Accessible Surface Research Articles

In silico sequential mutagenesis of the Carbohydrate Binding Module Family 32 (CBM32) enhances ligand binding affinity

Alginate lyase is a promising target for genetic modification for its degrading biofilm, contributing to bacterial proliferation and antimicrobial resistance. Apart from the main enzyme, the carbohydrate binding module (CBM) component can also be modified to enhance alginate lyase’s activity. This study aimed to perform sequential in silico mutagenesis, molecular docking of selected amino acid residues of Vibrio splendidus CBM32 and performed molecular dynamics (MD) simulations of the mutated structure to validate its ligand-binding efficacy. Seven residues were selected for mutagenesis based on the predicted bonds that formed between the CBM32 and the glucuronic acid ligand (LGU9). Four of seven sequential residue substitutions increased the ligand binding affinity cumulatively from -5.4 Kcal/mol to -6.9 Kcal/mol. The mutated CBM32 had similar MolProbity scores to the original V. splendidus CBM32 structure. From the post-MD simulation analysis, the mutated CBM32 had higher structural stability in a solvent system, a greater number of hydrogen bonds formed with ligand but a lower solvent-accessible surface area than the original structure. The sequential mutagenesis process significantly increased the ligand binding affinity of CBM32 while incurring a minimal change in the overall CBM32 structure. The information on these substituted residues would be beneficial for designing subsequent in vitro mutagenesis and enzymatic assays.

The Entropy of Mixing in Self-Assembly and the Role of Surface Tension in Modeling the Critical Micelle Concentration

A theory for the micelle formation of nonionic head-tail amphiphiles (detergents) in aqueous solutions is derived based on the traditional molecular thermodynamic modeling approach and a variant of the Flory–Huggins theory that goes beyond lattice models. The theory is used to analyze experimental values for the critical micelle concentration of n-alkyl-ß-D-maltosides within a mass action model. To correlate those parts of the micellization free energy, which depend on the transfer of hydrophobic molecule parts into the aqueous phase, with molecular surfaces, known data for the solubility of alkanes in water are reanalyzed. The correct surface tension to be used in connection with the solvent-excluded surface of the alky tail is ~30 mN/m. This value is smaller than the measured surface tension of a macroscopic alkane–water interface, because the transfer free energy contains a contribution from the incorporation of the alkane or alkyl chain into water, representing the change in free volume in the aqueous phase. The Flory–Huggins theory works well, if one takes into account the difference in liberation free energy between micelles and monomers, which can be described in terms of the aggregation number as well as the thermal de Broglie wavelength and the free volume of the detergent monomer.

Computational and theoretical insights into the cytotoxic prospects of compounds isolated from Elaeodendron buchananii against Leukemia

The present study investigated the cytotoxic prospects of isolated compounds from Elaeodendron buchananii against leukemia, using computational tools. Comprehensive literature searches revealed only buchaninoside, mutangin, methyl 3β-acetoxy-11α, 19α, 28-trihydroxyurs-12-en-23-oic acid, 3β, 11α, 19α-trihydroxyurs-12-en-23, 28-dioic acid, 3β-acetoxy-19α, 24, 28-trihydroxyurs-12-ene, 3-oxo-19α,28-dihydroxyurs-12-en-24-oic acid, and elabunin have been isolated from E. buchananii. The compounds were subjected to Density Functional Theory (DFT) and Molecular Dynamics (MD) analyses, with Fms-like tyrosine kinase (FLT3) and catalytic binding sites of Murine Leukemia Virus (MLV) as the target proteins in lukemia. Following DFT analysis, the structures of the compounds were optimized at the PW6B95D3/Def2-TZVP level of theory; their UV-Visible peaks were in the UV region, with mutangin, 3-oxo-19α,28-dihydroxyurs-12-en-24-oic acid and elabunin exhibiting one single peak. The potent Root-Mean-Square Deviation, Root-Mean-Square Fluctuation, solvent-accessible surface area and radius of gyration values indicated a strong and stable molecular interaction between the compounds and the proteins. These were further supported by high ∆G values, with MLV showing the best interaction. Per-residue decomposition plots also revealed high energy contributions in the interactions’ binding sites residues. These results indicate that the cytotoxic prospects of the isolated compounds against leukemia as indicated by its molecular interactions with FLT3 and MLV.

