The 50 most-cited articles in Langmuir, 2022

A mixed-valency bimetallic Ce/Zr MOF with Ce 3+ /Ce 4+ ions incorporated and an oxygen vacancy-rich single-component photocatalyst have been designed through the one-step solvothermal route to harness photons from the visible-light spectrum for green energy (H 2 ) generation and ciprofloxacin (CIP) degradation. The one-pot-engineered bimetallic Ce/Zr MOF shows visible-light-active characteristics accompanied by a narrower band gap, along with enhanced exciton separation and superior ligand-to-metal charge transfer (LMCT), due to the presence of an interconvertible Ce 3+ /Ce 4+ ions pair in comparison to its pristine MOF counterpart. The Ce ion insertion led to increase in electron density around the Zr 4+ ion, along with generation of some oxygen vacancies (OV), which cumulatively led to the rise in the photo-reaction output. The synthesized UNH (Ce/Zr 1:1) MOF displayed a boosted photocatalytic H 2 production rate of 468.30 μmol h –1 (ACE = 3.51%), which is around fourfolds higher than that of pristine MOFs. Moreover, for CIP photodegradation, the UNH (Ce/Zr 1:1) shows an enhanced…

Combating environmental pollution constantly requires new affinity tools to selectively recognize and sensitively detect them. Molecularly imprinted polymers (MIPs) are plastic antibodies that have exhibited great potential as recognition units in optical sensing platforms to monitor wide varieties of environmental pollutants, including ionic species, organic compounds, gases, and even manufactured nanoparticles. The construction, sensing strategies, and applications of molecular-imprinting-based optical sensors (MI-OSs) have been discussed in recent reviews, thus we deliberately set them aside. This Perspective elaborates on unanswered questions and main approaches being taken to address the challenges of MI-OS technologies, which have been less considered until now. Specifically, we highlight obscure technical aspects of MI-OS fabrication and validation that impact their practical applications and importantly offer conceivable solutions to related problems to bridge the research gap.

Membrane separation is of great significance due to its unique performance in treating wastewater. However, the simultaneous treatment of oily emulsions and other complex pollutants in water remains challenging. Herein, we have proposed a simple strategy to prepare a multifunctional titanium dioxide/silver nanoparticles/polyacrylonitrile (TiO 2 /AgNPs/PAN) nanofibrous membrane. The experimental results showed that the combination of the hierarchical structure composed of PAN nanofibers and Ag/TiO 2 nanoprotrusions contributed to the superhydrophilicity and superoleophobicity (UOCA = 153.3 ± 2.0°). Further, the nanofibrous membrane exhibited a rapid gravity-driven permeate flux (>1829.37 ± 83.51 L m –2 h –1 ) and an ultrahigh separation efficiency (>99.9%) for the surfactant-stabilized oil/water emulsions. Moreover, due to the synergistic effect between the PAN fibers and TiO 2 /Ag heterojunction, Rhodamine B dye in water can be removed quickly and efficiently (up to 97.67% in 90 min). More importantly, the obtained nanofibrous membrane exhibited ultrahigh stability in different…

Here, an S-scheme heterojunction was constructed on the basis of the modification of a Ni-based metal–organic framework (Ni-MOF) by different in situ treatment strategies. First, NiS 2, NiO, and Ni 2 P were derived in situ on the surface of Ni-MOF through surface sulfonation, oxidation, and phosphatizing treatments. They can efficiently accept the electrons from the conduction band of Ni-MOF as the trap centers, thus improving the hydrogen production activity. Additionally, phosphatizing makes the electronegativity of Ni-MOF/P stronger than that of the original Ni-MOF, which can enhance the absorption of protons, thus promoting the hydrogen evolution reaction. Next, the S-scheme heterojunction was successfully built by the coupling of 2D CeO 2 with Ni-MOF/P. The maximum hydrogen production rate of the hybrid catalyst (6.337 mmol g –1 h –1 ) is 14.18 times that of the untreated Ni-MOF due to the full utilization of photo-induced electrons. Finally, the probable hydrogen evolution mechanism was proposed by analyzing a series of characterization results and by the density functional…

It is believed that the strong surface hydration of zwitterionic polymers leads to excellent antifouling properties. This Perspective presents the recent developments in studies on such surface hydration in situ using sum frequency generation (SFG) vibrational spectroscopy. SFG research provides direct molecular level evidence that zwitterionic polymers have strong surface hydration, which prevents protein adsorption and marine animal attachment. The salt effect and protein interaction on surface hydration of zwitterionic polymers have also been examined using SFG. Possible future research directions on surface hydration of new zwitterionic polymers including zwitterionic hydrogels, copolymers, and mixed charged polymers are discussed. It is also important to combine experimental SFG studies with computer simulations to further elucidate the surface hydration to understand antifouling mechanisms.

The current work delivers preparation of MXene-based magnetic nanohybrid coating for flexible electronic applications. Herein, we report carbon dot-triggered photopolymerized polynorepinepherene (PNE)-coated MXene and iron oxide hybrid deposited on the cellulose microporous membrane via a vacuum-assisted filtration strategy. The surface morphologies have been monitored by scanning electron microscopy analysis, and the coating thickness was evaluated by the gallium-ion-based focused ion beam method. Coated membranes have been tested against uniaxial tensile stretching and assessed by their fracture edges in order to assure flexibility and mechanical strength. Strain sensors and electromagnetic interference (EMI) shielding have both been tested on the material because of its electrical conductivity. The bending strain sensitivity has been stringent because of their fast 'rupture and reform' percolation network formation on the coated surface. Increased mechanical strength, solvent tolerance, cyclic deformation tolerance, and EMI shielding performance were achieved by decreasing…

Over the past decade, droplet microfluidics has attracted growing interest in biology, medicine, and engineering. In this feature article, we review the advances in droplet microfluidics, primarily focusing on the research conducted by our group. Starting from the introduction to the mechanisms of microfluidic droplet formation and the strategies for cell encapsulation in droplets, we then focus on droplet transformation into microgels. Furthermore, we review three biomedical applications of droplet microfluidics, that is, 3D cell culture, single-cell analysis, and in vitro organ and disease modeling. We conclude with our perspective on future directions in the development of droplet microfluidics for biomedical applications.

