H-bonding Interactions Research Articles

A co-assembly process for high strength and injectable dual network gels with sustained doxorubicin release performance.

Adopting a non-covalent co-assembly strategy shows great potential in loading drugs efficiently and safely in drug delivery systems. However, finding an efficient method for developing high strength gels with thixotropic characteristics is still challenging. In this work, by hybridizing the low molecular weight gelator fluorenylmethyloxycarbonyl-phenylalanine (Fmoc-F) (first single network, 1st SN) and alginate (second single network, 2nd SN) into a dual network (DN) gel, gels with high strength as well as thixotropy were prepared efficiently. The DN gels showed high strength (103 Pa in SN gels and 105 Pa in DN gels) and thixotropic characteristics (yield strain <25%; recovery ratio >85% within 100 seconds). The application performance was verified by loading doxorubicin (DOX), showing better encapsulation capacity (77.06% in 1st SN, 59.11% in 2nd SN and 96.71% in DN) and sustained release performance (lasting one week under physiological conditions) than single network gels. Experimental and DFT results allowed the elaboration of the specific non-covalent co-assembly mechanism for DN gel formation and DOX loading. The DN gels were formed by co-assembly driven by H-bond and π-π stacking interactions and then strengthened by Ca2+-coupling. Most DOX molecules co-assembled with Fmoc-F and alginate through π-π stacking and H-bond interactions (DOX-I), with a few free DOX molecules (DOX-II) left. Proven by the release dynamics test, DOX was released through a diffusion-erosion process, in an order of DOX-I first and then DOX-II. This work suggests that non-covalent co-assembly is a useful technique for effective material strengthening and drug delivery.

Enhancing the antibacterial efficacy of vancomycin analogues: targeting metallo-β-lactamases and cell wall biosynthesis.

Vancomycin is a crucial last-resort antibiotic for tackling Gram-positive bacterial infections. However, its potency fails against the more difficult-to-treat Gram-negative bacteria (GNB). Vancomycin derivatives have shown promise as broad-spectrum antibacterials, but are still underexplored. Toward this, we present a novel strategy wherein we substitute the sugar moiety of vancomycin with a dipicolyl amine group, yielding VanNHdipi. This novel glycopeptide enhances its efficacy against vancomycin-resistant bacteria by up to 100-fold. A comprehensive approach involving microbiological assays, biochemical analyses, proteomics, and computational studies unraveled the impact of this design on biological activity. Our investigations reveal that VanNHdipi, like vancomycin, disrupts membrane-bound steps of cell wall synthesis inducing envelope stress, while also interfering with the structural integrity of the cytoplasmic membrane, setting it apart from vancomycin. Most noteworthy is its potency against critical GNB producing metallo-β-lactamases (MBLs). VanNHdipi effectively inactivates various MBLs with IC50 in the range of 0.2-10 μM resulting in resensitization of MBL-producing bacteria to carbapenems. Molecular docking and molecular dynamics (MD) studies indicate that H-bonding interactions between the sugar moiety of the vancomycin derivative with the amino acids on the surface of NDM-1 facilitate enhanced binding affinity for the enzyme. This work expands the scope of vancomycin derivatives and offers a promising new avenue for combating antibiotic resistance.

Negative cooperativity in the formation of H-bond networks involving primary anilines.