Alkylsulfonic acid functionalized aluminoborate: A highly efficient and regioselective solid acid catalyst for ring-opening addition of epoxide under solvent-free condition

Functionalized solid acid material has more accessible active surface and therefore is usually considered as an important substitute for conventional liquid mineral acid. In this work, a novel alkylsulfonic acid functionalized porous aluminoborate molecular sieve (PKU-1) has been prepared through 3-step post-synthetic method, and the high-density acidic sites were tailored and comprehensively characterized by various measurements. These acidity-controllable active sites exhibit high activity and specific regioselectivity towards alcoholysis reaction for the solvent-free production of methoxyl alcohol, and turnover frequency reaches ∼1000 h–1, which is much superior to previous reports. Comprehensive characterizations indicate catalytic centers exclusively come from –SO3H acid sites, rather than other type of Brönsted or Lewis acid sites. A plausible reaction mechanism was proposed to interpret the key role of –SO3H active sites on alcoholysis reaction based on the related experimental results. This work offers a promising solution to generate the controllable acidity and provides an available candidate in the environmentally benign catalysis for selective synthesis of some value-added compounds.

Molecular Dynamics Simulation of the Viscosity Enhancement Mechanism of P-n Series Vinyl Acetate Polymer-CO2.

Carbon dioxide (CO2) drive is one of the effective methods to develop old oil fields with high water content for tertiary oil recovery and to improve the recovery rate. However, due to the low viscosity of pure CO2, it is not conducive to expanding the wave volume of the mixed phase, which leads to difficulty utilizing the residual oil in vertical distribution and a low degree of recovery in the reservoir. By introducing viscosity enhancers, it is possible to reduce the two-phase fluidity ratio, expanding the degree of longitudinal rippling and oil recovery efficiency. It has been proven that the acetate scCO2 tackifier PVE can effectively tackify CO2 systems. However, little research has been reported on the microscopic viscosity enhancement mechanism of scCO2 viscosity enhancers. To investigate the influence of a vinyl acetate (VAc) functional unit on the viscosity enhancement effect of the CO2 system, PVE (Polymer-Viscosity-Enhance, P-3) was used as the parent, the proportion of VAc was changed, and the molecules P-1 and P-2 were designed to establish a molecular dynamics simulation model for the P-n-CO2 system. The molecules in the system under the conditions of 70 °C-10 MPa, 80 °C-10 MPa, and 70 °C-20 MPa were simulated; the viscosity of the system was calculated; and the error between the theoretical and simulated values of the viscosity in the CO2 system was relatively small. The difference between P-n molecular structure and system viscosity was analyzed at multiple scales through polymer molecular dynamics simulations and used the molecular radial distribution function, system density, accessible surface area, radius of gyration, minimum intermolecular distance, and minimum number of intermolecular contacts as indicators. This study aimed to elucidate the viscosity enhancement mechanism, and the results showed that the higher the proportion of VAc introduced into the molecules of P-n-scCO2 viscosities, the larger the molecular amplitude, the larger the effective contact area, and the greater the viscosity of the system. Improvement in the contact efficiency between the ester group on the P-n molecule and CO2 promotes the onset of solvation behavior. This study on the microscopic mechanism of scCO2 tackifiers provides a theoretical approach for the design of new CO2 tackifiers.

S-palmitoylation of MAP kinase is essential for fungal virulence.