The field of nanozyme aims to use nanomaterials to replace protein-based enzymes. Nanozymes have attracted extensive interest because of their stability, cost-effectiveness, and versatility. While the focus of the nanozyme field has mainly been the discovery of new nanozyme materials and the exploration of their analytical, biomedical, and environmental applications, the number of fundamental studies is growing. Nanozymes are related to two important fields: enzymology and heterogeneous catalysis. Although fitting nanozyme kinetic data to the Michaelis-Menten kinetics is a very common practice, using the surface science methods of heterogeneous catalysis can provide insights about their catalytic mechanisms. The definition of a nanozyme unit is critical to understanding and comparing nanozyme activities. In this perspective, we articulate the use of a surface science approach to study nanozymes and discuss the various application scenarios of using different nanozyme units.

The construction of interfacial effects and chemical bonds between catalysts is one of the effective strategies to facilitate photogenerated electron transfer. A novel hollow cubic CoS is derived from Co-ZIF-9 and the S–C bond is successfully constructed between CoS and g-C 3 N 4 . The S–C bond acts as a bridge for electronic transmission, allowing the rapid transmission of photoelectron to hydrogen evolution active site in CoS. In addition, the results of electrochemical impedance spectroscopy and time-resolved photoluminescence spectroscopy show that the S–C bond acts as a bridge to quickly transfer photogenerated carriers in the composite material, and achieves the effect of high-efficiency hydrogen evolution. The hydrogen production of SgZ-45 reaches 9545 μmol·g –1 in 5 h, which is 53 and 12 times that of g-C 3 N 4 and ZIF-9, respectively. The intrinsic mechanism of photoelectron transfer through S–C bonds can be further confirmed by density functional theory (DFT) calculations. This work provides new insights for building a chemical bond electron transfer bridge between MOF…

Surface area estimation using the Brunauer-Emmett-Teller (BET) analysis has been beset by difficulties. The BET model has been applied routinely to systems that break its basic assumptions. Even though unphysical results arising from force-fitting can be eliminated by the consistency criteria, such a practice, in turn, complicates the simplicity of the linearized BET plot. We have derived a general isotherm from the statistical thermodynamic fluctuation theory, leading to facile isotherm fitting because our isotherm is free of the BET assumptions. The reinterpretation of the monolayer capacity and the BET constant has led to a statistical thermodynamic generalization of the BET analysis. The key is Point M, which is defined as the activity at which the sorbate-sorbate excess number at the interface is at its minimum (i.e., the point of strongest sorbate-sorbate exclusion). The straightforwardness of identifying Point M and the ease of fitting by the statistical thermodynamic isotherm have been demonstrated using zeolite 13X and a Portland cement paste. The adsorption at Point M is…

Discharge of oily sewage and frequent oil spills have caused serious harm to human production, life, and ecological environment. Due to the presence of a large number of surfactants in water, these oil-water mixtures are easy to form oil-in-water emulsion, which is difficult to separate by traditional methods. At the same time, the water-soluble pollutants such as dyes and heavy metal ions in oily wastewater also cause great harm to the human body and the environment. A pine nut shell is a kind of common domestic waste material. Herein, an underwater superoleophobic pine nut shell membrane (PNSM) was prepared by the simple pumping filtration method, which realized the separation of oil-in-water emulsion and adsorption of dyes and heavy metal ions. In addition, the filter membrane can be used for separating corrosive emulsions of strong acid, strong alkali, and 3.5% NaCl solutions (simulated seawater). Besides, the PNSM showed excellent toughness and flexibility. Due to the abovementioned performance, this cost-efficient and environmentally friendly membrane can be a promising…

A novel Bi 4 Ti 3 O 12 /g-C 3 N 4 /BiOBr(BTO/CN/BOB) composite was synthesized by a solvothermal–mechanical mixed thermal method. The composition, structure, and micromorphology of the samples were analyzed. The BTO/CN/BOB composite photocatalyst shows better photocatalytic performance for tetracycline hydrochloride (TC) degradation compared to Bi 4 Ti 3 O 12 and binary composite photocatalysts. The highest degradation rate of TC can reach 89.84% using the BTO/CN/BOB photocatalyst under the optimal conditions, and BTO/CN/BOB still exhibits good photocatalytic properties after recycling. Moreover, it also shows good photodegradation activity for different kinds of antibiotics, implying its wide application prospect. The photocatalytic performance and reuse stability of BTO/CN/BOB were significantly improved, which may be because of the enhanced spectral absorption range and efficient electron transfer capability by the synergistic effect and interaction among Bi 4 Ti 3 O 12, BiOBr, and g-C 3 N 4 . Finally, the possible degradation pathway and electron transfer mechanism of the dual…