Networks of H-bonds can show non-additive behaviour, where the strength of one interaction perturbs another. The magnitude of such cooperative effects can be quantified by measuring the effect of the presence of an intramolecular H-bond at one site on a molecule on the association constant for formation of an intermolecular H-bond at another site. This approach has been used to quantify the cooperativity associated with the interaction of a primary amine with two H-bond acceptors. A series of compounds that have an intramolecular H-bond between an aniline NH2 group and a pyridine nitrogen were prepared, using polarising substituents on the pyridine ring to vary the strength of the intramolecular H-bond. The presence of the intramolecular interaction was confirmed by X-ray crystallography in the solid state and NMR spectroscopy in n-octane solution. UV-vis absorption titrations were used to measure the association constants for formation of an intermolecular H-bond with tri-n-butyl phosphine oxide in n-octane. Electron-donating substituents on the pyridine ring, which increase the strength of the intramolecular H-bond, were found to decrease the strength of the intermolecular H-bond between the aniline and the phosphine oxide. The results were used to determine the H-bond donor parameters for the anilines, α, and there is a linear relationship between the values of α and the H-bond acceptor parameter of the pyridine group involved in the intramolecular H-bond, β. The slope of this relationship was used to determine the cooperativity parameter (κ = -0.10), which quantifies the negative allosteric cooperativity between the two H-bonding interactions. Calculated molecular electrostatic potential surfaces of the anilines quantitatively reproduce the experimental result, which suggests that effects are electrostatic in origin, either due to polarisation of the NH bonds or due to secondary electrostatic interactions between the two H-bond acceptors.

Polymer solubility mechanism in ionic liquids: 1H-NMR spectra and two-parameter hydrogen bonding analysis.

Understanding the polymer solubility in ionic liquids (ILs) is important for polymer processing or polymeric material preparation. Previously, two-parameter H-bonding analysis has been proposed to clarify that polymer solubility in ILs is dominated by H-bonding interactions (Y. F. Yuan et al., Phys. Chem. Chem. Phys., 2021, 23, 21893-21900). In the present work, 1H-NMR spectra are adopted to characterize the H-bonding interactions between polymers and ILs, which provide a microscopic relation between polymer solubility and two-parameter H-bonding analysis.

Real-time observation of the exchange process between H2O and NO in the metal–organic framework Ni-MOF-74

Combination of in situ IR spectroscopy and ab initio calculations reveals the detailed exchange process of H2O and NO in Ni-MOF-74 and uncovers its unusual energetics and kinetics caused by H-bonding interaction.

Facile Synthesis of 5-Bromo-N-Alkylthiophene-2-Sulfonamides and Its Activities Against Clinically Isolated New Delhi Metallo-β-Lactamase Producing Klebsiella pneumoniae ST147.

New Delhi Metallo-β-lactamase producing Klebsiella pneumoniae (NDM-1-KP) sequence type (ST) 147 poses a significant threat in clinical settings due to its evolution into two distinct directions: hypervirulence and carbapenem resistance. Hypervirulence results from a range of virulence factors, while carbapenem resistance stems from complex biological mechanisms. The NDM-1-KP ST147 clone has emerged as a recent addition to the family of successful clones within the species. In this study, we successfully synthesized 5-bromo-N-alkylthiophene-2-sulfonamides (3a-c) by reacting 5-bromothiophene-2-sulfonamide (1) with various alkyl bromides (2) using LiH. We also synthesized a series of compounds (4a-g) from compound (3b) using the Suzuki-Miyaura cross-coupling reaction with fair to good yields (56-72%). Further, we screened the synthesized molecules against clinically isolated New Delhi Metallo-β-lactamase producing Klebsiella pneumoniae ST147. Subsequently, we conducted in-silico tests on compound 3b against a protein extracted from NDM-KP ST147 with PDB ID: 5N5I. The compound (3b) with favourable drug candidate status, MIC of 0.39 μg/mL, and MBC of 0.78 μg/mL. This low molecular weight compound exhibited the highest potency against the resistant bacterial strains. The in-silico tests revealed that the compound 3b against a protein extracted from NDM-KP ST147 with PDB ID: 5N5I demonstrated H-bond and hydrophobic interactions. The 5-bromo-N-alkylthiophene-2-sulfonamides displayed antibacterial efficacy against New Delhi Metallo-β-lactamase producing Klebsiella pneumoniae ST147. After the in-vivo trial, this substance might offer an alternative therapeutic option.