S-palmitoylation is an important reversible protein post-translational modification in organisms. However, its role in fungi is uncertain. Here, we found the treatment of the rice false fungus Ustilaginoidea virens with S-palmitoylation inhibitor 2 BP resulted in a significant decrease in fungal virulence. Comprehensive identification of S-palmitoylation sites and proteins in U. virens revealed a total of 4,089 S-palmitoylation sites identified among 2,192 proteins and that S-palmitoylated proteins were involved in diverse biological processes. Among the five palmitoyltransferases, UvPfa3 and UvPfa4 were found to regulate the pathogenicity of U. virens. We then performed quantitative proteomic analysis of ∆UvPfa3 and ∆UvPfa4 mutants. Interestingly, S-palmitoylated proteins were significantly enriched in the mitogen-activated protein kinase and autophagy pathways, and MAP kinase UvSlt2 was confirmed to be an S-palmitoylated protein which was palmitoylated by UvPfa4. Mutations of S-palmitoylation sites in UvSlt2 resulted in significantly reduced fungal virulence and decreased kinase enzymatic activity and phosphorylation levels. Simulations of molecular dynamics demonstrated mutation of S-palmitoylation sites in UvSlt2 causing decreased hydrophobic solvent-accessible surface area, thereby weakening the bonding force with its substrate UvRlm1. Taken together, S-palmitoylation promotes U. virens virulence through palmitoylation of MAP kinase UvSlt2 by palmitoyltransferase UvPfa4. This enhances the enzymatic phosphorylation activity of the kinase, thereby increasing hydrophobic solvent-accessible surface area and binding activity between the UvSlt2 enzyme and its substrate UvRlm1. Our studies provide a framework for dissecting the biological functions of S-palmitoylation and reveal an important role for S-palmitoylation in regulating the virulence of the pathogen.IMPORTANCES-palmitoylation is an important post-translational lipid modification of proteins. However, its role in fungi is uncertain. In this study, we found that S-palmitoylation promotes virulence of rice false smut fungus U. virens through palmitoylation of MAP kinase UvSlt2 by palmitoyltransferase UvPfa4. This enhances the enzymatic phosphorylation activity of the kinase, thereby increasing hydrophobic solvent-accessible surface area and binding activity between the UvSlt2 enzyme and its substrate UvRlm1. Our studies provide a framework for dissecting the biological functions of S-palmitoylation and reveal an important role for S-palmitoylation in regulating the virulence of the pathogen. This is the first functional study to reveal the role of S-palmitoylation in fungal virulence.

Unveiling the structural and physico-chemical properties of glutenin macropolymer under frozen storage: Studies on experiments and molecular dynamics simulation

Glutenin macropolymer (GMP) plays an important role in wheat gluten fractions, and extensively presents in the frozen dough. However, the effects of freezing treatment on GMP remain not abundantly understood. In this study, we investigated the structure and physico-chemical properties of GMP under frozen storage through experimental methods and bioinformatics algorithms. Results revealed that freezing treatment weakened the structure and properties of GMP to varying degrees, and GMP might have tolerance to short-term freezing storage. During frozen storage, portions of α-helix in GMP were converted into β-turn and random coil, slight changes in the tertiary structure, and its surface hydrophobicity increased by 4.8 %. SDS-PAGE profiles indicated that the depolymerization behavior mainly occurred above the Mw of 70.0 kDa. Slight changes were observed in the content of free thiol groups and disulfide bonds during frozen storage. Combination of fluorescence spectroscopy and intermolecular interactions suggested that hydrogen bonds and hydrophobic interactions were probably important indicators for evaluating the deterioration of GMP. Frozen storage resulted in an unfolded and open protein network. Moreover, freezing treatment led to a main conversion from strongly bond water to weakly bond water. However, no significant changes in water distribution were observed during the first 7 days of frozen storage. The viscoelastic loss of GMP primarily occurred in the first fourteen days, but tan δ did not significantly increased, indicating that protein has not been seriously deteriorated. Molecular dynamics simulation further supplemented and validated these experimental results from molecular level through analysis of root mean square deviation, root mean square fluctuation, solvent-accessible surface area, radius of gyration and the number of hydrogen bonds.

Green self-templated synthesis of P-doped mesoporous carbon from dual sodium salts with improved average pore size for capacitive deionization

