Efficient removal of chloroform from groundwater using activated percarbonate by cellulose nanofiber-supported Fe/Cu nanocomposites.

Chloroform (CF) is a recalcitrant halogenated methane (HM) that has received widespread attention due to its frequent detection in groundwater and its potential carcinogenic risk. In this study, TEMPO-oxidized cellulose nanofiber-supported iron/copper bimetallic nanoparticles (TOCNF-Fe/Cu), a novel composite catalyst, was synthesized to activate sodium percarbonate (SPC) for the removal of CF from groundwater. The results showed that over 96.3% of CF could be removed in a neutral reaction medium (pH 6.5-9) within 180 min using 0.66 g L-1 of TOCNF (0.32)-Fe/Cu (1) and 1 mM of SPC, which outperforms typical advanced oxidation processes. The reaction mechanism of the TOCNF-Fe/Cu-SPC system for the CF removal was elucidated. As demonstrated through electron paramagnetic resonance and quenching experiments, the TOCNF-Fe/Cu-SPC system was found to include •OH and O2•-, where the latter played a dominant role in the CF removal. DFT calculations indicated that TOCNF improved the electron transport capability of Fe/Cu and reduced the transition state energy. The Fe species on the surface of TOCNF-Fe/Cu were identified as the primary active sites for SPC activation, whereas the Cu species were beneficial to the regeneration of the Fe species. Additionally, TOCNF-Fe/Cu was found to have good recyclability and stability. The feasibility of the TOCNF-Fe/Cu-SPC system was further confirmed by applying it for the efficient removal of composite HMs from actually contaminated groundwater. Overall, the TOCNF-Fe/Cu-SPC system is an attractive candidate for the treatment of HM-contaminated groundwater.

Anisotropic cellulose nanocrystalline sponge sheets with ultrahigh water fluxes and oil/water selectivity.

Oily sewage caused by oil spill accidents has become a severe problem in the last decades. Hence, two-dimensional sheet-like filter materials for oil/water separation have received widespread attention. Porous sponge materials were developed using cellulose nanocrystals (CNCs) as raw materials. They are environmentally friendly and easy to prepare, with high flux and separation efficiency. The 1,2,3,4-butane tetracarboxylic acid cross-linked anisotropic cellulose nanocrystalline sponge sheet (B-CNC) exhibited ultrahigh water fluxes driven by gravity alone, depending on the aligned structure of channels and the rigidity of CNCs. Meanwhile, the sponge gained superhydrophilic/underwater superhydrophobic wettability with an underwater oil contact angle of up to 165.7° due to its ordered micro/nanoscale structure. B-CNC sheets displayed high oil/water selectivity without additional material doping or chemical modification. For oil/water mixtures, high separation fluxes of approximately 100,000 L·m-2·h-1 and separation efficiencies of up to 99.99 % were obtained. For a Tween 80-stabilized toluene-in-water emulsion, the flux reached >50,000 L·m-2·h-1, and the separation efficiency was above 99.7 %. B-CNC sponge sheets showed significantly higher fluxes and separation efficiencies than other bio-based two-dimensional materials. This research provides a facile and straightforward fabrication method of environmental-friendly B-CNC sponges for rapid, selective oil/water separation.

Lubricin-Inspired Loop Zwitterionic Peptide for Fabrication of Superior Antifouling Surfaces.

Biofouling represents great challenges in many applications, and zwitterionic peptides have been a promising candidate due to their biocompatibility and excellent antifouling performance. Inspired by lubricin, we designed a loop-like zwitterionic peptide and investigated the effect of conformation (linear or loop) on the antifouling properties using a combination of surface plasma resonance (SPR), surface force apparatus (SFA), and all atomistic molecular dynamics (MD) simulation techniques. Our results demonstrate that the loop-like zwitterionic peptides perform better in resisting the adsorption of proteins and bacteria. SFA measurements show that the loop-like peptides reduce the adhesion between the modified surface and the modeling foulant lysozyme. All atomistic MD simulations reveal that the loop-like zwitterionic peptides are more rigid than the linear-like zwitterionic peptides and avoid the penetration of the terminus into the foulants, which lower the interaction between the zwitterionic peptides and foulants. Besides, the loop-like zwitterionic peptides avoid the aggregation of the chains and bind more water, improving the hydrophilicity and antifouling performance. Altogether, this study provides a more comprehensive understanding of the conformation effect of zwitterionic peptides on their antifouling properties, which may contribute to designing novel antifouling materials in various biomedical applications.