A nanotrap infused ultrathin hybrid composite material for rapid and highly selective entrapment of 99TcO4.

99Tc is one of the potentially toxic radioactive substances owing to its long half-life and a high degree of environmental mobility. Hence, the sequestration of 99Tc from radioactive waste has become enormously important and a contemporary research priority. However, selective extraction of this species in its stable oxoanionic form (99TcO4 -) is very challenging on account of bottlenecks such as low charge density, less hydrophilic nature, etc. Herein, an ultrathin hybrid composite material has been strategically designed and fabricated by covalent anchoring of a chemically stable amino functionalized nanosized cationic metal-organic polyhedron with a positively charged robust ionic covalent organic framework. The resulting thin-layer-based hybrid composite presented multiple exfoliated exposed interactive sites, including a Zr(iv)-secondary building unit, amine and triaminoguanidine functional groups, which can selectively interact with TcO4 - oxoanions through a synergistic combination of electrostatic, H-bonding and various other supramolecular interactions. Thus synthesized function-tailored composite, by virtue of its multiple unique characteristics, manifested an ultrafast and very selective, high distribution coefficient (∼106 mL g-1), as well as recyclable entrapment of TcO4 - oxoanions from the complex mixture of superfluous (∼5000-fold) other interfering anions in both high and ultra-trace concentrations along with simulated nuclear waste and from different water systems. Dynamic flow-through experiments were conducted with the membrane of the hybrid material in simulated wastewater, which reduced the concentration of ReO4 - (surrogate of radioactive TcO4 -) to below the WHO permissible level with rapid sequestration kinetics and excellent selectivity over excessive competing anions.

Exploring the synergistic effect of aggregation and hydrogen bonding: a fluorescent probe for dual sensing of phytic acid and uric acid.

We synthesized an unoxidized bis-indolyl methane (BIM) derivative (probe 1) comprising of tetraphenylethylene (TPE) as the signalling moiety. The amphiphilic probe could form self-assembled nanoscopic aggregates in the aqueous medium. The emission of 1 in non-polar solvents originates from the LE state, while in polar solvents, it is dominated by TICT. Moreover, probe 1 exhibited a 'turn-on' fluorescence response for both uric acid (with a blue shift in emission maxima) and phytic acid (with a red shift in emission maxima). Therefore, the present system provides an exceptional opportunity to distinguish between phytic acid and uric acid by considering two different emission channels. Mechanistic investigations revealed that both H-bonding and electrostatic interactions between the probe and analytes could effectively cause restricted intramolecular rotations, leading to a turn-on response. Additionally, in the case of phytic acid, larger aggregates were observed with prominent CT characteristics. The change in the extent of charge transfer interaction in the formed adducts resulted in distinct fluorescence responses with phytic acid and uric acid. Furthermore, we explored the applicability of the present system in the screening of real-life samples, such as uric acid in urine samples and phytic acid in grains. The LOD for phytic acid and uric acid was found to be ∼5.48 nM and 10.4 nM, respectively. The quantitative nature of the system was confirmed, showing promising results in terms of recovery values (between 95.6% and 104.2%) and detection limits. Additionally, we also employed handy paper strips for the on-site monitoring of phytic acid and uric acid, thereby eliminating the need for complex instrumentation or trained technicians.

Direct synthesis of chiral β-arylamines via additive-free asymmetric reductive amination enabled by tunable bulky phosphoramidite ligands.

This report describes an additive-free iridium-catalyzed direct asymmetric reductive amination that enables the efficient synthesis of chiral β-arylamines, which are important pharmacophores present in a wide variety of pharmaceutical drugs. The reaction makes use of bulky and tunable phosphoramidite ligands for high levels of enantiomeric control, even for alkylamino coupling partners which lack secondary coordinating sites. The synthetic value of this succinct procedure is demonstrated by single-step synthesis of multiple drugs, analogs and key intermediates. Mechanistic investigations reveal an enamine-reduction pathway, in which H-bonding, steric repulsion, and CH-π and electrostatic interactions play important roles in defining the spatial environment for the "outer-sphere" hydride addition.