Electric and magnetic fields have enabled both technological applications and fundamental discoveries in the areas of bottom-up material synthesis, dynamic phase transitions, and biophysics of living matter. Electric and magnetic fields are versatile external sources of energy that power the assembly and self-propulsion of colloidal particles. In this Invited Feature Article, we classify the mechanisms by which external fields impact the structure and dynamics in colloidal dispersions and augment their nonequilibrium behavior. The paper is purposely intended to highlight the similarities between electrically and magnetically actuated phenomena, providing a brief treatment of the origin of the two fields to understand the intrinsic analogies and differences. We survey the progress made in the static and dynamic assembly of colloids and the self-propulsion of active particles. Recent reports of assembly-driven propulsion and propulsion-driven assembly have blurred the conceptual boundaries and suggest an evolution in the research of nonequilibrium colloidal materials. We highlight the…

This study demonstrates a simple and fast method to integrate superhydrophobicity, UV protection, and photothermal effect onto PET fabrics. The surface of PET fabric forms a hierarchical rough structure through in situ oxidative polymerization of the pyrrole (Py). The 1,4-conjugate addition reaction between pentaerythritol tetraacrylate, 3-aminopropyltriethoxysilane, and octadecyl acrylate not only endows the PET fabric with superhydrophobicity but also forms a cross-linked network structure which improves the stability of multifunctional coatings on the surface of the PET fabric. In addition, the wettability of the prepared PET fabric is investigated by adjusting the Py monomer and octadecyl acrylate concentration. The results reveal that the prepared PET fabrics exhibit obviously superhydrophobic behavior with a contact angle of 155.8°. The surface temperature of the superhydrophobic PPy/PET fabric can rise to 91 °C under a simulated sunlight which is much higher than the pristine PET fabric, while reaching basically the same steady-state in five heating/cooling cycles. The…

In recent years, photothermal materials that can convert light into heat energy have attracted extensive attention. In this work, we report a simple and effective approach to construct a self-cleaning photothermal superamphiphobic fabric. Dopamine (DA) can self-polymerize into polydopamine (PDA) and adhere to the surface of cotton fabric as a secondary reaction platform. Then, SiO 2 nanoparticles were in situ grown on the PDA@fabric surface by the sol–gel method. The PDA clusters can not only provide good photothermal conversion performance but also be integrated with SiO 2 to create micro–nano rough structures. Finally, the surface of SiO 2 was modified by the long chain of fluorosilane to decrease the fabric surface energy, resulting in superamphiphobicity. The contact angles of water, ethylene glycol, and pump oil on the modified fabric surface could reach 161.1, 158.1, and 142.2°, respectively, making the fabric resistant to contamination by water, common beverages, and oil. Due to the adhesion of the PDA layer, the strong binding force between the fabric and SiO 2 particles…

Over the last decade, the interest in carbon dots, graphene dots, or similar carbon-based nanoparticles has increased considerably. This interest is based on potentially high fluorescent quantum yields, controllable excitation-dependent emission, low toxicity, and convenient reaction conditions. Carbon dots are often seen as a promising alternative to classical semiconductor quantum dots that are typically made from toxic semiconductor materials. Surprisingly, aspects like the atomic structure, composition, mechanism of formation, and precise understanding of the photophysical properties of carbon dots are still mostly unknown. The large number of different precursor systems and the variety in synthesis routes make a direct comparison of different systems difficult. To advance this, we went for a systematic approach and compared the results of four synthesis routes using two different precursor systems. We used different spectroscopy and microscopy methods including fluorescence correlation spectroscopy to characterize the different reaction products. We found that for syntheses…

Using the dispersion-corrected density functional theory (DFT-D3) method, we systematically studied the adsorption of 15 kinds of transition-metal (TM) clusters on pristine graphene (Gr) and N-doped graphene (N-Gr). It has been found that TM n ( n = 1–4) clusters adsorbed on the N-Gr surface are much stronger than those on the pristine Gr surface, while 3d series clusters present similar geometries on Gr and N-Gr surfaces. The most preferred sites of TMs migrate from hollow to bridge to the top site on the Gr surface along the d series in the periodic table, while the preferred sites of TMs migrate in a much more complex manner on the N-Gr surface. It has also been found that charge transfer decreases along the d series for adsorbed clusters on both surfaces, but adsorbed clusters present less charge transfer on the N-Gr surface than on the Gr surface. What is more interesting is that some TM (Tc, Ru, and Re) clusters change the growth mechanism from the three-dimensional (3D) growth mode on the Gr surface to the two-dimensional (2D) growth mode on the N-Gr surface. At last, it has…

The adverse effects of electrochemical bubbles on the performance of gas-evolving electrodes have been extensively studied. However, the ways in which bubbles dynamically alter the electrochemically active surface area during bubble evolution are not well understood. Here, we study hydrogen evolution at industrially relevant current densities by using controlled microtexture to examine this fundamental relationship. Surprisingly, the most densely microtextured electrodes have the lowest performance on an active surface area basis. Using high-speed imaging, we show that the benefits of microtexture to release smaller bubbles more consistently are outweighed by the inactivation induced by bubbles growing within the denser microtexture, causing these performance limitations. Additionally, we show that the area beneath adhered bubbles is electrochemically active, contrary to currently held assumptions. Our study therefore has broad implications for electrode design to avoid ineffective use of precious catalyst materials, which is especially critical for porous electrodes and…

Hydrogel-based sensors serve as an ideal platform for developing personalized wearable electronics due to their high flexibility and conformability. However, the weak stretchability and inferior conductivity of hydrogels have severely restricted their large-scale application. Herein, a natural polymer-based conductive hydrogel integrated with favorable mechanical properties, good adhesive performance, and excellent fatigue resistance was fabricated via interpenetrating tannic acid (TA) into a chitosan (CS) cross-linked network in an acidic aqueous solution. The hydrogel was composed of a regular hierarchical porous structure, which was built by the hydrogen bonding between TA and CS. In addition, the hydrogels exhibited adjustable mechanical properties (maximum yield stress of 7000 Pa) and good stretchability (strain up to 320%). Benefiting from the abundant catechol groups of TA, the proposed hydrogels could repeatedly adhere to various material surfaces and could be easily peeled off without residue. Moreover, the hydrogel exhibited stable conductivity, high stretching sensitivity…

