Adsorption Interaction Research Articles

Water-based Synthesis of MIL-53(Al) at Room Temperature: An Eff ective Adsorbent for Oxytetracycline (OTC) Antibiotic Removal from Water

MIL-53(Al), a fl exible metal-organic framework, was synthesized by a facile method through a water-based method at room temperature, aligning with the principles of green chemistry. The objective was to investigate its effectiveness in removing pharmaceuticals and personal care products (PPCPs), specifi cally focusing on oxytetracycline (OTC). Our fi ndings revealed that MIL-53(Al) possesses a structure with both micropores and mesopores, with a specifi c surface area of 916 m2/g. MIL-53(Al) notably exhibited a higher OTC adsorption capacity than commercially available powder activated carbon (PAC). The adsorption kinetics followed a pseudo-second-order model, while the Langmuir model accurately described the experimental isotherms for OTC adsorption. MIL-53(Al) outperformed previously reported MOF-based adsorbents with a maximum of 1005 mg/g capacity at pH 7. The fl exible structure induces a breathing effect that signifi cantly improves intraparticle diffusion for OTC, contributing to its adsorption effi ciency. The adsorption of OTC was infl uenced by the solution pH, the acid dissociation constants of OTC, and the charged surface of the adsorbent. Pore fi lling, hydrogen bonding, π-π interaction, electrostatic interaction, and hydrophobic interaction were all associated with the adsorptive interaction between OTC and MIL-53(Al). The MIL-53(Al) also demonstrated good regeneration and reuse, with just a little decreased adsorption capacity after three reuse cycles. These fi ndings indicate that green material MIL-53(Al) has the potential to be an effective adsorbent for removing OTC from water matrices

Spectra metrology for interaction of heavy metals with extracellular polymeric substances (EPS) of Pseudomonas aeruginosa OMCS-1 reveals static quenching and complexation dynamics of EPS with heavy metals

The adsorption behavior and interaction mechanisms of extracellular polymeric substances (EPS) of Pseudomonas aeruginosa OMCS-1 towards chromium (Cr), lead (Pb), and cadmium (Cd) were investigated. EPS-covered (EPS-C) cells exhibited significantly higher (p < 0.0001; two-way ANOVA) removal of Cr (85.58 ± 0.39%), Pb (81.98 ± 1.02%), and Cd (73.88 ± 1%) than EPS-removed (EPS-R) cells. Interactions between EPS-heavy metals were spontaneous (ΔG<0). EPS-Cr(VI) and EPS-Pb(II) binding were exothermic (ΔH<0), while EPS-Cd(II) binding was endothermic (ΔH>0) process. EPS bonded to Pb(II) via inner-sphere complexation by displacement of surrounding water molecules, while EPS-Cr(VI) and EPS-Cd(II) binding occurred through outer-sphere complexation via electrostatic interactions. Increased zeta potential of Cr (29.75%), Pb (41.46%), and Cd (46.83%) treated EPS and unchanged crystallinity (CIXRD=0.13), inferred EPS-metal binding via both electrostatic interactions and complexation mechanism. EPS-metal interaction was predominantly promoted through hydroxyl, amide, carboxyl, and phosphate groups. Metal adsorption deviated EPS protein secondary structures. Strong static quenching mechanism between tryptophan protein-like substances in EPS and heavy metals was evidenced. EPS sequestered heavy metals via complexation with C-O, C-OH, CO/O-C-O, and NH/NH2 groups and ion exchange with –COOH group. This study unveils the fate of Cr, Pb, and Cd on EPS surface and provides insight into the interactions among EPS and metal ions for metal sequestration.

Dual-vacancies modulation of 1T/2H heterostructured MoS2-CdS nanoflowers via radiolytic radical chemistry for efficient photocatalytic H2 evolution

Precise defect engineering of photocatalysts is highly demanding but remains a challenge. Here, we developed a facile and controllable γ-ray radiation strategy to assemble dual-vacancies confined MoS2-CdS-γ nanocomposite photocatalyst. We showed the solvated electron induced homogeneous growth of defects-rich CdS nanoparticles, while the symbiotic •OH radicals etched flower-like 1T/2H MoS2 substrate surfaces. The optimal MoS2-CdS-γ exhibited a H2 evolution rate of up to 37.80 mmol/h/g under visible light irradiation, which was 36.7 times higher than that of bare CdS-γ, and far superior to those synthesized by hydrothermal method. The microscopic characterizations and theoretical calculations revealed the formation of such unprecedented dual-sulfur-vacancies ensured the tight interfacial contact for fast charge separation. Besides, the existence of 1T-MoS2 phase further improved the conductivity and strengthened the adsorption interaction with H+ intermediate. Therefore, the radiolytic radical chemistry offered a facile, ambient and effective synthetic strategy to improve the catalytic performances of photocatalytic materials.

