJ; formal analysis, NN; OD; investigation, KA; meth- ous solution using low cost abundantly available adsorbent. 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Cellulose polymers with β-amino ester pendant group: design, synthesis, molecular docking and application in adsorption of toxic metals from wastewater

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Abstract

Background: Cellulose polymers with multidentate chelating functionalities that have high efficiency for toxic metal ions present in water were designed, synthesized, and analyzed. The synthesis was carried out by reacting microcrys- talline cellulose extracted from the solid waste of the olive industry with tert-Butyl acetoacetate (Cell-AA), produced cellulose with β-ketoester functionality was then reacted with aniline and the amino acid glycine to produce Cell- β-AN and Cell-β-GL, respectively. Results: The adsorption efficiency of the three polymers toward Pb(II) and various toxic metal ions present in sewage was evaluated as a function of adsorbent dose, time, temperature, pH value, and initial ion concentration to deter- mine optimum adsorption conditions. The three polymers showed excellent efficiency toward about 20 metal ions present in a sewage sample collected from the sewer. The adsorption process follows the Langmuir adsorption iso- therm model with a second-order of adsorption rate, the calculated qe values (2.675, 15.252, 20.856 mg/g) were close to the experimental qe values (2.133, 13.91, 18.786 mg/g) for the three polymers Cell-AA, Cell-β-AG and Cell-β-AN, respectively. Molecular Dynamic (MD) and Monte Carlo (MC) simulations were performed on the three polymers com- plexed with Pb(II). Conclusion: The waste material of the olive industry was used as a precursor for making the target cellulose polymers with β-Amino Ester Pendant Group. The polymer was characterized by SEM, proton NMR, TGA, and FT-IR spectroscopy. The efficacy of adsorption was quantitative for metal ions present in a real sample of wastewater and the efficiency didn’t drop even after 7 cycles of use. The results indicate the existence of strong complexation. The thermodynamic study results showed a spontaneous bonding between of Pb(II) and the polymers pendant groups expressed by the negative value of the Gibbs free energy. Keywords: Water treatment, Persistent pesticides, Difenoconazole, Cellulose nanocrystalline, 2-furan carbonyl chloride, Cellulose, Monte Carlo, Glycine, Molecular dynamic, Adsorption, Wastewater Introduction Water contamination has become a critical global prob- *Correspondence: ohamed@najah.edu; sjodeh@najah.edu lem and a major health issue for living organisms and Chemistry Department, Faculty of Science, An-Najah National University, P.O. ecosystems. The issue was related to [1–3] industrial Box 7, Nablus, Palestine waste, agricultural waste, and the household cleaning Full list of author information is available at the end of the article © The Author(s) 2022. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http:// creat iveco mmons. org/ licen ses/ by/4. 0/. The Creative Commons Public Domain Dedication waiver (http:// creat iveco mmons. org/ publi cdoma in/ zero/1. 0/) applies to the data made available in this article, unless otherwise stated in a credit line to the data. Nairat et al. BMC Chemistry (2022) 16:43 Page 2 of 21 items that release toxic heavy metals, organic mate- evaluated toward Pb(II) and other metal ions from real rial, dyes and other to the sewage system [4–6]. Other wastewater samples. sources of toxic contaminants include medical, agricul- tural, plumbing, body care products. Among the toxic Experimental heavy metal ions that pose a risk and required immediate Material attention are Cd(II), Cu(II), Mn(II), Mg(II) Sr(II), Al(II), All chemicals and reagents used in this work were pur- Co(II), Ni(II), Cr(III), Zn(II) and Pb(II) ions [7, 8]. Recy- chased from Sigma-Aldrich chemical company (Jeru- cling of wastewater released from industrial and human salem) and used as received. The chemicals include activities has become a necessity. Among the most effec - tert-Butyl acetoacetate (t-BAA), lithium chloride tive technologies used in wastewater purification and anhydrous (LiCl), N,N-dimethylacetamide anhydrous recycling wastewater from toxic heavy metals and other (DMAc), aniline, glycine, lead(II) nitrate, acetic acid, contaminants are precipitation, membrane filtration, methanol and nitrogen gas (purity 99.9%). All reagents electrodialysis, electrochemical treatment, coagula- used were of analytical grade. Deionized water was used tion [9], flotation [10], cementation [11], solvent-solvent to prepare all solutions. Cellulose used in this work was extraction [12], ion exchange [13], chemical oxidation extracted from olive industry solid waste (Jeft) by a [14], reverse osmosis [15], and adsorption [16]. Amon chemical process that was developed at the laboratories these methods, adsorption received the highest atten- of An-Najah National University-Nablus/Palestine. tion due to its simplicity, availability, profitability, prac - ticality, ecofriendly, recyclability, relatively low cost, less Methods sludge production, high efficiency, and high selectivity Characterization [17–19]. The adsorption method mainly focuses on acti - Nicolet 6700 Fourier Transform Infrared (FT-IR) spec- vated carbon as the adsorbents. However, some withdraw trometer equipped with the Smart