Mesoporous carbon materials hold significant potential in capacitive deionization (CDI) technology owing to expansive accessible surface area, more adaptable pore structure, excellent conductivity properties and effective surface modification and functionalization. While templating is a common method for synthesizing mesoporous carbons, the commonly used hard and soft templating approaches among them suffer from the challenges of expensive precursors and templating agents, complex procedures, secondary contaminants and difficulties in template removal. In contrast, the self-templating method not only circumvents the traditional template removal or combustion steps but also eliminates the use of organic solvents and hazardous chemicals, thus minimizing environmental impact. In this paper, we have successfully synthesized phosphorus-doped mesoporous carbon with a large average pore size (paver) using a green and convenient self-templating method employing dual sodium salts of sodium alginate (SA) and sodium phytate (SP). Compared to single SA (6.76 nm) or SP (3.74 nm) self-templated carbonization, the average pore size of carbon materials obtained from dual self-templated carbonization with a proportional mixture (12.97 nm) is significantly improved. The larger average pore size provides a greater surface area for electrode-electrolyte interactions, allowing for easier access and faster diffusion of ions into the pores, thereby enhancing the electrochemical and capacitive deionization properties of the material. The resulting material demonstrates promising electrochemical and desalination performance as evidenced by possessing a specific capacitance of 175.8 A/g and an adsorption capacity of 19.65 mg/g, underlining its potential for application in capacitive deionization utilizing mesoporous carbon materials with large average pore size.

An orientational graphene/bamboo evaporator for efficient solar-powered steam generation and desalination

Solar-powered steam generation and desalination by interfacial solar steam generation (ISSG) are promising techniques for addressing the freshwater shortage. However, the insufficient conversion efficiency and complex pollutant components confine its further extension and application. This study innovatively constructs an orientational graphene/bamboo evaporator (GBE), maintaining a solvent-accessible surface area and reducing vaporization enthalpy by selective delignification and torrefaction. The GBE device features a channel oriented from bamboo, consolidating the parallel architecture with multilayer biofilm filtration that guides efficient bulk-water pumping, steam release, and pollutant interception. The GBE demonstrates full-spectrum optical absorption at 90.5 % and 33.4 s response time while maintaining operational stability across different salt concentrations and natural water environments. The GBE achieved an evaporation rate of 1.53 kg m-2h-1as 4.34 enhancement factor under 1 kW/m−2(−|-) illumination, surpassing microplastics (99.84 %) and tetracycline (99.87 %) desalination. This work provides a high-performance and innovative approach to bamboo evaporator design, offering a viable and alternative method to address freshwater shortage.

Molecular Dynamics Simulation Study on the Structural and Thermodynamic Analysis of Oxidized and Unoxidized Forms of Polyaniline.

The conducting polymer polyaniline (PANI) has shown significant interest for the development of electrified membranes (EMs) with superior antifouling characteristics. However, the blending and doping of PANI with other polymers and nanomaterials highly influence the properties of the membrane surface. PANI exists in two forms: oxidized, known as emeraldine salt (ES), and unoxidized, referred to as emeraldine base (EB). Therefore, understanding the different forms of PANI and the variations between the oxidized and unoxidized forms along the length of the polymer chain is intriguing. In this paper, we present the design of a novel copolymer consisting of EB and ES monomers with varying charge densities and different segmental arrangements. We present various intra- and intermolecular structural properties of the PANI chains using all-atom molecular dynamics (MD) simulations. Herein, we present a detailed conformational free energy analysis to understand the conformational transitions of the PANI chains. Our results show increased radius of gyration (Rg) values with increased charge density. Furthermore, we also present the H-bonding, free energy analysis, reduced density gradient (RDG), and solvent-accessible surface area (SASA) values for the observed conformational transitions of PANI. Therefore, these observations are crucial in understanding the complex behavior of chains for designing target-specific polymeric materials.

Ab Initio Investigation of Per- and Poly-fluoroalkyl Substance (PFAS) Adsorption on Zerovalent Iron (Fe0).

In this study, dispersion-corrected density functional theory (DFT) calculations were employed to investigate the adsorption of per- and poly-fluoroalkyl substances (PFAS) onto zerovalent iron (Fe0). The main objective of this investigation was to shed light on the adsorption properties, including adsorption energies, geometries, and charge transfer mechanisms, for four PFAS molecules, namely, perfluorooctanesulfonic acid (PFOS), perfluorobutanesulfonic acid (PFBS), perfluorooctanoic acid (PFOA), and perfluorobutanoic acid (PFBA), on the most thermodynamically accessible Fe0 surface facets. Additionally, the DFT investigation examined the role of PFAS chain length, functional group, protonation/deprotonation state, and solvation in water in their adsorption to Fe0. Overall, the adsorption of the four PFAS molecules on various Fe0 surfaces exhibited thermodynamically favorable energetics. Nevertheless, solvation in water resulted in less exothermic adsorption energies, and the presence of preadsorbed oxygen blocked the Fe0 surface, preventing PFAS adsorption. Additionally, the inclusion of a monolayer of Ni on top of the Fe0 surface reduced the stability of PFAS adsorption compared to pristine Fe0. Results of the computational investigation were compared to experimental results from the literature for qualitative validation.