Carrier-based immobilization of Aerococcus viridansl-lactate oxidase

l-Lactate oxidase has important applications in biosensing and finds increased use in biocatalysis. The enzyme has been characterized well, yet its immobilization has not been explored in depth. Here, we studied immobilization of Aerococcus viridansl-lactate oxidase on porous carriers of variable matrix material (polymethacrylate, polyurethane, agarose) and surface functional group (amine, Ni2+-loaded nitrilotriacetic acid (NiNTA), epoxide). Carrier activity (Ac) and immobilized enzyme effectiveness (ɳ) were evaluated in dependence of protein loading. Results show that efficient immobilization (Ac: up to 1450 U/g carrier; ɳ: up to 65%) requires a hydrophilic carrier (agarose) equipped with amine groups. The value of ɳ declines sharply as Ac increases, probably due to transition into diffusional regime. Untagged l-lactate oxidase binds to NiNTA carrier similarly as N-terminally His-tagged enzyme. Lixiviation studies reveal quasi-irreversible enzyme adsorption on NiNTA carrier while partial release of activity (≤ 25%) is shown from amine carrier. The desorbed enzyme exhibits the same specific activity as the original l-lactate oxidase. Collectively, our study identifies basic requirements of l-lactate oxidase immobilization on solid carrier and highlights the role of ionic interactions in enzyme-surface adsorption.

Fabrication of polyethersulfone/sulfonated polysulfone loose nanofiltration membranes for enhanced selectivity of pharmaceuticals and personal care products and minerals

Nanofiltration (NF) membranes have a high removal rate for pharmaceutical and personal care products (PPCPs) in drinking water, but they also reject critical minerals (e.g., calcium and magnesium) that are beneficial to health. Herein, polyethersulfone (PES)/sulfonated polysulfone (SPSf) loose NF membranes were fabricated using non-solvent induced phase separation (NIPS) to enable efficient rejection of PPCPs while preserving high mineral permeability. The resultant loose NF membrane showed increased negative charge owing to the -SO3- groups of SPSf. It also exhibited a high water permeance of ∼20.8 L m-2 h−1 bar−1 characterized by high PPCPs/minerals selectivity (i.e., rejection of PPCPs > 90 % and rejection of Mg2+ < 5 %). The filtration performance of resultant membrane indicated that the ionic PPCPs (e.g., Indomethacin, Diclofenac Sodium, Levofloxacin, Norfloxacin) were removed by the electrostatic repulsion and adsorption, while the removal of non-ionic PPCPs (e.g., Bisphenol A, Carbamazepine) was primarily dominated by the synergy of adsorption and size exclusion. Therefore, the superior removal rate of hydrophilic PPCPs was due to enhanced PPCP-membrane adsorptive interaction. This study provides a profound understanding of the selective separation mechanism of loose NF membranes for micropollutants and minerals.

Understanding the photo-sensitive essence of organic-inorganic hybrids for the targeted detection of azithromycin

Being a macrolide antibiotic, the antiviral and anti-inflammatory properties of azithromycin (AZM) were taken advantage of during the COVID-19 pandemic which led to the overuse of AZM resulting in excessive release and accumulation in the waterways and ecosystem causing unpleasant threats to humankind. This demands the necessity for a highly sensitive material being capable of recognizing AZM in wastewater. Mindful of the optical attributes of organic ligand structures, we have constructed a hybrid material by chelating Zn2+ with pyridyl benzimidazole (PBI). The prepared sensor material ZnPBI was characterized using various microscopic and spectroscopic techniques including XRD, FT-IR, HR-SEM, HR-TEM, etc. The proposed sensor material exhibited proficient detection performance selectively towards AZM with a very low detection limit of 72 nM. Two linear ranges between 0 – 70 μM and 70–100 μM were observed corresponding to two different mechanistic pathways. To the best of our knowledge, the utilization of a metal-organic complex (MOC) for the fluorometric detection of AZM has not been explored so far. It is creditworthy to cite that the long-term structural stability of the sensor material was maintained for 100 days in water and it can be reused three times without any depreciation in the sensing activity. A combination of energy transfer routes, adsorption and electrostatic interactions for AZM detection are described experimentally and theoretically which provides insights into the role of MOC as sensing probes.