Split Pea micro-ATR backs such as processing costs have led the scientist to accessory (Thermo Fisher Scientific, Waltham, MA, search for other means [20]. More desirable adsorbents USA) was used in this work. The following IR param - -1 are those made from renewable, low-cost materials, eters were used: resolution 4  cm , spectral range 400– -1 especially those derived from agricultural waste materi-4000  cm , number of scans 128. Thermo-gravimetric als [21] and biological adsorbent [22, 23]. Natural based analysis (TGA) and differential scanning calorimetry adsorbents made from cellulose [24], lignin, chitosan and (DSC) measurements were performed using a TG/DSC hemicellulose received the most attention. They are eco - Star System (Mettler-Toledo) coupled with a MS-Ther - nomically feasible, environmentally friendly, and highly mostar GSD320 (Pfeiffer Vacuum) Mass Spectrometer. efficient for removal of heavy metal ions from wastewa - TG/DSC analysis was performed with Pt crucibles, in N −1 −1 ter [25]. Cellulosic based adsorbents and related obtained flow (20  mLmin ) at a heating rate of 5 ºC min in the from waste materials such as Kenaf [26, 27], cotton lint- range 25–1100 ºC by a HT1100 oven connected to a MX5 ers [28], wheat straw [29], wood sawdust [30], rice husk microbalance (thermostatic at 22  ºC). The STARE soft - [31] were prepared and investigated for the adsorption of ware v.10.0 (Mettler Toledo) controlled the process. several metals such as those mentioned above. Nanopar- Metal ions concentrations were determined using ticle adsorbents made from natural materials such as cel- Flame Atomic Absorption Spectrometer (FAAS, ICE3500 lulose nanocrystalline (CNC) were the most promising, AA System, Thermo scientific, United Kingdom) and the especially. Despite all the rapid progress in the nanocellu- inductively coupled plasma mass spectrometry (ICP- TM lose adsorbents still many celluloses-based materials and MS) via an iCAP RQ ICP-MS (Thermo Fisher Sci - derivatives have not been explored in wastewater purifi - entific, Waltham, MA, USA). All analysis studies were cation. In this work, new cellulose-based adsorbents were performed in triplicate and the mean of the three runs prepared and used in wastewater purification. The new was reported. The error range in the experimental data adsorbents were prepared by functionalizing microcrys- was analyzed using Excel Microsoft software, a certainty talline cellulose with β-ketoester to form cellulose with interval of 95% was used. The data analysis was per - 1,3-dicarbonyl pendant group, which then converted to a formed using the t-test. All variations were considered Schiff base by reacting it with aniline and the amino acid statistically when p ˂  0.05 for the analysis of t-test. The glycine. Microcrystalline cellulose used in this work was flame type was air-C H . 2 2 extracted from olive industry solid waste (OISW) [32, 33]. The prepared polymer showed an excellent affinity Preparation of cellulose acetoacetate (Cell‑AA) for various heavy metals since the functional groups are A sample of microcrystalline cellulose (5.0  g, 0.15  mol/ considered multidentate chelating agents. The adsorp - anhydrous glucose repeat unit) was added to a 0.5  L tion efficiency of the three cellulose-based polymers was one necked round bottomed flask containing 200.0  ml Nair at et al. BMC Chemistry (2022) 16:43 Page 3 of 21 OH OH OH OH OH OH OH OH OH OH OH OH O O O O O O O O O O O O O HO OH HO HO OH HO OH HO HO HO OH HO LiCl/DMAc O O O O O O OH OH OH OH OH OH O O OH OH OH O O O O O O O O O O O HO OH O HO OH HO OH HO OH O O O O O Cell-AA O O O NH MeOH, HOAc NH NH NH O O O OH OH OH OH OH O O O OH OH OH OH O O O O O O O O O O O HO OH O HO OH HO OH HO OH O O O O O NH NH HN NH Cell- -AN Fig. 1 Preparation of cellulose acetoacetate from Cellulose and t-BAA distilled water and stirred magnetically for 2  h at room (2.697  mol) in a 500  ml round bottomed flask equipped temperature. The cellulose was collected from water by with a magnetic stir bar and condenser, the flask was con - suction filtration then suspended in 200 ml methanol for nected to a trap via the condenser and kept under nitro- one hour. This process was repeated three times to acti - gen gas. The mixture was stirred at room temperature vate the cellulose and remove water. The activated cel - until a clear solution was obtained (about two hours). lulose was collected by suction filtration then suspended Then, a 33.5  ml of a t-butyl acetoacetate (t-BAA) (9.6  g, in a 130.0 ml anhydrous DMAc two times, the first time 61.5  mmol) was added dropwise to the solution under a was done for an hour, while the second time was carried blanket of nitrogen and heated to 120  ºC using oil bath out overnight. The activated cellulose was then collected in a 2  h period and stirred overnight. The reaction was by suction filtration and transferred to was added to a transferred to a 1 L beaker, then 500 ml of distilled water solution of LiCl in DMAc (8.0%, 150  mL) prepared by was added dropwise to the reaction and then placed in dissolving a 9.75 g of anhydrous LiCl in a 150 ml DMAc the refrigerator overnight. Nairat et al. BMC Chemistry (2022) 16:43 Page 4 of 21 Fig. 2 FT-IR spectrum for Cell-AA Fig. 3 FT-IR spectrum for Cell-β-AN Nair at et al. BMC Chemistry (2022) 16:43 Page 5 of 21 O O O O O OH OH OH OH OH O O O OH OH OH OH O O O O O O O O O O HO OH O HO OH HO OH HO OH O O O O O O