SesA: A Program for the Analytic Computation of Solvent-Excluded Surface Areas.

The surface area of a molecule, an inherent geometric property of its structure, plays important roles in its solvation and functioning. Here we present an accurate and robust program, sesA, for the analytic computation of solvent-excluded surface (SES) areas. The accuracy and robustness are achieved through the analytic computations of all the solvent-accessible surface (SAS) regions for a surface atom and probe-probe intersections. The detailed comparisons of the areas for a large set of protein structures by sesA and msms, a de-facto standard for analytic SAS and SES computations, confirm sesA's accuracy to a good extent and in the same time reveal significant differences between them. The unprecedented accuracy and robustness of sesA make it possible to analyze in great detail the surface areas of any molecules in general and biomolecules in particular.

G-quadruplex formation in RNA aptamers selected for binding to HIV-1 capsid.

HIV-1 capsid protein (CA) is essential for viral replication and interacts with numerous host factors to facilitate successful infection. Thus, CA is an integral target for the study of virus-host dynamics and therapeutic development. The multifaceted functions of CA stem from the ability of CA to assemble into distinct structural components that come together to form the mature capsid core. Each structural component, including monomers, pentamers, and hexamers, presents a variety of solvent-accessible surfaces. However, the structure-function relationships of these components that facilitate replication and virus-host interactions have yet to be fully elucidated. A major challenge is the genetic fragility of CA, which precludes the use of many common methods. To overcome these constraints, we identified CA-targeting aptamers with binding specificity for either the mature CA hexamer lattice alone or both the CA hexamer lattice and soluble CA hexamer. To enable utilization of these aptamers as molecular tools for the study of CA structure-function relationships in cells, understanding the higher-order structures of these aptamers is required. While our initial work on a subset of aptamers included predictive and qualitative biochemical characterizations that provided insight into aptamer secondary structures, these approaches were insufficient for determining more complex non-canonical architectures. Here, we further clarify aptamer structural motifs using focused, quantitative biophysical approaches, primarily through the use of multi-effective spectroscopic methods and thermodynamic analyses. Aptamer L15.20.1 displayed particularly strong, unambiguous indications of stable RNA G-quadruplex (rG4) formation under physiological conditions in a region of the aptamer also previously shown to be necessary for CA-aptamer interactions. Non-canonical structures, such as the rG4, have distinct chemical signatures and interfaces that may support downstream applications without the need for complex modifications or labels that may negatively affect aptamer folding. Thus, aptamer representative L15.20.1, containing a putative rG4 in a region likely required for aptamer binding to CA with probable function under cellular conditions, may be a particularly useful tool for the study of HIV-1 CA.

Klebsiella pneumoniae Lipopolysaccharide as a Vaccine Target and the Role of Antibodies in Protection from Disease.

Klebsiella pneumoniae is well recognized as a serious cause of infection in healthcare-associated settings and immunocompromised individuals; however, accumulating evidence from resource-limited nations documents an alarming rise in community-acquired K. pneumoniae infections, manifesting as bacteremia and pneumonia as well as neonatal sepsis. The emergence of hypervirulent and antibiotic-resistant K. pneumoniae strains threatens treatment options for clinicians. Effective vaccination strategies could represent a viable alternative that would both preempt the need for antibiotics to treat K. pneumoniae infections and reduce the burden of K. pneumoniae disease globally. There are currently no approved K. pneumoniae vaccines. We review the evidence for K. pneumoniae lipopolysaccharide (LPS) as a vaccine and immunotherapeutic target and discuss the role of antibodies specific for the core or O-antigen determinants within LPS in protection against Klebsiella spp. disease. We expand on the known role of the Klebsiella spp. capsule and O-antigen modifications in antibody surface accessibility to LPS as well as the in vitro and in vivo effector functions reported for LPS-specific antibodies. We summarize key hypotheses stemming from these studies, review the role of humoral immunity against K. pneumoniae O-antigen for protection, and identify areas requiring further research.