Design and synthesis of Meldrum's acid based 7-azaindole anchored 1,2,3-triazole hybrids as anticancer agents.

A series of Meldrum's acid, 7-azaindole and 1,2,3-triazole hybrids were synthesized and evaluated for their in vitro anticancer activity against five different cancer cell lines viz. MCF-7 (breast cancer), HeLa (cervical cancer), DU-145 (prostate cancer), HepG2 (liver cancer) and K562 (myelogenous leukemia cell). Among the series, compound 6b containing a 4-methyl substitution showed potent activity against HeLa cell line. Cell cycle analysis revealed that compound 6b induced cell cycle arrest at the G2/M phase and induced apoptosis. Apoptotic activity was further confirmed by Hoechst staining and Annexin V-FITC assay. Compound 6b has been found to exhibit higher activity in all four cell lines, with IC50 values of 6.67 ± 0.39 μM, 4.44 ± 0.32 μM, 12.38 ± 0.51 μM and 9.97 ± 0.25 μM against MCF-7, HeLa, DU-145 and HepG2 cell lines respectively. Compounds 6m (9.68 ± 0.10 μM) and 6n (9.52 ± 0.38 μM), which have dimethoxy and trimethoxy substitutions, respectively, have demonstrated significant anticancer activity against HeLa cells compared to the other cells. The molecular docking study of ligand 6b against the crystal structure of EGFR and Mcl-1 scored notable binding energy values and displayed important interactions like H-bond, π-cation and other hydrophobic interactions.

Mixed-ligand based water-stable Mn(II)-MOF for quick, sensitive, and reusable IFE-PET-RET facilitated detection of formaldehyde and Cr(VI)-oxoanions in real-field samples like food and industrial water: experimental and theoretical insights.

We report the luminescence-based detection of Group-1 carcinogen formaldehyde (FA) and Cr(VI)-oxoanions with a mesoporous Mn(II)-MOF (1), featuring a uninodal 4-c net topology and linear 1D square channels forming a polymeric 2D network. The Mn-MOF i.e., [Mn(phen)(hia)(H2O)]∞ was solvothermally constructed using π-conjugated, chelating phenanthroline (phen) and µ3-η2:η1 binding 5-hydroxyisophthalic acid (hia) ligands. The 2D rod-like crystallites of 1 demonstrated excellent phase purity, high thermal and photostability, and robustness under harsh conditions. The SCXRD and XPS studies established the structural framework and elemental composition, while the Hirshfeld surface analysis and NCI-RDG plot confirmed the presence of π-π stacking and weak interactions in 1. We explored the bright-blue emission of 1 for recyclable and fast-responsive (∼70 s) 'turn-off' detection of FA, with a low limit of detection (LOD) of 8.49 µM. Based on this, a 04-input-03-output molecular logic gate was proposed, which can be useful as a molecular switch for future applications. Furthermore, a unique experimental setup using the MOF film demonstrated ∼57% quenching upon exposure to FA vapor (an indoor VOC). Additionally, 1 exemplified itself as an efficient probe towards Cr(VI)-oxyanions, depicting LODs of 79 and 170 ppb, Stern-Volmer constants (KSV) of 16.13 × 104 and 12.73 × 104 M-1, and response times of ∼48 and ∼40 s for CrO42- and Cr2O72-, respectively. DFT calculations and specific wet-chemical investigations elucidated the FA detection to be triggered by photo-induced electron transfer (PET), while the Cr(VI)-sensing involved a combination of PET, the inner-filter effect (IFE), resonance energy transfer (RET), and electrostatic H-bonding interactions. The FA detection was validated using food samples (fish and meat) and wastewater specimens, achieving excellent recovery rates of ∼92-95%. Furthermore, the MOF's efficacy in recognizing the Cr(VI)-species in complex matrices (coal mine wastewater, sewage, and tap water) was investigated to yield high KSV values (3.10-5.17 × 104 and 2.16-7.03 × 104 M-1 for CrO42- and Cr2O72-), which demonstrated the probe's consistency and reliability.