Precise control over the stimuli-responsive noncovalent interactions operative in a complex molecular system has emerged as a convenient way to realize applications in the detection and sensing of trace analytes, metal ion separation, uptake–release, in situ nanoparticle synthesis, and catalytic activity. This feature article focuses on the attributes and advantages of noncovalent host–guest interactions involving cucurbituril homologues (CBs) with a wide range of organic and inorganic guests, starting from organic dyes to drugs, proteins, surfactants, metal ions, and polyoxometalates. The unique structural features of CBs provide interaction sites for cations at the portals, polyanions at the periphery, and hydrophobic groups in its cavity. The facile complexation and consequent compositional and geometrical arrangements of guests such as naphthalenediimides, coumarins, porphyrins, and triphenylpyrylium ions with the host CBs led to remarkable changes in many molecular properties, especially aggregation, the proton binding and release affinity, and novel emissive dimers, and each…

Tribocatalysis, as a new approach in environmental purification, has drawn increasing attention in the past few years. In this work, we successfully convert mechanical energy to chemical energy by Bi 12 TiO 20, which was synthesized by a hydrothermal method. Under magnetic stirring, electrons transfer from the surface of Bi 12 TiO 20 to the polytetrafluoroethylene-sealed magnetic bar due to their friction. Moreover, the holes that remain on Bi 12 TiO 20 provide oxidation properties in the process for organic matter degradation. According to a series of tests, it is noticed that the shape of the stirring bar and the material of the reaction vessel have a remarkable influence on the removal efficiency of contaminants. Simultaneously, multiple tests reveal the high stability of Bi 12 TiO 20 . A great potential for Bi 12 TiO 20 to control water pollutants under dark conditions during collection of ambient mechanical energy was clearly demonstrated in this study.

Researchers are looking for new, clean, and accessible sources of energy due to rising global warming caused by the usage of fossil fuels and the irreversible harm that this does to the environment. Water salinity is one of the newest and most accessible renewable energy sources, which has sparked a lot of interest. Reverse electrodialysis (RED) has been utilized in the past to turn saline water into electricity. NRED, a reverse electrodialysis method utilizing nanofluidics, has gained popularity as nanoscale research advances. Developing and evaluating NRED systems is time-consuming and expensive due to the method's novelty; thus, modeling is required to identify the best locations for implementation and to comprehend its workings. In this work, we examined the influence of bipolar soft layer and nanochannel geometry on ion transfer and power production simultaneously. To achieve this, the two trumpet and cigarette geometries were coated with a bipolar soft layer so that both negative (type (I)) and positive (type (II)) charges could be positioned in the nanochannel's small…

In the present investigation, a novel, green, and economical dual-functionalized pullulan/kaolin hydrogel nanocomposite ( f -PKHN) was fabricated and subsequently applied for the liquid-phase decontamination of paracetamol (PCT), a pharmaceutical pollutant. Pullulan and kaolin were functionalized with l -asparagine and gallic acid, respectively. The physicochemical facets of the functionalized pullulan/kaolin hydrogel nanocomposite and its interactive behavior with PCT were elucidated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX), and elemental mapping. The process parameters along with the isotherm, kinetics, and thermodynamics were methodically appraised via a batch technique to unveil the adsorption performance of the as-fabricated hydrogel nanocomposite. The adsorption isotherm and kinetics of PCT uptake by f -PKHN conform well to Freundlich and pseudo-second-order models, respectively. Relying…

Oceanic oil spill and the discharge of industrial oily wastewaters can cause significant threats to the ecological environment and human health. Herein, we design a durable TiO 2 /PDA-based superhydrophobic paper for efficient oil/water separation. Bioinspired from mussel adhesive proteins, the mechanical durability of the as-prepared superhydrophobic paper is enhanced by the deposition of polydopamine (PDA) onto cellulosic fibers via self-polymerization of dopamine. The TiO 2 /PDA-based superhydrophobic paper shows a high water contact angle of 168.2° and an oil contact angle of ∼0°, exhibiting excellent superhydrophobicity and superoleophilicity. Furthermore, the as-prepared superhydrophobic paper possesses excellent chemical stability, thermal stability, and mechanical durability in terms of being immersed in corrosive solutions and solvents and boiling water and being subjected to the sandpaper abrasion test, respectively. More importantly, the separation efficiency of the TiO 2 /PDA-based superhydrophobic paper for an oil/water mixture is 97.2%, and it maintains a separation…

The empirical laws of dry friction between two solid bodies date back to the work of Amontons in 1699 and are pre-dated by the work of Leonardo da Vinci. Fundamental to those laws are the concepts of static and kinetic coefficients of friction relating the pinning and sliding friction forces along a surface to the normal load force. For liquids on solid surfaces, contact lines also experience pinning and the language of friction is used when droplets are in motion. However, it is only recently that the concept of coefficients of friction has been defined in this context and that droplet friction has been discussed as having a static and a kinetic regime. Here, we use surface free energy considerations to show that the frictional force per unit length of a contact line is directly proportional to the normal component of the surface tension force. We define coefficients of friction for both contact lines and droplets and provide a droplet analogy of Amontons' first and second laws but with the normal load force of a solid replaced by the normal surface tension force of a liquid. In…