Spatial evolution characteristics of asphalt surface structure and its influence on surface interaction properties

Air-asphalt surface structure (asphalt surface structure) is widely found in asphalt mixture and is the main structure that directly interacts with air, precipitation and sunlight. To explore the physicochemical properties of asphalt surface structure, the spatial evolution characteristics and interaction properties were studied by combining theory, test and simulation. Firstly, the gestation, generation and development of asphalt surface structure were explained theoretically, and the categories of asphalt surface structure were proposed. Secondly, the spatial evolution characteristics of asphalt surface structure were analyzed by the combination of macro and micro tests. Finally, the relationship between asphalt surface structure and air (N2, O2) and precipitation (H2O) was discussed by using molecular dynamics. It was found that, theoretically, asphalt surface structure can be divided into "initial surface structure", "stable surface structure" and "aged surface structure", and the "stable surface structure" is the ideal surface state. The low temperature environment is conducive to the adsorption of air (N2, O2) by the asphalt surface structure, the "initial surface structure" has a relatively high adsorption interaction capacity. Additionally, the interaction between precipitation and asphalt surface structure is gradually enhanced with the increase of temperature, and the interaction between "aged surface structure" and precipitation is relatively stronger. The study further expands the exploration of asphalt surface structure and provides a theoretical explanation for asphalt aging behavior.

Activated rice husk biochar for azo dye removal: batch adsorption, kinetics and thermodynamic studies

&lt;p&gt;The study aimed to analyze the adsorption behaviour of an activated rice husk biochar adsorbent in batch mode to expunge azo dye concentrations depletion from liquid solvents. The biochar adsorbent was formulated using different chemical synthesis processes, and its surface region was assessed using Nitrogen retention. The existence of the particular azo dyes was verified through SEM and EDX examinations. Additionally, XRD analysis was conducted to examine the intensity and crystalline structure of the activated biochar adsorbent. A batch mode study was conducted to ascertain the ideal adsorption parameters, including pH, contact time, biochar dose, and azo dye concentration. The adsorption kinetic studies supported the notion of a favourable adsorption interaction occurring through the mutual influence of the adsorbed matter and the adsorbing substrate. Most isotherm studies were well-fitted with regression values of isotherm models, indicating an adsorption process with non-uniform monolayer formation. Thermodynamic investigations validated that the binding forces between the adsorptive and the adsorbing phase are endothermic, and a significant amount of spent adsorbent was successfully recovered using a strong hydrochloric acid desorption process.&lt;/p&gt;

Adsorption interactions between typical microplastics and enrofloxacin: Relevant contributions to the mechanism

Microplastics (MPs) are increasingly contaminating the environment and they can combine with antibiotics as carriers to form complex contaminants. In this study, we systematically investigated the interactions between the antibiotic enrofloxacin (ENR) and MPs comprising polyethylene (PE), polyvinyl chloride (PVC), and polystyrene (PS). Characterization was performed by using conventional techniques and the mechanisms involved in interactions were initially explored based on adsorption kinetics, isotherms, and resolution experiments, and the adsorption capacities of the MPs were determined. In addition, the extended Derjaguin–Landau–Verwey–Overbeek theory was used to investigate the interaction mechanisms. The results showed that the interactions were weaker in strong acidic and alkaline environments, and the interactions were also inhibited at higher salt ion concentrations. The saturation adsorption amounts of ENR on PVC, PE, and PS were 74.63 μg/g, 103.09 μg/g, and 142.86 μg/g, respectively. The interactions between MPs and ENR were dominated by hydrophobic interactions, followed by van der Waals forces and acid–base forces. This study provides new insights into the adsorption behavior of ENR by MPs.

Investigations of the reaction mechanism of sodium with hydrogen fluoride to form sodium fluoride and the adsorption of hydrogen fluoride on sodium fluoride monomer and tetramer.