Electronic structure and complexation behavior of methyl substituted phosphonate ligands with uranyl nitrate

Quantum chemical calculations were applied to investigate the electronic structures and complexation behaviour of methyl-substituted phosphonic acids with uranyl (VI) nitrate. The Natural Bond Orbital (NBO) analysis indicated that the methyl groups in substituted phosphonic acids exhibit electron-withdrawing properties. Additionally, the methyl groups directly bonded to the phosphoryl P atom prefer a gauche orientation relative to the P=O group in compounds such as MPn, DMMP and DMPn. Weak to moderate H-bonding interactions provided extra stability to Pn, MHPn, MPn and DMPn complexes with U(VI). The ν(P=O) values were red-shifted in all the complexes, implying a moderate weakening of the P=O bond upon complexation. Furthermore, the complexation energy values indicated an increasing complexation tendency in 1:2 complexes, particularly when the methyl groups were introduced. This trend was observed in the sequence Pn → MHPn → MPn and DMHP → DMMP → DMPn.

Metal-free functionalization of tyrosine residues in short peptides and study of the morphological alterations.

An efficient functionalization of tyrosine residues in phenolic regions is achieved under metal-free conditions. The strategy involves the conversion of a tyrosine residue to 4-amino phenylalanine or 4-amino-3-methoxy phenylalanine in short peptides through a controlled oxidative dearomatization. This transformation is achieved in one pot with good yields and excellent regioselectivity. Consequently, the self-assembly of the peptide compounds has been studied at the nanoscopic level before and after functionalization. The results suggest that the peptide derivatives comprising amide groups promote intermolecular H-bonding interactions and the difference in -OH and -NH2 functional groups is found to be responsible for the morphological changes. Morphological transitions from 1D nanowires to 2D nanosheets were observed during functional group modification.

Description of an original molecular ordering process into a disordered crystalline form: the atypical low-temperature transformation of the disordered form III of linezolid.

Form III of linezolid was prepared by heating the commercial form above 150 °C and subsequently analyzed upon cooling down to -160 °C, by low- and high-frequency Raman spectroscopy, differential scanning calorimetry and powder X-ray diffraction (PXRD). It was observed that form III was preserved down to 0 °C. At lower temperatures a soft mode was clearly detected by low-frequency Raman spectroscopy associated with the detection of additional Raman bands distinctive of additional intermolecular H-bond interactions. Raman spectroscopy investigations performed in a wide frequency range revealed a continuous transformation characterized by both displacive and order-disorder signatures. By contrast, PXRD highlighted the absence of symmetry breaking, Bragg peaks being still indexed in the same unit cell from room temperature down to -160 °C. Additionally, a significant broadening of Bragg peaks was observed with decreasing temperature interpreted as being a consequence of a distribution of frozen molecular conformations.

Supramolecular polymerization of [6]helicene-based cyano-luminogens: on the overall efficiency of self-assembled circularly polarized emitters.

The synthesis of the [6]helicene-based luminophores 1 and 2 is reported. These chiral systems, endowed with cyano-stilbene fragments, form supramolecular polymers by the operation of intermolecular H-bonding interactions between the amides present in the peripheral side chains. The dissimilar disubstitution of 1 and 2 plays a crucial role in their self-assembling features. Thus, 1 does not show an efficient π-stacking of the central aromatic moiety. Instead, its self-assembling process results in a zig-zag arrangement of the monomeric units to form the aggregated species. On the other hand, 2 presents an efficient overlap of the aromatic backbones that affords a co-facial arrangement of the monomeric units. The solvent-dependent studies indicate that both [6]helicenes self-assemble following a cooperative supramolecular polymerization mechanism with a higher degree of cooperativity and stability for compound 2. The enantioenriched samples of both 1 and 2 display a rich dichroic pattern that changes when the supramolecular polymerization takes place. Furthermore, the presence of the cyano-stilbene moieties gives rise to an aggregation induced emission effect. The inherent chirality of both the monomeric and aggregated species of 1 and 2 provides the systems with CPL-emitting properties, presenting a remarkable overall CPL-efficiency, quantified by the BCPL parameter, that increases upon supramolecular polymerization.