Developing an efficient, low-cost, and non-noble metal oxide-based nanohybrid material for overall water splitting is a highly desirable approach to promote clean energy harnessing and to minimize environmental issues. Accordingly, we proposed an interfacial engineering approach to construct layered porous graphitic carbon nitride (g-C 3 N 4 )-stabilized Co 2 SnO 4 inverse spinel nanohybrid materials as highly active bifunctional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline medium. Here, a Co 2 SnO 4 /g-C 3 N 4 nanohybrid with a layered porous g-C 3 N 4 stabilized cubelike inverse spinel has been synthesized with an enhanced surface area via a simple one-pot hydrothermal method. Besides, detailed structural and morphological characterizations were carried out using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission-scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), Fourier transform infrared (FT-IR), and Brunauer–Emmett–Teller (BET) analysis.…

To ensure the quality and reliability of products bonded by epoxy resin adhesives, elucidation of the microscopic adhesion mechanism is essential. The adhesive interaction and bonding strength between epoxy resins and hydroxylated γ-alumina (001) surfaces were investigated by using a combined molecular dynamics (MD) and density functional theory (DFT) study. The curing reaction of an epoxy resin consisting of diglycidyl ether of bisphenol A (DGEBA) and 4,4'-diaminodiphenyl sulfone (DDS) was simulated. The resin structure was divided into fragmentary structures to study the interaction of each functional group with the alumina surface using DFT calculations. From the characteristics of the adhesive structures and the calculated adhesion energies, it was found that the fragments forming hydrogen bonds with hydroxy groups on the alumina surface resulted in large adhesion energies. On the other hand, the fragments adsorbed on the alumina surface via dispersion interactions resulted in small adhesion energies. The adhesion forces evaluated from the Hellmann-Feynman force calculations…

The stimuli responsive pesticide delivery system (PDS) has drawn increasing attention in recent years, a system which can effectively improve the utilization of pesticides. In the current research, we report a pH responsive PDS by using carboxymethyl cellulose (CMC) modified Zr-based metal organic frameworks (UiO-66-NH 2 ) as the nanocarrier for acetamiprid (ATP). UiO-66-NH 2 -CMC possesses a large surface area and abundant pores, which can effectively load ATP, and the loading rate is as high as 90.79%. Compared with free ATP, the ATP@UiO-66-NH 2 -CMC nanopesticide exhibits pH responsive controlled release behavior, and the pesticide can sustained release to the medium. In addition, it also shows improved leaf affinity, which makes it easier to wet the leaf surface and improve the utilization of pesticide. Therefore, ATP@UiO-66-NH 2 -CMC displays better antipest activity against aphids than free ATP does. Meanwhile, ATP@UiO-66-NH 2 -CMC shows no negative effects on the germination and growth of maize, showing good biosafety. Moreover, the ATP@UiO-66-NH 2 -CMC nanopesticide does not…

Carbon dots (CDs) with long-lived room-temperature phosphorescence (RTP) or long afterglow properties draw much attention. However, most room-temperature phosphorescent materials are metal containing, and the exploitation of long-lived color-tunable RTP materials faces great challenges. Here, we report metal-free boron-doped CDs (B-CDs) for room-temperature phosphorescence with tunable color and an ultralong lifetime. B-CDs were obtained by simply calcining a mixture of boric acid and 1,3,5-benzenetricarboxylic acid in the atmosphere. The as-prepared B-CDs were characterized through UV-vis spectroscopy, photoluminescence spectroscopy, and so forth. Under the excitation of 310 nm UV light, B-CDs show RTP that appears as blue with a phosphorescence lifetime of 1042 ms, and after switching the excited wavelength to 365 nm, the RTP appears as green with a phosphorescence lifetime of 590 ms. Due to the unique RTP properties, B-CDs display promising applications in anticounterfeiting and information encryption.

Surfactants with their intrinsic ability to solubilize lipids are widely used as antibacterial agents. Interaction of surfactants with the bacterial cell envelope is complicated due to their propensity to aggregate. It is important to discern the interactions of micellar aggregates and single surfactants on the various components of the cell envelope to improve selectivity and augment the efficacy of surfactant-based products. In this study, we present a combined experimental and molecular dynamics investigation to unravel the molecular basis for the superior kill efficacy of laurate over oleate observed in contact time assays with live E. coli . To gain a molecular understanding of these differences, we performed all-atom molecular dynamics simulations to observe the interactions of surfactants with the periplasmic peptidoglycan layer and the inner membrane of Gram-negative bacteria. The peptidoglycan layer allows a greater number of translocation events for laurate when compared with oleate molecules. More interestingly, aggregates did not translocate the peptidoglycan layer,…

Molecularly imprinted ratiometric fluorescence (MIR-FL) nanosensors feature recognition selectivity, detection sensitivity, application universality, visualization accuracy, and device portability, and have gained popularity. However, the fluorescence intensity, nanostructure, color range, and practical application of the sensor still face severe difficulties to be solved. New strategies combined with various technologies have been developed to construct MIR-FL nanosensors for expanded applications. This Perspective highlights current resarch challenges and future prospects involving constructions and applications of MIR-FL nanosensors including dual-emission and triple-emission modes. The postimprinting mixing/modification strategies, microdevices, and multitarget detection are focused, and technology synergy, sensitivity/reproducibility improvement, application diversity/portability, etc. are proposed.