O O OH H N OH OH O O H NH NH N OH O O O OH OH OH OH OH O O O OH OH OH OH O O O O O O O O O O O O HO OH O HO OH HO OH HO OH O O O O O NH NH HN NH O O HO HO HO HO Fig. 4 Preparation of cellulose β-aminoacetonate using glycine Fig. 5 FT-IR spectrum for Cell-β-GL The resulted gel was filtered by suction filtration then first stirring was done for 15  min, while the second one transferred to a 1000  ml beaker containing 500  ml of was carried out for 30 min. Product was collected by suc- methanol for washing. This step was repeated twice, the tion filtration and dried at 100 ºC, yield was about 86.7%. Nairat et al. BMC Chemistry (2022) 16:43 Page 6 of 21 Preparation of cellulose β‑glycine ester (Cell‑β‑GL) OH A 2.0 g of cell-AA polymer was suspended in acetic acid (40  ml), then 2.0  g (1.587  ml, 26.6  mmol) of glycine was Pb(II) added at once. Reflux was done for 6  h at 70  ºC. The Pb(II) O resulting polymer was washed two times with water, diluted solution of sodium bicarbonate (1.0%), water and O O finally two times with methanol, and dried at 90 ºC. HO OH HO OH Fig. 6 Representative structures show the interaction between Adsorption study Cell-β-GL and Cell-β-AN and the metal ion Pb(II) All experiments were performed in plastic vials (50  ml each) that were held in a shaker and placed in a water bath equipped with a thermostat. The effect of various variable such as metal ion concentration (C ), adsorp- tion time, pH value, adsorbent dosage, and temperature on adsorption efficiency was evaluated. The adsorption study was performed on the Pb(II) metal ion. A sample of each mixture was withdrawn using a 5.0  ml plastic syringe, then filtered through a 0.45 µm syringe filter. The collected filtrate was analyzed by FAAS at 217.0  nm for determining the residual metal ion concentration and thus to determine the adsorption efficiency according to Eq. 1 and 2, respectively. C − C o e R (% ) = 100 (1) C − C o e Q = V (2) C and C are the initial and equilibrium concentration in 0 e ppm of metal ion in solution respectively, Q (ppm) is the equilibrium adsorption capacity of the adsorbent (mg/g), m is the weight of the adsorbent (g), and V is the volume of the solution (L). Wastewater purification A sample of sewage water collected from the Beit Dajan wastewater purification planet (Nablus-Palestine) was Fig. 7 The SEM images of a Cell-β-AN and b Cell-β-GL at a used in this study. The sample was first analyzed by ICP- magnification of 250x 500x, respectively AES (Water Center, An-Najah National University, Nab- lus, Palestine) to determine the metals content and their concentrations. Then three 10  ml samples of the waste - Preparation of cellulose β‑aniline ester (Cell‑βAN) ‑ water were placed in two Erlenmeyer flasks, a 100  mg A 2.0  g sample of cell-AA polymer was suspending in a of each cellulose-based polymer (Cell-AA, Cell-β-AN, 100 ml methanol, then 2.0 ml (2.04 g, 21.9 mmol) of ani- Cell-β-GL) was added to each flask. The pH of the solu - line was added in one portion, followed with a 2.0  ml tion was adjusted to 8.0. The mixtures were shaken at (2.1  g, 34.96  mmol) of acetic acid, added at once as a room temperature for 30 min using a thermostat shaker. catalyst. The mixture was refluxed for 8  h. The resulting A 5.0 mL sample of each mixture was withdrawn and fil - polymer was filtered, washed with water (3 x 20 mL) and tered through a 0.45  µm syringe filter and analyzed by dried in an oven at 110 ºC. ICP-AES for residual metal ions concentrations. Nair at et al. BMC Chemistry (2022) 16:43 Page 7 of 21 110 10 TGA for Cell-β-AN TGA for Cell-AA 90 8 DTG for Cell-β-AN DTG for Cell-AA 70 6 50 10 50 4 40 40 30 30 2 20 20 10 0 -10 -2 -10 0200 400600 800 -100 0 100 200 300 400 500 600 700 800 900 Temperature Temprature ( C) TGA for Cell-β-GL DTG for Cell-β-GL 80 C -5 0100 200 300 400 500 600 700 800 900 Temperature ( C) Fig. 8 TGA and DTG analysis results of A Cell-AA, B Cell-β-AN C Cell-β-GL polymers DFT calculations scheme (D30) [40]. The adsorption energy is evaluated DFT was performed using the Dmol3 software. Geom- using the well-known method [41–44]. The non-covalent etry optimization (spin unrestricted) using the double interaction (NCI) was calculated using Multiwfn soft- numerical plus polarization basis set (DNP) along with ware [45]. The NCI surface is plotted using software the the PBE functional within the m-GGA approximation is Visual Molecular Dynamics [46]. used. Grimee DFT-D was used to provide dispersion cor- Molecular Dynamic simulations were with the universal rection effects. The COSMO method is used to include force field [47] to obtain detailed molecular details to eluci - water as a solvent [34–37]. For the ELF—analysis, a sin- date the adsorption process of the between lead ions and the gle point geometry calculation (using geometry coordi- Cell-β-AN or Cell-β-GL surface. The adsorption is modelled nates generated by the Dmol software in the previous using an 8 monomeric cellulose unit with a side chain modi- step) was performed using the Orca software [38] at the fied by 8 GL or AN moiety, containing an upper layer com - density functional theory level with the M06 exchange- posed of 400 water molecules and 3 Pb(II) ions. The MD is correlation functional and the def2-TZVP basis set [39]. performed under NVT ensemble at 298.15 K, with 1 fs time The van der Waals interactions were accounted for by an step and a total simulation time of 2500  ps [37, 48–57]. A atom-pair dispersion correction using the zero-damping Nose thermostat is used for temperature control [58]. mass% mass% DTG (%/min) mass% DTG (%/min) DTG (%/min) Nairat et al. BMC Chemistry (2022) 16:43 Page 8 of 21 60 B Cell-AA Cell-AA Cell-β-AN Cell-β-AN Cell-β-GL Cell-β-GL Polymer dosage (mg) time (min) 70 70 Cell-AA Cell-β-AN 60 Cell-AA 60 C Cell-β-GL Cell-β-AN Cell-β-GL 10 20 30 40 50 60 10 20 30 40 50 60 70 o Lead solution concentration (ppm) Temperature ( C) Cell-β-GL Cell-β-AN Cell-AA 246 81012 PH value Fig. 9 The effect of a: adsorbent dose, b adsorption time, c temperature, d pH, and e initial ion concentration on the metal removal by the three adsorbents The prepared Cell-AA was characterized by FT-IR, Result and discussion obtained spectrum is shown in Fig.  2. The most sig - Synthesis of cellulose‑acetoacetate polymers (Cell‑AA) nificant peaks for Cell-AA were observed at 1742 and Cellulose functionalized with acetoacetate group was -1 1709  cm assigned to the carbonyls of ester and ketone, prepared according to a procedure reported in the lit- respectively. The IR spectrum also shows three bands at erature with major modification [59]. Cellulose was -1 about 1152, 1057 and 1033  cm corresponding to the dissolved in 8.0 wt% LiCl/DMAc solution at room tem- vibration of C–O–C of ester, pyranose ring skeletal and perature then reacted with tert-butyl β-ketoester at about to β-glycosidic linkage respectively. The broad peak at 110 °C for 6 h (Fig. 1). The yield after product purification -1 3439  cm attributed to the O-H bond stretching. was about 86.7%. Metal removal (%) Percent removal of lead ions % Adsorption % removal Percent removal of lead ions Nair at et al. BMC Chemistry (2022) 16:43 Page 9 of 21 is not sharp, because it overlaps with the OH group peak 100.2 which has almost the same wavenumber. The carbonyl of Cell-AA 100.0 -1 the ester group appears at 1740  cm , IR spectrum shows Cell-β-AN -1 99.8 Cell-β-GL two bands at about 1157 and 1033  cm  of C–O–C ring of pyranose ring skeletal and to β-glycosidic linkage vibra- 99.6 −1 tion, respectively. The adsorption peak at 2922  cm   is 99.4 corresponding to symmetric and asymmetric stretching 99.2 vibration of the C–H bond. The two peaks at about 3010 -1 99.0 and 1582  cm could be attributed to =C-H and C=C stretching vibrations in an aromatic part of Cell-β-AN as 98.8 shown in Fig. 3. 98.6 The cellulose β-glycinocetoester (Cell-β-GL) was pro - 98.4 duced from reacting cellulose acetoacetate with the 01234567 8 amino acid glycine, acetic acid was used as a solvent and Recycle nubber a catalyst as proposed in Fig.  4. The FT-IR spectrum of the Cell-β-GL is shown in Fig.  5. The broad strong peak Fig. 10 Adsorption efficiency, effect of adsorbent recycling -1 at 1713  cm composed of several overlapped peaks that could be attributed to C=O of ester and carboxyl groups. -1 The broad peak at about 3300  cm is attributed to the stretching hydrogen bonded hydroxyl group of alcohol and carboxyl. Table 1 Percent removal of metal ions present in sewer using The IR spectrum also shows three bands at about 1152, the three adsorbents. -1 1050 and 1030  cm for C-O–C of ester, pyranose ring Metal Ions Initial conc. (ppm) % Removal skeletal and to β-glycosidic linkage vibration respectively. −1 The adsorption peak at 2963  cm is corresponding to Cell‑ AA Cell‑β ‑ AN Cell‑β ‑ GL symmetric and asymmetric stretching vibration of the Al(III) 12.936 84.539 95.371 82.195 C-H bond. Ba(II) 34.307 94.753 95.737 92.316 The cellulose-based Schiff bases were designed to have B(III) 97.531 98.052 97.575 97.947 a high affinity for various metals. As shown in Fig.  6, the Cr(IV ) 27.844 89.585 85.270 84.789 coordination sites bi and tridentate ligand with binding Cu(II) 3.773 52.293 90.125 45.593 sites contain amines, carbonyl and hydroxyl. Fe(III) 205.49 98.686 99.745 98.201 Pb(II) 7.473 87.957 61.165 89.476 SEM analysis Mn(II) 19.822 87.388 90.582 84.893 The SEM images of the two polymers Cell-β-GL and Ni(II) 4.139 85.504 59.839 72.363 Cell-β-AN are shown in Fig.  7, the images show the sur- V(III) 1.973 8.768 59.253 64.587 face morphology that appears as a spongy. This explains Zn(II) 13.07 68.631 95.371 82.195 the high affinity of the polymers for the metal ions. Polymer solubility in water The solubilities of the three polymers in water was deter - mined by suspending 0.5  g of each of the polymers in 50  ml water and stirring for about 6  h. Then collected Cell-AA was reacted with aniline, which undergoes a by suction filtration, dried in an oven at 100  °C, and condensation reaction with the Ketone carbonyl to form weighed. Negligible reduction in the weight was noticed. Cell-β-AN functionality. The reaction is summarized in Fig 1. The FT-IR spectrum of the Schiff base Cell-β-AN TGA analysis and thermal stability (Fig.  3). The disappearance of the ketone domain at TGA was performed on the three polymers, results are 1709 and the presence of an amine group C-N at about -1 shown in Fig. 8. All polymers show about the same trend, 1271  cm is an indication that the amine linkage is -1 a major drop in the mass appears at 200  °C that could formed. The peak at 3473  cm is due to N-H vibration of -1 be related to the loss of the pendant group. Complete the secondary amine groups. The peak at 1740  cm  could decomposition started at about 400 °C. The polymers are be attributed to C=O of the ester group. The broad