The reaction between Na and HF is a typical harpooning reaction which is of great interest due to its significance in understanding the elementary chemical reaction kinetics. This work aims to investigate the detailed reaction mechanisms of sodium with hydrogen fluoride and the adsorption of HF on the resultant NaF as well as the (NaF)4 tetramer. The results suggest that the reaction between Na and HF leads to the formation of sodium fluoride salt NaF and hydrogen gas. Na interacts with HF to form a complex HF···Na, and then the approaching of F atom of HF to Na results in a transition state H···F···Na. Accompanied by the broken of H-F bond, the bond forms between F and Na atoms as NaF, then the product NaF is yielded due to the removal of H atom. The resultant NaF can further form (NaF)4 tetramer. The interaction of NaF with HF leads to the complex NaF···HF; the form I as well as II of (NaF)4 can interact with HF to produce two complexes (i.e., (NaF)4(I-1)···HF, (NaF)4(I-2)···HF, (NaF)4(II-1)···HF and (NaF)4(II-2)···HF), but the form III of (NaF)4 can interact with HF to produce only one complex (NaF)4(III)···HF. These complexes were explored in terms of noncovalent interaction (NCI) and quantum theory of atoms in molecules (QTAIM) analyses. NCI analyses confirm the existences of attractive interactions in the complexes HF···Na, NaF···HF, (NaF)4(I-1)···HF, (NaF)4(I-2)···HF, (NaF)4(II-1)···HF and (NaF)4(II-2)···HF, and (NaF)4(III)···HF. QTAIM analyses suggest that the F···Na interaction forms in the HF···Na complex while the F···H hydrogen bonds form in NaF···HF, (NaF)4(I-1)···HF, (NaF)4(I-2)···HF, (NaF)4(II-1)···HF and (NaF)4(II-2)···HF, and (NaF)4(III)···HF complexes. Natural bond orbital (NBO) analyses were also applied to analyze the intermolecular donor-acceptor orbital interactions in these complexes. These results would provide valuable insight into the chemical reaction of Na and HF and the adsorption interaction between sodium fluoride salt and HF. The calculations were carried out at the M06-L/6-311++G(2d,2p) level of theory which were performed using the Gaussian16 program. Intrinsic reaction coordinate (IRC) calculations were carried out at the same level of theory to confirm that the obtained transition state was true. The molecular surface electrostatic potential (MSEP) was employed to understand how the complex forms. Quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) analysis was used to know the topology parameters at bond critical points (BCPs) and intermolecular interactions in the complex and intermediate. The topology parameters and the BCP plots were obtained by the Multiwfn software.

Highly efficient capture of iodine vapor by [Mo3S13]2− intercalated layered double hydroxides

From the swollen LDH, bulky [Mo3S13]2− anions are facilely introduced into the LDH interlayers to assemble the Mo3S13-LDH composite, which exhibits excellent iodine capture performance and good irradiation resistance. The positive-charged LDH layers may disperse the [Mo3S13]2− uniformly within the interlayers, providing abundant adsorption sites for effectively trapping iodine. The Mo-S bond serving as a soft Lewis base has strong affinity to I2 with soft Lewis acidic characteristic, which is conducive to improvement of iodine capture via physical sorption. Besides, chemisorption has a significant contribution to the iodine adsorption. The S22−/S2− in [Mo3S13]2− can reduce the I2 to [I3]− ions, which are facilely fixed within the LDH gallery in virtue of electrostatic attraction. Meanwhile, the S22−/S2− themselves are oxidized to S8 and SO42−, while Mo4+ is oxidized (by O2 in air) to Mo6+, which combines with SO42− forming amorphous Mo(SO4)3. With the collective interactions of chemical and physical adsorption, the Mo3S13-LDH demonstrates an extremely large iodine adsorption capacity of 1580 mg/g. Under γ radiation, the structure of Mo3S13-LDH well maintains and iodine adsorption capability does not deteriorate, indicating the good irradiation resistance. This work provides an important reference to tailor cost-effective sorbents for trapping iodine from radioactive nuclear wastes.