Oxygen vacancy modulation holds great promise for enhancing the photocatalytic activity for efficient nitrogen fixation under mild conditions. In this work, the two-dimensional WO 3– x nanosheets with rich oxygen vacancies were prepared using solvothermal synthesis. The WO 3– x nanosheets (rich oxygen vacancies) display nice photocatalytic activity for N 2 reduction to ammonia with a high yield rate of 82.41 μmol·g cat –1 ·h –1 under irradiation of visible light (420 nm), which is 3.59 times higher than that of the WO 3– x nanoparticles (poor oxygen vacancies). Electron spin resonance (ESR), N 2 adsorption–desorption isotherms, and transient photocurrent responses in the N 2 or Ar atmosphere experiments proved that the rich oxygen vacancies, which are induced by the nanosheet structure, could serve as active sites for the chemisorption of N 2 and facilitate the electron transfer from unsaturated sites to activated N 2 . Moreover, based on the analysis of banding energy, the oxygen vacancies not only boosted the ability of visible light harvesting but also elevated the defect energy…

C) has attracted extensive attention and is regarded as a promising research area in the near future owing to its good biocompatibility, high stability, band gap adjustability, rich valence states, and excellent catalytic activity. This Perspective summarizes the recent progress and achievements for the molybdenum carbide-based catalysts. First, the crystal and band structures of molybdenum carbides are generally presented. Second, various modifying strategies for molybdenum carbides are outlined to enhance the photocatalytic performance, including doping engineering, vacancy engineering, morphology and structure engineering, and the establishment of molybdenum carbide-based composite catalysts. Finally, potential applications in the photocatalysis area of molybdenum carbide-based photocatalyst are generalized. Future development trends and perspective for this promising material are also discussed.

Hydrogels have emerged as multifunctional interface materials between implantable bioelectronic devices and biotissues. The soft and wet materials with low and alterable mechanical properties can match the mechanical, chemical, electrical, and biological properties of biotissues and thus diminish the mechanical and electrical mismatch. Interactions at the hydrogel-biotissue and hydrogel-device interfaces have attracted broad research interest. Great efforts have been devoted to establishing instant, strong, and conformal adhesion at the interface by chemical bonding, electrostatic interaction, hydrogen bonding, supramolecular recognition, hydrophobic association, and even topological entanglements at the interfaces. This Perspective provides a brief account of representative progress on the hydrogel-tissue adhesive that forms seamless and conformal interface adhesion and applications in implantable devices for physiological, cardiac, and neuronal signal collection and electrical stimulation. Major challenges such as wet adhesion and the stability of the adhesive hydrogel-tissue…

High Resolution Image Download MS PowerPoint Slide Fungal cellulases generally contain a reduced amount of β-glucosidase (BG), which does not allow for efficient cellulose hydrolysis. To address this issue, we implemented an easy co-immobilization procedure of β-glucosidase and cellulase by adsorption on wrinkled mesoporous silica nanoparticles with radial and hierarchical open pore structures, exhibiting smaller (WSN) and larger (WSN-p) inter-wrinkle distances. The immobilization was carried out separately on different vectors (WSN for BG and WSN-p for cellulase), simultaneously on the same vector (WSN-p), and sequentially on the same vector (WSN-p) in order to optimize the synergy between cellulase and BG. The obtained results pointed out that the best biocatalyst is that prepared through simultaneous immobilization of BG and cellulase on the same vector (WSN-p). In this case, the adsorption resulted in 20% yield of immobilization, corresponding to an enzyme loading of 100 mg/g of support. 82% yield of reaction and 72 μmol/min·g activity were obtained, evaluated for the hydrolysis…

A green synthetic strategy to design biomass-derived porous carbon electrode materials with precisely tailored structure and morphology has always been a challenging goal because these materials can fulfill the demands of next-generation supercapacitors and other electrochemical devices. Potassium hydroxide (KOH) is extensively utilized as an activator since it can produce porous carbon with high specific surface area and well-developed porous channels. The exploitation of sodium hydroxide (NaOH) as an activating agent is less referenced in the literature, although it offers some advantages over KOH in terms of low cost, less corrosiveness, and simple handling procedure, all of which are appealing particularly from an industrial viewpoint. The motivation for this present study is to fabricate porous carbon spheres in a sustainable manner via a spray drying approach followed by a carbonization process, using Kraft lignin as the carbon precursor and NaOH as an alternative activation agent instead of the high-cost and high-corrosive KOH for the first time. The structure of carbon…

Establishment of an efficient and robust artificial photocatalytic system to convert solar energy into chemical fuels through CO 2 conversion is a cherished goal in the fields of clean energy and environmental protection. In this work, we have explored an emergent low- Z nitrogen-rich carbon nitride material g-C 3 N 5 (analogue of g-C 3 N 4 ) for CO 2 conversion under visible light illumination. A significant enhancement of the CH 4 production rate was detected for g-C 3 N 5 in comparison to that of g-C 3 N 4 . Notably, g-C 3 N 5 also showed a very impressive selectivity of 100% toward CH 4 as compared to 21% for g-C 3 N 4 . The photocatalytic CO 2 conversion was performed without using sacrificial reagents. We found that 1% K doping in g-C 3 N 5 enhanced its performance even further without compromising the selectivity. Moreover, 1% K-doped g-C 3 N 5 also exhibited better photostability than undoped g-C 3 N 5. We have also employed density functional theory calculation-based analyses to understand and elucidate the possible reasons for the better photocatalytic performance of…