Improving the pore properties of porous aromatic frameworks in two aspects via partition strategy

Microporous solids are famous for their high surface area and pore size at the molecular scale, which are crucial for the applications of adsorption, separation and catalysis. An ideal porous solid would simultaneously have a high surface area and nanopores with the desired opening size. However, due to the uncontrollable reaction process of porous organic frameworks (POFs), the acquisition of such a solid is still technically limited. Herein, we reported a simple but platform-wide pore partition strategy to improve the porosity of porous aromatic frameworks (PAFs) in two aspects. This strategy was achieved by introducing a partition unit with flexible linkage to segment the original voids of PAFs into multiple micropore domains. The obtained partitioning PAFs have 130%-217% increments in surface area due to the creation of extra accessible surfaces while the pores are segmented into smaller ones. Notably, the partitioning PAFs showed significantly increased adsorption capacity for CO2 due to their improved surface area. At the same time, the narrowed pore size allowed selective capture of dye molecules by their size differences. Similar to their parent PAFs, the partitioning PAFs retained their high stability in harsh environments. A simple and universal pore partition strategy will be an important step in improving PAF porosity to desired functions.

Computational exploration of novel ketoprofen derivatives: Molecular dynamics simulations and MM-PBSA calculations for COX-2 inhibition as promising anti-inflammatory drugs

Computer-aided drug design is widely employed to identify novel compounds for therapeutic applications. Ketoprofen (KTP), a commonly used and marketed nonsteroidal anti-inflammatory drug (NSAID), is effective in treating pain, fever, inflammation, and some cancers. In this research, we explored the behavior of six analogues designed by structurally modifying the KTP molecule. Specifically, KTP-A and KTP-B contain a –CN group at the ortho position, KTP-C and KTP-D have a –CN group at the meta position, and KTP-E and KTP-F feature a –CF3 group at the meta position. To assess these analogues, we conducted molecular dynamics simulations (MD) to study their inhibitory effects on human cyclooxygenase 2 (COX-2), providing detailed insights into the structure and dynamics of the protein both with and without ligands. MD simulation, enhanced by technological advances, has proven to be a powerful tool for new drug discovery. We further quantified the binding affinity of these drug molecules toward COX-2 using molecular mechanics Poisson-Boltzmann surface area (MM-PBSA) binding free energy calculations. The dynamic properties were evaluated through analyses of root mean square deviations (RMSD), root mean square fluctuations (RMSF), radius of gyration (Rg), solvent-accessible surface area (SASA), covariance matrix, principal component analysis (PCA), and Gibbs free energy landscapes (FEL). Ultimately, this study confirms that the six KTP derivatives are promising candidates for the treatment of inflammation, with KTP-B standing out as particularly effective.

Inhibiting Emulative Oxygen Adsorption via Introducing Pt-Segregated Sites into the Pd Surface for Enhanced H2 Sensing in Air.

Pd-modified metal sulfide gas sensors exhibit excellent hydrogen (H2) sensing activity through spillover effects. However, the emulative oxygen adsorption often occupies an exposed Pd surface and thus limits the effective Pd-H interaction, impeding the H2 sensing performance in air. Herein, we develop an edge-rich Pt-shell/Pd-core structure to adjust the selective adsorption between oxygen and hydrogen for effective H2 sensing in an air atmosphere. Detailedly, through accurately regulating the rate of Pt deposition onto the icosahedron Pd surface, an edge-rich Pt-shell/Pd-core structure can be first achieved. It has been found that marginal Pt aggregations can segregate the oxygen molecules around the Pt species and induce easier Pt-O bonding, further guiding accessible Pd surfaces for effective Pd-H interactions, which can be verified by 1H ssNMR, in-situ Raman, ex-situ XPS, and density functional theory analyses. The final ZnS/PdPt sensor exhibits an ultrasensitive response (8608 to 4% H2) and a wide detected range (0.5 ppm-4%) in air, exceeding most reported hydrogen sensors.