Purification of Pesticide-Contaminated Water Using Activated Carbon from Prickly Pear Seeds for Environmentally Friendly Reuse in a Circular Economy

This study proposes an innovative approach based on the concept of the circular economy. It involves treating deltamethrin-contaminated water using an activated carbon (AC) adsorption technique based on a highly adsorbent plant waste derived from prickly pear seeds (PPSs). Activated carbon was prepared from PPS via a simple pyrolysis process preceded by chemical impregnation with phosphoric acid. Thus, a whole range of physicochemical tests were carried out, including iodine number (QI2), methylene blue number (QMB), Bohem dosage, pHZC, Brunauer–Emmett–Teller analysis (BET), and scanning electron microscopy (SEM). The QI2 and QMB were, respectively, 963.5 (mg g−1) and 8.3 (mg g−1). The pHzc of activated carbon was 2.5, and the surface area BET was 1161.3 m2 g−1. Adsorption kinetics, isotherms, and thermodynamic studies of pesticides using activated carbon were established. The obtained results revealed that the adsorption of the pesticide by the activated carbon appeared to be chemisorption with an adsorption capacity of 1.13 mg g−1. The adsorption capacity increased with increasing temperature, which explains an endothermic adsorption interaction. These results are in agreement with the results found using the density functional theory (DFT) and showed that activated carbon has an interesting adsorption power, which makes it as efficient as commercial activated carbon and predisposes it to the depollution of aqueous solutions contaminated with pesticides.

Hierarchical Porous Aerogels With Multiple Adsorptive Interactions for Dye Wastewater Purification.

Aerogels present a huge potential for removing organic dyes from printing and dyeing wastewater (PDW). However, the preparation of aerogels with multiple dye adsorption capabilities remains a challenge, as many existing aerogels are limited to adsorbing only a single type of dye. Herein, a composite aerogel (CG/T-rGO) with the addition of carboxymethyl chitosan, gelatin and tannic acid reduced graphene oxide (T-rGO) was synthesized by freeze-drying technology. The electrostatic interactions between dye molecular and GEL/CMCS (CG) networks, as well as the supramolecular interactions (H-bonds, electrostatic interactions and π-π stacks) between T-rGO, have endowed the aerogel with the ability to adsorb multiple types of dye, such as methylene blue (MB) and methyl orange (MO). Results exhibited that the prepared CG/T-rGO aerogel possessed strong mechanical strength and a porous 3D network structure with a porosity of 96.33 %. Using MB and MO as adsorbates, the adsorption capacity (88.2 mg/g and 66.6 mg/g, respectively) and the mechanism of the CG/T-rGO aerogel were investigated. The adsorption processes of aerogel for MB and MO were shown to follow the pseudo-second-order kinetic model and Langmuir isotherm model, indicating the chemical adsorption of a monolayer. The proposed aerogel in this work has promising prospects for dye removal from PDW.

Metal-support interactions in metal oxide-supported atomic, cluster, and nanoparticle catalysis.

Supported metal catalysts are essential to a plethora of processes in the chemical industry. The overall performance of these catalysts depends strongly on the interaction of adsorbates at the atomic level, which can be manipulated and controlled by the different constituents of the active material (i.e., support and active metal). The description of catalyst activity and the relationship between active constituent and the support, or metal-support interactions (MSI), in heterogeneous (thermo)catalysts is a complex phenomenon with multivariate (dependent and independent) contributions that are difficult to disentangle, both experimentally and theoretically. So-called "strong metal-support interactions" have been reported for several decades and summarized in excellent review articles. However, in recent years, there has been a proliferation of new findings related to atomically dispersed metal sites, metal oxide defects, and, for example, the generation and evolution of MSI under reaction conditions, which has led to the designation of (sub)classifications of MSI deserving to be critically and systematically evaluated. These include dynamic restructuring under alternating redox and reaction conditions, adsorbate-induced MSI, and evidence of strong interactions in oxide-supported metal oxide catalysts. Here, we review recent literature on MSI in oxide-supported metal particles to provide an up-to-date understanding of the underlying physicochemical principles that dominate the observed effects in supported metal atomic, cluster, and nanoparticle catalysts. Critical evaluation of different subclassifications of MSI is provided, along with discussions on the formation mechanisms, theoretical and characterization advances, and tuning strategies to manipulate catalytic reaction performance. We also provide a perspective on the future of the field, and we discuss the analysis of different MSI effects on catalysis quantitatively.