The zeolitic imidazolate framework-8 (ZIF-8) nanozyme has been synthesized using hydrophobic amino acid (AA) to regulate crystal growth. The as-synthesized ZIF-8 reproduces both the structural and functional properties of natural carbonic anhydrase (CA). Structurally, Zn 2+ /2-methylimidazole coordinated units mimic very well the active center of CA while the hydrophobic microdomains of the adsorbed AA simulate the CA hydrophobic pocket. Functionally, the nanozymes show excellent CA-like esterase activity by giving specific enzyme activity of 0.22 U mg –1 at 25 °C in the case of Val–ZIF-8. More strikingly, such nanozymes are superior to natural CA by having excellent hydrothermal stability, which can give highly enhanced esterase activity with increasing temperature. The specific enzyme activity of Val–ZIF-8 at 80 °C is about 25 times higher than that at 25 °C. In addition, AA–ZIF-8 also shows an excellent catalytic efficiency toward carbon dioxide (CO 2 ) hydration. This study puts forward the important role of hydrophobic microdomains in biomimetic nanozymes for the first time and…

The balance between hydration and Derjaguin-Landau-Verwey-Overbeek (DLVO) forces at solid-liquid interfaces controls many processes, such as colloidal stability, wetting, electrochemistry, biomolecular self-assembly, and ion adsorption. Yet, the origin of molecular scale hydration forces and their relation to the surface charge density that controls the continuum scale electrostatic forces is poorly understood. We argue that these two types of forces are largely independent of each other. To support this hypothesis, we performed atomic force microscopy experiments using intermediate-sized tips that enable the simultaneous detection of DLVO and molecular scale oscillatory hydration forces at the interface between composite gibbsite:silica-aqueous electrolyte interfaces. We extract surface charge densities from forces measured at tip-sample separations of 1.5 nm and beyond using DLVO theory in combination with charge regulation boundary conditions for various pH values and salt concentrations. We simultaneously observe both colloidal scale DLVO forces and oscillatory hydration forces…

N and S codoped carbon dots having good water solubility have been successfully made by a novel hydrothermal method and characterized by FTIR, XPS, and TEM. The as-synthesized CDs were carbon particles rich in polar functional groups less than 10 nm in size. Electrochemical measurements, gravimetry, and surface analysis methods were utilized to examine the inhibition characteristics and adsorption mechanism of CDs on the carbon steel in acid pickling solutions. Electrochemical measurements verified that the CDs displayed adequate protection with high inhibition efficiency of 97.8%. The long-term weight-loss experiments up to 72 h further confirmed the excellent corrosion inhibition at room temperature and 313 K. The results presented are helpful for the formulation of more effective acid pickling corrosion inhibitors.

In the present study, first, Fe 3 O 4 nanoparticles were functionalized using glutaric acid and then composited with CQDs. Doxorubicin (DOX) drug was loaded to evaluate the performance of the nanocomposite for targeted drug delivery applications. The XRD pattern confirmed the presence of characteristic peaks of CQDs and Fe 3 O 4 . In the FTIR spectrum, the presence of carboxyl functional groups on Fe 3 O 4 /CQDs was observed; DOX (positive charge) is loaded onto Fe 3 O 4 /CQDs (negative charge) by electrostatic absorption. FESEM and AFM images showed that the particle sizes of Fe 3 O 4 and CQDs were 23–75 and 1–3 nm, respectively. The hysteresis curves showed superparamagnetic properties for Fe 3 O 4 and Fe 3 O 4 /CQDs (57.3 and 8.4 emu/g). The Fe 3 O 4 hysteresis curve showed superparamagnetic properties (Ms and Mr: 57.3 emu/g and 1.46 emu/g. The loading efficiency and capacity for Fe 3 O 4 /CQDs were 93.90% and 37.2 mg DOX/g MNP, respectively. DOX release from Fe 3 O 4 /CQDs in PBS showed pH-dependent release behavior where after 70 h at pH 5 and 7.4, about 50 and 21% of DOX were…

In recent years, lead-free perovskite materials are exponentially emerging in photovoltaic and optoelectronic applications due to their low toxicity and superior optical properties. On the other hand, the demand for flexible, wearable, and lightweight optoelectronic devices is significantly growing in sensor and actuator technologies. In this scenario, lead-free perovskite-based flexible piezoelectric polymer composites have sparked considerable attention in this field due to their excellent piezo-, pyro-, ferroelectric, and photovoltaic properties. Thus, in this work, a long-term stable lead-free Cs 3 Bi 2 I 9 -PVDF composite is introduced. The in situ growth of the Cs 3 Bi 2 I 9 perovskite induces 92% yield of the electroactive phase in the PVDF matrix. The possible mechanism behind the electroactive β-phase transformation is presented via interfacial interactions of PVDF moieties with the Cs 3 Bi 2 I 9 (CBI) perovskite, which also give rise to long-term environmental stability. Next, a piezoelectric nanogenerator (PNG) has been fabricated with the Cs 3 Bi 2 I 9 -PVDF composite…

Lipid-shelled nanobubbles (NBs) are emerging as potential dual diagnostic and therapeutic agents. Similar to their micron-scale counterparts, microbubbles (1-10 μm), they can act as ultrasound contrast agents as well as locally enhance therapeutic uptake. Recently, it has been shown that the reduced size of NBs (<1 μm) promotes increased uptake and accumulation in tumor interstitial space, which can enhance their diagnostic and therapeutic performance. However, accurate characterization of NB size and concentration is challenging and may limit their translation into clinical use. Their submicron nature limits accuracy of conventional microscopy techniques, while common light scattering techniques fail to distinguish between subpopulations present in NB samples (i.e., bubbles and liposomes). Due to the difficulty in the characterization of NBs, relatively little is known about the influence of size on their therapeutic performance. In this study, we describe a novel method of using a commercially available nanoparticle tracking analysis system, to distinguish between NBs and…