Nontoxic Black Phosphorus Quantum Dots Inhibit Insulin Amyloid Fibrillation at an Ultralow Concentration.

Amyloid are protein aggregates formed by cross ß structures assemblies. Inhibiting amyloid aggregation or facilitating its disassembly are considered to be two major effective therapeutic strategies in diseases involving peptide or protein fibrillation such Alzheimer's disease or diabetes. Using thioflavin-T fluorescence, far-UV circular dichroism spectroscopy, and atomic force microscopy, we found nontoxic and biocompatible black phosphorus quantum dots (BPQDs) appear to have an exceptional capacity to inhibit insulin aggregation and to disassemble formed mature fibrils, even at an ultralow concentration (100 ng/mL). The inhibition of fibrillation persists at all stages of insulin aggregation and increases PC12 cells survival when exposed to amyloid fibrils. Molecular dynamics simulations suggest that BPQDs are able to stabilize the α-helix structure of insulin and obliterate the ß-sheet structure to promote the fibril formation. These characteristics make BPQDs be promising candidate in preventing amyloidosis, disease treatment, as well as in the storage and processing of insulin.

Three-dimensional printing of black phosphorous/polypyrrole electrode for energy storage using thermoresponsive ink.

Three-dimensional (3D) printing techniques bring the possibility of making electronic devices in any desired shape and dimensions. Here, we report on a printable black phosphorous nanosheet/polypyrrole composite ink for constructing a high-performance supercapacitor (SC) electrode. The printed BPNS/PPy electrode shows a good energy storage performance with a specific capacitance of up to 417 F g-1 and an excellent cycling stability.

Zwitterionic Peptide Enhances Protein-Resistant Performance of Hyaluronic Acid-Modified Surfaces.

A convenient and efficient approach for the surface modification of antifouling materials is highly desirable in numerous applications like affinity-based biosensors. Herein, we fabricated a hybrid antifouling coating on Au surfaces, with thiolated hyaluronic acid (HA) being chemically adsorbed to Au surfaces by the "graft to" approach, followed by a self-assembly of a smaller zwitterionic peptide named p-EK to obtain HA/p-EK-modified surfaces. The real-time sensorgrams of surface plasmon resonance biosensor manifested the successful modification of HA and p-EK on Au surfaces, indicating that there were some bare Au substrates on the HA-modified surfaces for peptide binding. The obtained HA/p-EK surfaces exhibited high hydrophilicity with a water contact angle of 9°. Quartz crystal microbalance and surface plasmon resonance experiments verified that further grafting the zwitterionic p-EK peptide on HA-modified surfaces could enhance the antifouling performance by one time. The improved protein resistance could be mainly contributed by the modification of the zwitterionic peptide that shields the exposed Au substrates from interacting with protein foulings. This strategy by grafting a smaller zwitterionic peptide might provide a novel way to achieve an enhanced protein-resistant performance of the macromolecular coating obtained by the "graft to" surface modification approach.

Polydopamine-Assisted Surface Coating of MIL-53 and Dodecanethiol on a Melamine Sponge for Oil-Water Separation.

A superhydrophobic and superoleophilic porous composite was successfully prepared via a polydopamine-assisted surface coating of MIL-53(Fe) and 1-dodecanethiol (DDT) on a melamine formaldehyde (MF) sponge. The as-prepared sponge composite (MIL-DDT@MF) has a high water contact angle (WCA) of 151.8°, which is probably attributed to both the rough surface derived from in situ growth of MIL-53 nanocrystals and the low surface energy due to grafting of hydrophobic 1-dodecanethiol. The MIL-DDT@MF sponge can effectively absorb oil or organic solvent with an absorption capacity of up to 54.1 (for petroleum) to 120.2 (for chloroform) times its own weight. In addition, the MIL-DDT@MF sponge retained a high absorption capacity and maintained approximately 78% of its original value after 50 cycles of reuse. Moreover, the MIL-DDT@MF sponge can selectively absorb the oil/organic solvent from water and achieve continuous oil-water separation. The separation efficiency of n-hexane, dichloromethane, and crude oil from water or seawater can reach above 95%. The superhydrophobic and superoleophilic MIL-DDT@MF sponge has potential as a promising absorbent for treatment of oily wastewater.

Three-Dimensionally Printed Bioinspired Superhydrophobic Packings for Oil-in-Water Emulsion Separation.