The crucial role of hydrogen bonding in shaping the structures of zinc-based coordination polymers using tridentate N, N, O donor reduced Schiff base ligands and bridging acetates.

In this manuscript we report the synthesis and characterization of two new polynuclear zinc(ii) complexes, [Zn2L1(μ-OAc)3]n·H2O (1) and [Zn2L2(μ-OAc)3]n (2) using two tridentate ligands, HL1 {4-chloro-2-(((2-(methylamino)ethyl)amino)methyl)phenol} and HL2 {2,4-dibromo-6-(((3-(methylamino)propyl)amino)methyl)phenol}. The structures were confirmed by single-crystal X-ray diffraction analysis. Both complexes form 1D chains. The energy of H-bonding interaction in the solid state structures of the complexes has been estimated by DFT calculation and the crucial role of hydrogen bonding in shaping their structures has been highlighted.

Selective separation of methylene blue from aqueous solution using Mn/Pd decorated chemically modified MoS2 nanocomposites

The presence of dyes in wastewater is posing as serious threat to human health. There are a huge number of physical, chemical, biological and hybrid methods available for the removal of colorants (dyes) from aqueous environment. In this work, we demonstrate the fabrication of new nanocomposites, MoS2-COOH/gly@M (M= Mn, Pd), with high adsorption property fabricated by chemically immobilizing manganese and palladium metallic centers onto the glycine- modified molybdenum disulfide (MoS2) material. The chemical and physical properties of adsorbents were analyzed using Fourier transform infrared spectrometer (FT-IR), thermal gravimetric analysis (TGA), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) companied by energy dispersive X-ray and mapping (EDAX & MAP) analyses. Zeta potential (ξ) technique was also used to measure the surface charge of adsorbents. Performances of nanocomposites were investigated on the sewage as adsorbent for dye removal. Synthesized nanocomposites revealed selective adsorption of methylene blue (MB) dye from aqueous mixture of MB and methyl orange (MO). Results displayed the equivalent high adsorption capacity for MB and MO up to 553 and 619 mg/g, respectively (green reaction condition= 120 min contact time, ,25 °C, pH 2.0 and pH 7.0, in the presence of 2 mg adsorbent and 50 mg/L (30 mL) initial concentration of MO and MB). The remarkable adsorption capacity of dye by MoS2-COOH/gly@M (M= Mn, Pd) nanocomposites can be attributed to the intermolecular interactions due to the presence of the amine, hydroxyl, and carboxyl functionalities. To describe the adsorption mechanism of MO and MB dye by synthesized nanomaterials, the pseudo-first-order and pseudo-second-order kinetics were further studied. Isotherm models displayed that the adsorption of MB and MO onto the MoS2-COOH/gly@M (M= Mn, Pd) nanocomposites is more correspondent with the Freundlich model with high-correlation coefficients. The results showed that the electrostatic attraction and H-bonding interaction were the basic cause of the adsorption of these anionic and cationic dyes on the surface of the nanocomposites. One of the distinguished properties of adsorbents is their capability to selectively adsorb MB from an admixture of MO and MB. The adsorption selectively has expanded in the following order: MoS2 < MoS2-COOH/gly@Mn < MoS2-COOH/gly@Pd. Based on the results, this new type of nanocomposites has potential to act as an effective and affordable adsorbent material for dye removal from an industrial sewage.