Superhydrophobic (SH) polylactic acid (PLA) surfaces were previously produced by various methods and used especially in biomedical applications and oil/water separation processes after 2008. However, the wettability of SH-PLA patterns containing micropillars has not been investigated before. In this study, PLA patterns having regular microstructured pillars with 12 different pillar diameters and pillar-to-pillar distances were prepared by hot pressing pre-flattened PLA sheets onto preformed polydimethylsiloxane (PDMS) soft molds having micro-sized pits. PDMS templates were previously prepared by photolithography using SU-8 molds. Apparent, advancing, and receding water contact angle measurements were carried out on the PLA patterns containing micropillars, and the morphology of the patterns was examined by optical and SEM microscopy. The largest contact angle obtained without the surface modification of the pure PLA pattern was 139°. Then, PLA micropatterns were hydrophobized using three types of silanes via chemical vapor deposition method, and SH-PLA patterns were obtained having…

Metal organic frameworks (MOFs) have been used to encapsulate an array of enzymes in a rapid and facile manner; however, the stability of MOFs as supports for enzymes has not been examined in detail. This study examines the stability of MOFs with different compositions (Fe-BTC, Co-TMA, Ni-TMA, Cu-TMA, and ZIF-zni) in buffered solutions commonly used in enzyme immobilization and biocatalysis. Stability was assessed via quantification of the release of metals by inductively coupled plasma optical emission spectroscopy. The buffers used had varied effects on different MOF supports, with incubation of all MOFs in buffers resulting in the release of metal ions to varying extents. Fe-BTC was completely dissolved in citrate, a buffer that has a profound destabilizing effect on all MOFs analyzed, precluding its use with MOFs. MOFs were more stable in acetate, potassium phosphate, and Tris HCl buffers. The results obtained provide a guide for the selection of an appropriate buffer with a particular MOF as a support for the immobilization of an enzyme. In addition, these results identify the…

The interaction of particles with fluid interfaces is ubiquitous in synthetic and natural work, involving two types of interactions: particle-interface interactions (trapping energy) and interparticle interactions. Therefore, it is urgent to gain a deep understanding of the main forces controlling the trapping of particles at fluid interfaces, and their assembly to generate a broad range of structures characterized by different degrees of order. This Perspective tries to provide an overview of the main contributions to the energetic landscape controlling the assembly of particles at fluid interfaces, which is essential for exploiting this type of interfacial systems as platforms for the fabrication of interface-based soft materials with technological interest.

Bubble evolution plays a fundamental role in boiling and gas-evolving electrochemical systems. One key stage is bubble departure, which is traditionally considered to be buoyancy-driven. However, conventional understanding cannot provide the full physical picture, especially for departure events with small bubble sizes commonly observed in water splitting and high heat flux boiling experiments. Here, we report a new regime of bubble departure owing to the coalescence of two bubbles, where the departure diameter can be much smaller than the conventional buoyancy limit. We show the significant reduction of the bubble base area due to the dynamics of the three-phase contact line during coalescence, which promotes bubble departure. More importantly, combining buoyancy-driven and coalescence-induced bubble departure modes, we demonstrate a unified relationship between the departure diameter and nucleation site density. By elucidating how coalescing bubbles depart from a wall, our work provides design guidelines for energy systems which can largely benefit from efficient bubble departure.

Liposomes are promising spherical vesicles for topical drug delivery to the eye. Several types of vesicles were formulated in this study, including conventional, PEGylated, and maleimide-decorated PEGylated liposomes. The physicochemical characteristics of these liposomes, including their size, zeta potential, ciprofloxacin encapsulation efficiency, loading capacity, and release, were evaluated. The structure of these liposomes was examined using dynamic light scattering, transmission electron microscopy, and small angle neutron scattering. The ex vivo corneal and conjunctival retention of these liposomes were examined using the fluorescence flow-through method. Maleimide-decorated liposomes exhibited the best retention performance on bovine conjunctiva compared to other types of liposomes studied. Poor retention of all liposomal formulations was observed on bovine cornea.

Aqueous polyelectrolyte-surfactant complexes (PESCs) are very rich with respect to their properties and the structures formed by them. By design they normally contain hydrophobic micellar surfactant aggregates complexed by long polyelectrolyte chains, thereby combining the formation of small hydrophobic domains given by the surfactant with large-scale structuring due to the presence of the polyelectrolyte chain. In addition, they contain highly polar regions of surfactant head groups in contact with polyelectrolyte, forming a shell around the micellar aggregates, which often also possesses a certain hydrophobic character. Accordingly, the ability for solubilization of water-insoluble compounds of different sorts is particularly versatile in PESCs. Their solubilization sites with very different polarities and hydrophobic characters make them very flexible in adapting to the requirements of a given drug molecule. This renders them attractive for potential applications in drug delivery. In addition, modification of the rheological properties via self-assembly and network formation can…

Superhydrophobic surfaces decorated with macrostructures have attracted extensive attention due to their excellent performance of reducing the contact time of impacting droplets. In many practical applications, the surface is not perpendicular to the droplet impact direction, but the impacting dynamics in such scenarios still remain mysterious. Here, we experimentally investigate the dynamics of droplet impact on inclined ridged superhydrophobic surfaces and reveal the effect of We n (the normal Weber number) and α (the inclination angle) on the contact time τ. As We n increases, τ first decreases rapidly until a platform is reached; if We n continues to increase, τ further reduces to a lower platform, indicating a three-stage variation of τ in low, middle, and high We n regions. In the middle and high We n regions, the contact time is reduced by 30 and 50%, respectively, and is dominated by droplet spreading/retraction in the tangential and lateral directions, respectively. A quantitative analysis demonstrates that τ in the middle and high We n regions is independent of We n and α,…