Adsorption of rare bases on transition metal doped γ-graphyne nanosheets: a DFT study.

Detection of rare bases (RBs) is key to understanding biological complexity, rapidly diagnosing genetic diseases and advancing personalized medicine. Electrochemical sensors are one of the most promising methods for RB detection, but their low responsiveness limits their effectiveness. Therefore, enhancing selectivity and sensitivity is necessary. γ-Graphyne (γ-GY) has garnered significant attention due to its sp2 and sp hybrid carbon bonds and layered two-dimensional planar structure, as well as its extensive conjugated system, and sizable triangular hole. In this study, the structural characteristics, electronic properties, and sensing parameters of the adsorption involving RBs with both γ-GY and transition metal (Fe, Co, and Ni)-doped γ-graphyne (TM-GY) nanosheets are investigated using density functional theory calculations to evaluate the potential of nanosheets for sequencing RBs in DNA. The result shows that the adsorption interaction between RBs and γ-GY is weak physical adsorption, making it difficult to distinguish RBs. In contrast, the adsorption of RBs with TM-GY is stronger chemisorption and can be completely separated by translocation time and sensing response. Through translocation time calculations, we demonstrate the high selectivity of Ni-GY for RBs. Furthermore, sensitivity analysis reveals that Fe-GY exhibits excellent responsiveness to RBs. Our work reveals that the TM-GY nanosheets hold promise for detecting RBs compared with the γ-GY, and may provide valuable insights for the design of graphyne-based biosensors and catalysts.

Engineering a sustainable cadmium sulfide/polyethyleneimine-functionalized biochar/chitosan composite for effective chromium adsorption: optimization, co-interfering anions, and mechanisms.

A novel eco-friendly adsorbent was fabricated by mixing mushroom-derived cadmium sulfide and polyethyleneimine-functionalized biochar that was fabricated from coffee waste with a chitosan biopolymer. The green-synthesized CdS/PEI-BC/CTS composite was analyzed using several characterization methods to identify its morphological, compositional, and structural characteristics. In addition, the adsorption property of the composite was investigated for hexavalent chromium as a model for anionic heavy metals. The best adsorption conditions to efficiently adsorb Cr(vi) onto CdS/PEI-BC/CTS were scrutinized in the batch mode. The experimental results elucidated that the higher adsorption efficacy for Cr(vi) was 97.89% at pH = 3, Cr(vi) concentration = 50 mg L-1, CdS/PEI-BC/CTS dose = 0.01 g, and temperature = 20 °C. The impact of co-interfering anionic species on Cr(vi) adsorption was identified in simulated wastewater. The recycling property of the CdS/PEI-BC/CTS composite was assessed for ten runs to ensure the applicability of the green composite. The adsorption mechanism and interaction types were proposed on the basis of kinetic and isotherm studies, along with analysis tools. The mechanistic study proposed that the Cr(vi) adsorption onto CdS/PEI-BC/CTS occurred via chemical and physical pathways, including protonation, electrostatic interactions, reduction, and coordination bonds.

Fluorescence nanoprobes bearing low temperature-derived biochar nanoparticles as efficient quenchers for the detection of single-stranded DNA and 17β-estradiol and their analytical potential.

Bagasse-derived biochar nanoparticles obtained under a low pyrolysis condition (400 °C) were first revealed to be capable of highly efficiently quenching the fluorescence of 6-carboxyfluorescein, with a significantly improved quenching rate constant over that of other quenchers and high-temperature prepared ones, and were designated as bagasse-derived quencher nanoparticles (BQNPs). The BQNPs are suitable for the construction of fluorescence nanoprobes, taking advantage of their various beneficial properties, including low cost, environmental friendliness, high dispersibility, and rich functional groups that allow their easy and versatile molecular modification. They were demonstrated to be capable of stably binding single-stranded oligonucleotides through both adsorption and covalent interactions and were utilized for the construction of both BQNPs/DNA and BQNPs/aptamer probes. The BQNPs/DNA probe had strong resistance against degradation by deoxyribonuclease I and showed high precision and selectivity for the detection of single-stranded DNA, with a limit of detection of 1.04 nM. Moreover, the BQNPs/aptamer probe demonstrated the rapid and sensitive detection of 17β-estradiol (E2) with a limit of detection of 0.4 ng mL-1 with no cross-reactivity with the analogues, and it was also applied for real environmental sample detection and demonstrated reasonable signal recoveries. Benefiting from their strong quenching ability, low cost, and great dispersibility, the BQNPs show great potential for the development of cost-effective and sensitive fluorescence sensors.