peak -1 considered thermally stable since it synthesized mainly at 3430  cm   could be attributed to the stretching of the for wastewater purification. hydrogen bonded hydroxyl group (O–H). The amine peak adsorption effeciency Nairat et al. BMC Chemistry (2022) 16:43 Page 10 of 21 0.36 0.32 0.28 0.24 0.20 0.16 Cell-AA 0.12 Cell-AA Cell-β-AG Cell-β-AN 0.08 Cell-β-AN Cell-β-AG 0.04 0.00 5 678 91011121314151617 1.61.8 2.02.2 2.42.6 2.83.0 Ce (mg/L) LnCe Fig. 11 A Langmuir adsorption model and B Freundlich adsorption model of Pb(II) ions on three adsorbents Table 2 Langmuir and Freundlich parameters for the adsorption the aqueous solution. So, the optimum pH value was of Pb(II) ions by cellulose-based polymers selected to be 9.0. Pb(II) Concentration effect on adsorption Cell‑ AA Cell‑β ‑ AG Cell‑β ‑ AN The effect of the initial lead ions concentration on adsorption efficiency was also investigated, the other Langmuir isotherm variables being kept constant (pH 4.3, time 30 min, solu- Q (mg/g) 2.4587 2.1256 2.1254 tion volume 10 mL and temperature at 30 °C). The maxi - K (L/mg) 0.1524 0.1202 0.1965 mum percentage of lead ions removal was about 44.4% by R 0.9625 0.8958 0.8548 cell-AA, 57.29% by Cell-β-AN and 63.7 % by Cell-β-GL Freundlich isotherm at 10 ppm initial concentration of Pb(II) (Fig. 9e). At con- 1/n 1.2154 0.9587 1.2548 centration higher than 10 ppm the rate of adsorption K (L/mg) 16.325 23.3254 17.325 decreases with increasing the concentration of lead ions. R 0.8536 0.9621 0.93254 The results show that, at a concentration of 10.0 ppm or lower, there are sufficient binding sites, and the adsorp - tion process is controlled by ion diffusion [60]. As the Adsorption of Pb(II) concentration increases, the availability of the binding pH effect on adsorption sites decreases until the binding site are almost saturated, The effect of the pH value on adsorption efficiency for and the adsorption process is controlled by the adsorbent the three polymers was studied, the other parameters dosage. were kept constant (adsorbent dose 40.0  mg, time 30 min, solution volume 10  mL and temperature at 30  °C). The results are shown in Fig 9d. At low pH value (about Contact time effect on adsorption 3.0) the amine presents in ammonium form (-NR H ), The effect of the contact time on %removal was evalu - 2 2 also the carboxyl and hydroxyl groups are in protonated ated under conditions of pH 4.3, initial ion concentration form (COOH and OH), so the adsorption efficiency was 10  ppm, volume of adsorbate 10  ml, adsorption tem- low. As the pH value increased the amines, carbonyl and perature 30 °C and adsorbent dose 50.0  mg. Results are hydroxyl groups start to shift to the Lewis base form, shown in Fig. 9b, the figure shows a sharp increase in the causing the hydroxyl, carbonyl and amine to behave as adsorption of Pb(II) after 30  min for all three polymers, a stronger chelating agent due to the availability of O which could have related to the availability of plenty of and N lone pairs of electrons. The highest efficiency was binding sites on the outer surface of the adsorbent. Then observed at pH 9. At pH value higher than 9, the adsorp- a slow increase was observed, the adsorption rate reached tion efficiency started to decline, this decrease could equilibrium after about 120 min, so at this period almost be related to formation of soluble metal oxide complex all adsorption sites are occupied [60]. A contact time of which reduced the adsorption efficiency of Pb(II) from Ce/Qe (g/l) LnQe Nair at et al. BMC Chemistry (2022) 16:43 Page 11 of 21 Table 3 The pseudo-second-order model for adsorption of Pb(II) ions onto cell-AA, cell-β-AN, and cell-β-AG Cell AA Cellβ AN Cellβ AG 2 2 2 K (g/ Q (mg/g) R K (g/mg.min) Q (mg/g) R K (g/ Q (mg/g) R 2 cal 2 cal 2 cal mg.min) mg.min) Pb(II) 0.3356 427.3254 0.9885 0.4325 548.3224 0.9750 0.465 632.2134 0.9887 Cell AA Cellβ AN Cellβ AG 2 2 2 K Z R K Z R K Z R id id id Pb(II) 0.1625 5.9021 0.9402 0.1503 5.8507 0.9514 0.1844 5.6977 0.9465 Parameters explain the intra-particle diffusion of Pb(II) ions onto cell-AA, cell-β-AN, and cell-β-AG. Nairat et al. BMC Chemistry (2022) 16:43 Page 12 of 21 2.0 A B 1.5 1.0 Cell-β-AN Cell-β-AN 0.5 Cell-β-AG Cell-β-AG Cell-AA Cell-AA 0.0 020406080100 120140 020406080100 120140 t (min) t (min) Cell-β-AN Cell-β-AG Cell-AA 345678 9101112 1/2 1/2 t (min ) Fig. 12 A Pseudo first-order model B Pseudo-second order model and C Intra-particle diffusion model for the adsorption of Pb(II) ions onto cell-AA, cell-β-AN, and cell-β-AG at various concentrations Table 4 Thermodynamic parameters for the adsorption of Pb(II) 2.50 ions onto cell-AA, cell-β-AN, and cell-β-AG 2.25 Pb(II) 2.00 ∆G° (KJ/mol) ∆H° (KJ/mol) ∆S° (J/K.mol) 1.75 1.50 Cell-AG − 17.2525 13.20211 74.92155 1.25 Cell-β-AG − 18.2314 Cell-β-AG − 18.8021 1.00 Cell-β-AN 0.75 Cell-β-AG Cell-AA 0.50 30  min was chosen as an equilibrium time for the three 0.25 polymers. 