The separation of oil-water emulsions has attracted considerable attention in recent years. The main challenge is to find new cost-effective ways to develop a separation technology that has the potential for scaling up treatment. In this study, benefitting from the idea in traditional chemical engineering processes, we report on three-dimensionally printed superhydrophobic poly(lactic acid) (PLA) packings for oil-in-water emulsion separation. Superhydrophobicity was achieved through a bioinspired modification process including selective solvent etching and nanoparticle decoration. The obtained superhydrophobic PLA packing has an air-water contact angle of 150° and a water adhesion force of 22 µN. A maximum separation efficiency of 95% was achieved while retaining a relatively high flux of 7.5 kL m-2 h-1 by tailoring the internal geometry. Our approach demonstrates a promising method to fabricate packings with user-defined and functional features. The relatively low-cost and efficient fabrication process is beneficial in industrial applications.

Interactions of Transition Metal Dichalcogenide Nanosheets With Mucin: Quartz Crystal Microbalance With Dissipation, Surface Plasmon Resonance, and Spectroscopic Probing.

Ultrathin 2-dimensional transition metal dichalcogenides (TMDs) have become a class of high-potential materials in biomedicine due to their intriguing properties. They have been applied to solve biomedical challenges, such as biosensing, bioimaging, drug delivery, and cancer therapy. However, studies of the interactions between these materials and biomolecules are insufficient. Mucous tissue serves as a barrier to foreign hazardous substances and a gel layer for substance exchange. The main organic matter of mucous tissue is mucin, so it was selected as a model biomolecule to study its interactions with six different TMD nanosheets (NSs), including single-layered (SL), few-layered (FL), and small few-layered (SFL) MoS2 and WS2 NSs, using quartz crystal microbalance (QCM) with a dissipation monitor (QCM-D) and surface plasmon resonance (SPR). Additionally, UV absorption, fluorescence, and circular dichroism (CD) spectroscopy were applied to investigate the mechanism of the interactions and to study the conformational change of mucin. We found that the TMD NSs could adsorb on the mucin layer and affect its viscoelasticity. The results indicated that the SL WS2 NSs exhibited the highest initial absorption rate and the maximum absorption amount, while the SL MoS2 NSs exhibited the highest initial desorption rate. During the adsorption, the viscoelasticity variations of the mucin layer caused by the WS2 nanosheets were weaker than those caused by the MoS2 nanosheets. Furthermore, the conformational changes of mucin caused by the SL MoS2, SL WS2, and SFL MoS2 NSs were higher than those resulting from other TMD NSs. These findings provide important information on the interactions between TMD NSs and mucin and provide useful insights into the interfacial behavior of TMD NSs before they enter tissues.

Fluorescent silicon nanoparticles inhibit the amyloid fibrillation of insulin.

Amyloid fibrillation of proteins is likely a key factor leading to the development of amyloidosis-associated diseases. Inhibiting amyloid fibrillation has become a crucial therapeutic strategy. Water-soluble, fluorescent silicon nanoparticles (SiNPs) have great potential in biomedicine for various therapeutic and diagnostic purposes; however, it is unclear whether SiNPs have the ability to inhibit amyloid fibrillation. Herein, insulin was chosen as a protein model, and SiNPs of varying sizes were synthesized upon UV irradiation. The influence of size and concentration of the SiNPs on insulin fibrillation was investigated, and it has been observed that these variables were crucial in regulating insulin fibrillation. Using an average particle size of 6.6 nm and increasing the concentration of the SiNPs to 5.0 µg mL-1, the Thioflavin T (ThT) fluorescence intensity decreased significantly by 90%, with an increased lag time of 76.8 h, compared to that of the control. Insulin aggregates were short, thin fibrils or clusters when incubated with SiNPs, compared to the long, thick fibrils formed for insulin alone. Additionally, we found that the SiNPs prevent the conformational transition of insulin from its initial structure to ß-sheets, and thus inhibit nucleation, which is necessary for the formation of large fibrils. The inhibitory activity is attributed to the interactions between the SiNPs and insulin during the nucleation period. Our results demonstrate that the SiNPs disrupt insulin amyloid fibrillation, and thus, may play a useful role in new therapeutic and diagnostic strategies for amyloid-related disorders.

Self-Assembled Microporous Peptide-Polysaccharide Aerogels for Oil-Water Separation.

We report a new kind of peptide-polysaccharide aerogel which was formed by the coassembly of the fluorenylmethyloxycarbonyl-diphenylalanine (Fmoc-FF) peptide and the polysaccharide konjac glucomannan (KGM). The porosity and hydrophobicity of the hybrid aerogels could be facilely tailored by modifying the mass ratio of Fmoc-FF and KGM. The aerogels with tunable architecture showed good performance for the separation of a wide variety of oil-water mixtures. The results provide an opportunity for the design of peptide materials as a new class of biocompatible absorbents with potential applications in biomedicine and separation.