Calixarene incorporated molecular imprinting on covalent organic framework for supramolecular recognition and specific extraction of citrinin

Specific recognition and selective extraction of mycotoxin in environmental and food matrixes is significant to guarantee public health. Covalent organic frameworks (COFs) are promising adsorbents with tailorable functionality, but their low binding affinity and poor selectivity hamper their wide application for selective extraction of trace mycotoxin from complex matrix. Herein, we report calixarene incorporated molecular imprinting on COF to prepare molecularly imprinted calix[4]arene-containing COF (MICOF-CX4) for supramolecular recognition and specific adsorption of citrinin. Calixarene with host-guest chemistry was used as a functional monomer, while amine units with different topologies and function groups were selected to regulate MICOF-CX4 to match with citrinin. The complementary shape and supramolecular interactions of MICOF-CX4 gave highly selective recognition for citrinin. Moreover, MICOF-CX4 with vast accessible surface and plentiful imprinting sites exhibited faster adsorption kinetics and 4-fold higher adsorption capacity for citrinin adsorption than no-imprinted COF-CX4. Combination of MICOF-CX4 based solid-phase extraction with high-performance liquid chromatography-mass spectrometry allowed interference free determination of trace citrinin in real samples with a low detection limit of 0.03 ng mL−1, good precision of 4.5 % and quantitative recovery of 88.2 %−101.4 %. The cooperative functions of calixarene and molecular imprinting make COF promising adsorbent for specific adsorption of trace targets in complex matrixes.

Fluorine-doped carbon dots decorated on iron-cobalt selenide nanosheets as superior electrocatalysts for oxygen evolution in seawater

Developing oxygen evolution reaction (OER) catalysts that can efficiently and stably operate at high current densities in seawater electrolysis is urgently demanded but challenging. In this study, selenium-vacancies-rich iron-cobalt selenide nanosheets (FeCoSe-VSe) decorated with fluorine-doped carbon dots (FCDs) are rationally designed and prepared on nickel foams (NF) through the successive processes of hydrothermal treatment and selenization. Benefiting from the large accessible surface area and abundant active sites provided by FCDs and selenium vacancy defects, as well as the coupled interface between FCDs and FeCoSe-VSe that optimizes the oxygen adsorption energy and accelerates the kinetic process, the FCDs/FeCoSe-VSe/NF composite exhibits excellent OER catalytic activities with a low overpotential of 258 mV at a current density of 200 mA cm−2 in 1 M KOH and a small Tafel slope of 34.7 mV dec–1. In the electrolytes of simulated and natural seawater, the overpotentials of the FCDs/FeCoSe-VSe/NF electrode are slightly higher, measured to be 264 and 297 mV, respectively. More profoundly, the introduction of FCDs enhances the corrosion resistance of the catalyst in alkaline electrolytes, ensuring the long-term stability. This work offers a guidance to improve the electrochemical performances of catalysts for high-efficiency seawater oxidation.

Destabilisation of Alzheimer's amyloid-β protofibrils by Baicalein: mechanistic insights from all-atom molecular dynamics simulations.

Alzheimer's disease (AD) is the most common form of dementia and the fifth leading cause of death globally. Aggregation and deposition of neurotoxic Aβ fibrils in the neural tissues of the brain is a key hallmark in AD pathogenesis. Destabilisation studies of the amyloid-peptide by various natural molecules are highly relevant due to their neuroprotective and therapeutic potential for AD. We performed molecular dynamics (MD) simulation to investigate the destabilisation mechanism of amyloidogenic protofilament intermediate by Baicalein (BCL), a naturally occurring flavonoid. We found that the BCL molecule formed strong hydrophobic contacts with non-polar residues, specifically F19, A21, V24, and I32 of Chain A and B of the pentameric protofibril. Upon binding, it competed with the native hydrophobic contacts of the Aβ protein. BCL loosened the tight packing of the hydrophobic core by disrupting the hydrogen bonds and the prominent D23-K28 inter-chain salt bridges of the protofibril. The decrease in the structural stability of Aβ protofibrils was confirmed by the increased RMSD, radius of gyration, solvent accessible surface area (SASA), and reduced β-sheet content. PCA indicated that the presence of the BCL molecule intensified protofibril motions, particularly affecting residues in Chain A and B regions. Our findings propose that BCL would be a potent destabiliser of Aβ protofilament, and may be considered as a therapeutic agent in treating AD.