0.00 0.00300 0.00315 0.00330 0.00345 -1 1/T (K ) Temperature effect on adsorption Fig. 13 Adsorption thermodynamics of Pb(II) ions onto cell-AA, The effect of temperature on the adsorption rate of Pb(II) cell-β-AN, and cell-β-AG ions was studied under the conditions shown above at 15, 22, 30, 40 and 60  C. The highest adsorption rate was Ln(Qe-Qt) linKd Qt(mg/g) t/Qt (min,g/mg) Nair at et al. BMC Chemistry (2022) 16:43 Page 13 of 21 Fig. 14 A Different energy terms during the exploration of random MC configurations (3 000 000) and B Probability of the adsorption energy distributions during MC for the adsorbate ions onto modified cellulose surface found to be at 30  °C. At temperature higher than 30  °C, concentration of 10.0  ppm and a pH value of 4.3. The the percentage of removal tends to decrease as the tem- adsorption time was performed for 30  min at room perature rises as shown in Fig.  9c. This result is an indi - temperature. The results show that the amount of metal cation that the adsorption process is spontaneous at low extracted increased by increasing the polymer dosage. temperature. At high temperature values, over 30 °C, the The highest removal of about 60.5% was achieved using a percentage of metal removal decrease could be related to 40.0 mg of Cell-β-GL polymers. the kinetic energy of the adsorbed particle on the adsor- bent surface increase, which leads to an increase in the Desorption studies possibility of de-complexing from the adsorbent surface. The regeneration experiment was repeated seven times using the same adsorbent to determine the efficiency of Adsorbent dose effect on adsorption the polymers and the result are shown in Fig.  10. The The effect of adsorbent dosage on %removal is sum - adsorption efficiency decreases slightly as the number marized in Fig.  9a. The experiment was performed of regeneration cycles increases. In the seventh time, the using various amounts of adsorbents ranging from Cell-AA, Cell-β-GL and Cell-β-AN polymers absorption 5.0 mg to 50.0  mg and 10  ml solutions of Pb(II) with a of lead metals were 99%, 98.5% and 98.7% respectively. Nairat et al. BMC Chemistry (2022) 16:43 Page 14 of 21 2+ Fig. 15 Lowest energy configurations of Pb Pb ions onto the corresponding modified cellulose surfaces as obtained from MD Wastewater purification from metals unfavorable. However, when the R value is between Samples of sewage water were taken from the Beit Dajan 1 and 0, this indicates favorable adsorption, whereas wastewater treatment plant in Palestine. Three samples of when R = 1 indicates the presence of linear adsorp- this water were prepared to be treated with the prepared tion [20]. polymers according to the optimum conditions. The C 1 1 concentrations of the metal ions in each of the sewage = C + e (3) Q q q K e max max L samples prior and after using the polymers are summa- rized in Table  1. Metal ions concentrations were meas- Where C represents the equilibrium concentration of ured using ICP-MS. Excellent efficiency was achieved the adsorbate (mg/L), Qe is the amount of the adsorbate against some metal ions present in the wastewater sam- adsorbed per unit mass of cellulose-based polymers at ples because polymers contain several coordination sites equilibrium (mg/g), q is the adsorption capacity equi- max including hydroxyl, amine, and aromatics groups. librium (mg/g), and K is usually, the Langmuir affinity constant (L/mg). R = (4) Adsorption analysis 1 + K LC Isotherm C is the initial adsorbate concentration. Langmuir (Eq.  3) and Freundlich isotherm (Eq.  5) o models were applied to investigate the adsorption In (q ) = In k + In C (5) equilibrium between Pb(II) ion solution and the three e F e adsorbents [20]. Both models were used to assess the metal ion dispersion on the adsorbent surface at the K is the Freundlich constant that deals with adsorption equilibrium stage. The value of the correlation coef- capacity (mg/g) and n is the heterogeneity coefficient ficients, R (Eq.  4) can lead to the type of isotherm which leads to how favorable the adsorption process model of the adsorption process. The R ratio was (g/L). defined as a dimensionless quantity indicating that Figure  11 summarizes all adjustment parameters. sorption is favorable or not, since if the value of R The correlation coefficients of the Freundlich iso- is higher than 1, this indicates that the adsorption is therm model is lower for Cell-AA while it is higher for Nair at et al. BMC Chemistry (2022) 16:43 Page 15 of 21 1/2 Cell-β-AG and Cell-β-AN than those of the Langmuir From (Fig.  12C) (Qt vs. t) K and Z were calculated id isotherm model (Table  2), reflecting that the adsorp- and reported in Table  3. All graphs plotted in Fig.  16 tion of Pb(II) ions obey the Freundlich isotherm model didn’t cross the origin, indicating the occurrence of more for Cell-β-AG and Cell-β-AN and Langmuir isother- than one rate-limiting process. mal model for Cell-AA. The results indicate a single- Based on initial graphs linearity presented in Fig.  12B layer adsorption behavior with a heterogeneous energy it can be conclude that, at the outset of the adsorption distribution of the active sites along with the interac- process, the adsorption of Pb(II) on the three polymers tions between adsorbent and adsorbate. However, in takes place initially by an instantaneous adsorption step the case of Cell-AA polymer the Pb(II) cation are dis- (on the external surface), which caused a chemical com- tributed equally and homogeneously across the porous plexation between the metal ions and functional groups, surfaces of the cellulose based polymers [61].COOH, NR and the OH [21, 24, 63–70]. The other steps The separation factor R , which has been calculated were also linear, showing a progressive adsorption of for different quantities of adsorbent, ranges from 0< Pb(II) ions and the step of limiting intraparticle diffusion R <1 (Table 2). This reflects the high degree of affinity