A comprehensive adsorption and desorption study on the interaction of DNA oligonucleotides with TiO2 nanolayers.

The utilization of TiO2 nanolayers that possess excellent biocompatibility and physical properties in DNA sensing and sequencing remains largely to be explored. To examine their applicability in gene sequencing, a comprehensive study on the interaction of DNA oligonucleotides with TiO2 nanolayers was performed through adsorption and desorption experiments. TiO2 nanolayers with 10 nm thickness were fabricated via magnetron sputtering onto a 6-inch silicon wafer. A simple chip block method, validated via quartz crystal microbalance experiments with dissipation monitoring (QCM-D), was proposed to study the adsorption behaviors and interaction mechanisms under a variety of critical influencing factors, including DNA concentration, length, and type, adsorption time, pH, and metal ions. It is determined that the adsorption takes 2 h to reach saturation in the MES solution and the adsorption capacity is significantly enhanced by lowering the pH due to the isoelectric point being pH = 6 for TiO2. The adsorption percentages of nucleobases are largely similar in the MES solution while following 5T = 5G > 5C > 5A in HEPES buffer for an adsorption duration of 2.5 h. Through pre-adsorption experiments, it is deduced that DNA oligonucleotides are horizontally adsorbed on the nanolayer. This further demonstrates that mono-, di-, and tri-valent metal ions promote the adsorption, whereas Zn2+ has strong adsorption by inducing DNA condensation. Based on the desorption experiments, it is revealed that electrostatic force dominates the adsorption over van der Waals force and hydrogen bonds. The phosphate group is the main functional group for adsorption, and the adsorption strength increases with the length of the oligonucleotide. This study provides comprehensive data on the adsorption of DNA oligonucleotides onto TiO2 nanolayers and clarifies the interaction mechanisms therein, which will be valuable for applications of TiO2 in DNA-related applications.

Dynamic sampling of liquid metal structures for theoretical studies on catalysis.

Liquid metals have recently emerged as promising catalysts that can outcompete their solid counterparts for many reactions. Although theoretical modelling is extensively used to improve solid-state catalysts, there is currently no way to capture the interactions of adsorbates with a dynamic liquid metal. We propose a new approach based on ab initio molecular dynamics sampling of an adsorbate on a liquid catalyst. Using this approach, we describe time-resolved structures for formate adsorbed on liquid Ga-In, and for all intermediates in the methanol oxidation pathway on Ga-Pt. This yields a range of accessible adsorption energies that take into account the at-temperature motion of the liquid metal. We find that a previously proposed pathway for methanol oxidation on Ga-Pt results in unstable intermediates on a dynamic liquid surface, and propose that H desorption must occur during the path. The results showcase a more accurate way to treat liquid metal catalysts in this emerging field.

Molecular simulation of adsorption behavior for phenol aqueous solution into layered graphene oxides

Graphene oxide (GO) adsorbents possess layered structures with nanoscale interlayer channels, which have been proposed as effective adsorbents for the removal of harmful phenol from aqueous solutions. However, the relevant adsorption process and behavior remain largely unexplored, and, particularly, the interlayer insertion and interaction mechanism need to be clarified. Herein, molecular dynamics simulation was performed to comprehensively investigate the dynamics process and interaction for phenol adsorption into GO interlayers. It is theoretically demonstrated that the adsorption process is thermodynamically spontaneous. The time evolution of molecular insertion amounts and interaction energy were applied to describe the dynamics process, in which different adsorption stages were revealed. Our simulation findings show that the interlayer phenol movement is the rate-limiting step in the adsorption process. Furthermore, by analyzing the interlayer structure and morphology, it is illustrated that the phenol molecules are discretely and disorderly scattered with a lying-down conformation within the GO interlayer. The adsorption interaction is the combination of the π–π and hydrogen-bonding interactions, in which the π-π interaction provides a dominant contribution. The effects of interlayer widths and surface oxidization degrees were thoroughly investigated. Our simulations provide new insight and useful guidance for the development of GO adsorbents.