Pressure-Induced Aggregation of Associating Liquids as a Driving Force Enhancing Hydrogen Bond Cooperativity.

The behavior of hydrogen bonds under extreme pressure is still not well understood. Until now, the shift of the stretching vibration band of the X-H group (X = the donor atom) in infrared spectra has been attributed to the variation in the length of the covalent X-H bond. Herein, we combined infrared spectroscopy and X-ray diffraction experimental studies of two H-bonded liquid hexane derivatives, i.e., 2-ethyl-1-hexanol and 2-ethyl-1-hexylamine, in diamond anvil cells at pressures up to the GPa level, with molecular dynamics simulations covering similar thermodynamic conditions. Our findings revealed that the observed changes in the X-H stretching vibration bands under compression are not primarily due to H-bond shortening resulting from increased density but mainly due to cooperative enhancement of H-bonds caused by intensified molecular clustering. This sheds new light on the nature of H-bond interactions and the structure of liquid molecular systems under compression.

Using a simple coating strategy to evolve polylactic acid into sand-fixation material with nutrient-rich reservoir by strong H-bonding interaction at phase interface

Developing simple and eco-friendly methods for polylactic acid (PLA) modification and establishing strong interfacial interactions between phases are still worthwhile research topics. Only by enabling sand barriers to continuously provide water and fertilizer for sand-fixing plants can effective control of desertification be truly achieved. Herein, a simple and eco-friendly coating functionalmodification strategy for PLA was introduced, involving in-situ curing of urea-aldehyde (UF)/polyacrylic acid (PAA) prepolymer after coating on PLA and then continuous rolling. During the preparation process, –NH in the amide group and –OH in the carboxyl group of UF/PAA form strong intermolecular H-bonding with C = O of PLA, resulting in high interfacial bonding strength and significant improvement in mechanical and hydrophilic properties of the modified PLA mesh. Wind erosion resistance, water absorption and holding capacity, nutrient content, and plant growth of the treated sand all display a very positive response. Effective surface coating modification evolves PLA into a “nutrient-rich reservoir” for sand-fixing plants without affecting its performances, thus truly achieving the desired but never achieved effective combination of natural sand fixation and mechanical sand barrier fixation, exhibiting great significance for further improving application performances and expanding applying fields of PLA through surface functional modification that is easy to industrialize.

Highly efficient adsorption of ciprofloxacin from aqueous solutions by waste cation exchange resin-based activated carbons: Performance, mechanism, and theoretical calculation

This study focused on the preparation of a highly efficient activated carbon adsorbent from waste cation exchange resins through one-step carbonization to remove ciprofloxacin (CIP) from aqueous solutions. Scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectrometry, and X-ray photoelectron spectroscopy were used to characterize the physicochemical properties of the carbonized materials. The CIP removal efficiency, influencing factors, and adsorption mechanisms of CIP on the carbonized resins were investigated. Density functional theory (DFT) computations were performed to elucidate the adsorption mechanisms. The CIP removal reached 93 % when the adsorbent dosage was 300 mg/L at 25 °C. The adsorption capacity of the carbonized resins to CIP gradually decreased with an increasing pH from 3.0 to 7.0 and sharply declined with a pH from 7.0 to 11.0. The adsorption process better fitted by the pseudo second-order kinetic and Langmuir models, indicating that the interaction between CIP and the carbonized resins was monolayer adsorption. The maximum adsorption capacity fitted by the Langmuir model was 384.4 mg/g at 25 °C. Microstructural analysis showed that the adsorption of CIP on the carbonized resins was a joint effect of H-bonding, ion exchange, and graphite-N adsorption. Computational results signified the strong H-bonding and ion exchange interactions existed between CIP and carbonized resins. The high adsorption and reusability suggest that waste cation exchange resin-based activated carbons can be used as an effective and reusable adsorbent for removing CIP from aqueous solutions.