rate. of the three adsorbents for the studied metal ions. The results presented in Table  3 reveal that the Z values reflect an expansion in the upper layer of the adsorbent and Adsorption kinetics a decrease in the outer mass transfer although the inner The kinetic of the adsorption of metal ion Pb(II) by the mass transfer potential was increasing. The energy of acti - three adsorbents was evaluated using the kinetic mod- vation of the adsorption process was computed at 298 and els: pseudo-first order (Eq.  6) and pseudo-second order 323 K according to Eq. 8. models (Eq.  7) [62]. Weber and Morris developed Eq.  8 These findings are important for understanding how describing the intraparticle diffusion [62]. temperature influences adsorption performance of three polymers. The activation energy computed was nearly zero, ln(q − q ) = ln q − K t e t e 1 (6) suggesting a spontaneous adsorption process. 1 1 t Thermodynamics study = + (7) q K 2 q The thermodynamic parameters free energy, standard t 2q e enthalpy, and standard entropy for adsorption of Pb(II) by the three polymers were calculated using the following 1/2 Q = K t + Z (8) id equations [52]. The aim of this study is to understand the -1 spontaneity and the nature of adsorption. where Q (mg g ) is adsorption capacity at any time t, k t id 1/2 (mg/g min ) is the intraparticle diffusion rate constant, K = C /C c ads e (9) and Z (mg/g) is a constant proportional to the thickness of the boundary layer. G =−RTlnK (10) Table 3 and Fig. 12 summarize the values of all param- eters obtained using the above equations. The plots of S H Ln (q -q ) versus t (Fig.  12A) provide the value of K , e t 1 In K − (11) whereas the values of K and the adsorption capacity q R RT 2 e were derived from the slope and intercept of the plot of where K is an apparent constant of the thermodynamics; t/Qt versus t (Fig. 12B), while K and Z were deduced by id and C and C are respectively the amount adsorbed at 1/2 ads e tracing Qt vs t (Fig. 12C). equilibrium (mg/L) and concentration of metal ion in the The experimental results show that the correlation solution (mg/L), R is the universal gas constant (8.314 J/ coefficient (R ) for the pseudo-second order kinetics mol K); T is the solution temperature [54]. The (ΔG ) (J model (0.91 to 0.973) was greater than the value obtained -1 mol ) value was determined according to Eq.  10. The ln by pseudo-first order (0.891). Also, the qe values (2.675, K vs. 1/T was mapped as illustrated in Fig. 13, the slopes 15.252, 20.856  mg/g) which are close to the experimen- and crossings were utilized to determine various thermo- tal qe values (2.133, 13.91, 18.786  mg/g) for the three dynamics parameters as shown in Table 4. polymers Cell-AA, Cell-β-AG and Cell-β-AN, respec- 0 0 The value obtained for ΔS and ΔH are positive, tively, indicating that the adsorption process follows the whereas the entropy raised at the solid/solution interface pseudo-second order model for adsorption of Pb on the induced as a result of the adsorption process. The find - surfaces of the three polymers obey the pseudo-second ings further indicate that, the free energies for the three order (Table 3 and Fig. 12B). Nairat et al. BMC Chemistry (2022) 16:43 Page 16 of 21 2+ Fig. 16 The change of the adsorption energy (and corresponding energy terms) for the P b ions onto the modified cellulose surfaces obtained during the MD polymers were negative reflecting a spontaneous process intra-particle diffusion and adsorption of ions across the of adsorption at various temperatures. adsorbent particles. The results indicate that the metal removal occurs at various stages. In the first stage, metal ions migrate from Monte Carlo and molecular dynamic simulations the solution to the outer surface of the adsorbent, then Recognizing the adsorbate molecules’ preferred adsorp- diffuse across the boundary-layer to the outer surface of tion arrangement on the Cell-β-AN or GL surface is cru- the adsorbents, followed by coordination of metals ions cial for determining the various energy outputs. at the binding sites on the adsorbent surface, and lastly, Nair at et al. BMC Chemistry (2022) 16:43 Page 17 of 21 2+ Fig. 17 Noncovalent interaction surfaces and the plot of RDG vs sign(λ)ρ for the van der Waals interactions among the P b ions and the modified cellulose moieties 2+ Fig. 18 Electron localization function (ELF) analysis of the “bonding” between Pb ions and the side groups of the modified cellulose Nairat et al. BMC Chemistry (2022) 16:43 Page 18 of 21 Table 5 Mayer bond order for selected bonding atoms in the The assessment of the interaction nature amid the 2+ 2+ Pb / modified cellulose structures. Pb ions and the modified cellulose structures is per - formed via the NCI surface plot and the reduced density System Bonding atoms Mayer bond gradient (RDG) vs. sign (λ) (Fig.  17) [79, 80]. The green - order ish-blueish colored surface and the spikes with nega- tive sign (λ) values in the 2D NCI plot support that the Pb(II)|| GL Pb-O 0.313 van der Waals interactions are presented in the formed Pb-O 0.412 structures. Pb-N 0.197 The ‘bonding’ interaction among the Pb(II) ions and Pb(II)|| AN Pb-O 0.339 the side groups of the modified cellulose is discernible Pb-N 0.507 via the ELF analysis, where the low values of ELF indicate the low degree of covalence of these formed bonds [79]. This "binding" is also evident when Mayer’s binding order 2+ The interaction of the adsorbate ions Pb with the analysis is applied as shown in Fig. 18 and Table 5. modified cellulose surface enables the calculation of this The Mayer bond order ruptures the electron density method’s adsorption energetics. This is performed quan - in such a mode that the degree of bonding is calculated titatively by use the equation below to determine the in a modest way, where a perfectly fulfilled double bond adsorption energy (Eads) [71–77] : has a value of 2, a triple bond has a value of 3, and so on as shown in Table 5 [80]. The bond order values point to E = E adsorption Pb(II)/Cell−β−GLorAN 2+ (12) that the interaction of the P b ions is moderately strong − (Cell − β − GLorAL + Pb(II)) paralleled to other types of coordinative binding [81]. where E is the total energy of the sim- Pb(II)/Cell−β−GLorAL ulated adsorption system, Cell − β − GLorAN and Pb(II) Conclusion is the total energy of the adsorbate ions. Cellulose used in this study was extracted from olive Figure 14 shows the energy terms and the energy evolu- industry solid waste, it was successfully functional- tion during MC for the most sable or low energy adsorp- ized with the pendant group β-amino ester by first tion sites of adsorbates in the vicinity of the modified introducing 1,3-dicarbonyl to the cellulose repeat unit cellulose surface obtained through an excessive number then reacting it with aniline and the amino acid gly- of randomly generated Monte Carlo calculations. cine. The structures of the target polymers were identi - The experimental findings are supported by a strikingly fied by FT-IR spectroscopy and other techniques. The superior negative value of Eads of the adsorbate ions onto prepared three polymers showed excellent efficiency the both modified cellulose surface. toward removal of toxic metal ions from wastewater. The method for measuring and imaging the dynamics The optimum value of various parameters (contact of inhibitor adsorption on the materials surface is used time, pH value, adsorbent dose, temperature, and initial in MD simulation. Fig.  15 shows the adsorbate ions final concentration of lead ion) that lead to highest adsorp- structure on the modified cellulose surfaces. tion efficiency were determined. The adsorption mech - As can be seen in Fig. 16, where the adsorption energy anism follows the Langmuir isotherm model. Kinetic of the lead ions is calculated over the course of the entire data revealed that the adsorption of Pb(II) obeys the trajectory, the adsorption of the lead ions occurs spon pseudo second order. Thermodynamic study showed taneously (as indicated by the relatively high adsorp- negative Gibbs free energies, indicating a spontane- tion energy values), and the results are consistent with ous adsorption process of Pb(II) by the three polymers. those obtained experimentally [77, 78]. The mean of the Theoretical calculation using Monte Carlo (MC) and adsorption energy is calculated after the system equi- Molecular Dynamic (MD) simulation models were con- libration (last 2000 ps of the MD trajectory). The inter - ducted to confirm the experimental results of strong action is based mostly on the electrostatic one with a interaction and spontaneous adsorption between Pb(II) contribution through van der Waals forces. and the functional groups on the cellulose polymers. The relatively small changes of the adsorption energy The polymers quantitatively removed metal ions pre - (black line) energy as observed in Fig.  16, indicate that sent in a real sample of sewage and showed good des- the system has reached the lowest energy. orption properties. To better understand this interaction DFT calculations Acknowledgments involving a monomeric system of modified cellulose were The authors would like to thank the Palestinian Water Authority and the Midle performed. East Desalination Research Center (MEDRC) for the financial support of this work. Nair at et al. BMC Chemistry (2022) 16:43 Page 19 of 21 Author contributions 8. Abdel-Ghani NT, Hefny M, El-Chaghaby GA. Removal of lead from aque- Conceptualization, OH and SJ; formal analysis, NN; OD; investigation, KA; meth- ous solution using low cost abundantly available adsorbent. Int J Environ odology, OH resources, SS; supervision, OH and SJ; validation, MA writing— Sci Technol. 2007;4(1):67–73. original draft, OH and NN writing—review and editing, MA and OD; software, 9. Peng H, Guo J. Removal of chromium from wastewater by membrane AB. All authors read and approved the final manuscript. filtration, chemical precipitation, ion exchange, adsorption electroco - agulation, electrochemical reduction, electrodialysis, electrodeionization, Funding photocatalysis and nanotechnology: a review. Environ Chemis Lett. This research received some funding from Middle East Desalination Research 2020;18(3):1–14. Center (MEDRC) and Palestine Water Authority (PWA)” grant number 10. Taseidifar M, Makavipour F, Pashley RM, Rahman AM. Removal of heavy MEDRC- 20-2022 metal ions from water using ion flotation. Environ Technol Innov. 2017;8:182–90. Data availability 11. 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BMC Chemistry – Springer Journals

Published: Jun 10, 2022

Keywords: Water treatment; Persistent pesticides; Difenoconazole; Cellulose nanocrystalline; 2-furan carbonyl chloride; Cellulose; Monte Carlo; Glycine; Molecular dynamic; Adsorption; Wastewater

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