Bioinspired Peptide-Coated Superhydrophilic Poly(vinylidene fluoride) Membrane for Oil/Water Emulsion Separation.

Polyvinylidene fluoride (PVDF) membranes are limited in the field of oil-in-water emulsion treatment because the intrinsic hydrophobicity of PVDF can cause serious membrane fouling. Here, a superhydrophilic PVDF membrane (PVDF@PDA-GSH) was fabricated using a facile, versatile, mussel-inspired method. The pristine PVDF membrane was coated with dopamine under mild alkaline conditions by a dip-coating method, followed by addition of glutathione (GSH) via a simple reaction. GSH was successfully coated onto the membrane surface and confirmed by X-ray photoelectron spectroscopy and energy dispersive X-ray spectrometry. Hierarchical surface structure and superhydrophilicity were examined by scanning electron microscopy and contact angle, respectively, giving the PVDF@PDA-GSH membrane excellent wettability and antifouling ability. The water flux of PVDF@PDA-GSH was several-fold higher than conventional filtration membranes, and the oil rejection ratio was nearly 99%. The PVDF@PDA-GSH membrane also showed favorable reusability because the flux recovery ratio (FRR) remained above 90% after five cycles. In general, these results indicated that this modification might provide a good method for the fabrication of superhydrophilic PVDF membranes with good prospects for water filtration applications.

Molecularly Imprinted Core-Shell CdSe@SiO2/CDs as a Ratiometric Fluorescent Probe for 4-Nitrophenol Sensing.

4-Nitrophenol (4-NP) is a priority pollutant in water and is both carcinogenic and genotoxic to humans and wildlife even at very low concentrations. Thus, we herein fabricated a novel molecularly imprinted core-shell nanohybrid as a ratiometric fluorescent sensor for the highly sensitive and selective detection of 4-NP. This sensor was functioned by the transfer of fluorescence resonance energy between photoluminescent carbon dots (CDs) and 4-NP. This sensor was synthesized by linking organosilane-functionalized CDs to silica-coated CdSe quantum dots (CdSe@SiO2) via Si-O bonds. The nanohybrids were further modified by anchoring a molecularly imprinted polymer (MIP) layer on the ratiometric fluorescent sensor through a facile sol-gel polymerization method. The morphology, chemical structure, and optical properties of the resulting molecularly imprinted dual-emission fluorescent probe were characterized by transmission electron microscopy and spectroscopic analysis. The probe was then applied in the detection of 4-NP and exhibited good linearity between 0.051 and 13.7 µg/mL, in addition to a low detection limit of 0.026 µg/mL. Furthermore, the simplicity, reliability, high selectivity, and high sensitivity of the developed sensor demonstrate that the combination of MIPs and ratiometric fluorescence allows the preparation of excellent fluorescent sensors for the detection of trace or ultra-trace analytes.

Oriented Enzyme Immobilization at the Oil/Water Interface Enhances Catalytic Activity and Recyclability in a Pickering Emulsion.

Enzyme-loaded water-in-oil Pickering emulsion is a promising system for biphasic catalytic reactions. In this paper, we report on oriented enzyme immobilization at the oil/water interface in a Pickering emulsion, in which CHO-Janus silica nanoparticles (CHO-JNPs) are utilized as a stabilizer of the emulsion and support for the enzyme to enhance both catalytic activity and recyclability. The catalytic performance of this immobilized enzyme (lipase from Candida sp.) was evaluated by esterification of hexanoic acid and 1-hexanol in a water/heptane biphasic medium. The results show that the specific catalytic activity of the immobilized enzyme (33.2 U mL-1) was 6.5 and 1.4 times higher than that of free enzyme (5.1 U mL-1) and encapsulated enzyme in the liquid core (23.3 U mL-1), respectively. Moreover, the immobilized enzyme demonstrated good stability and recyclability, retaining 75% of its activity after 9 cycles. We expect that oriented enzyme immobilization at the oil/water interface will be an important strategy for enhancing catalytic performance in Pickering emulsions.

Molecular cloning and expression analysis of duplicated polyphenol oxidase genes reveal their functional differentiations in sorghum.

Polyphenol oxidase (PPO) is believed to play a role in plant growth, reproduction, and resistance to pathogens and pests. PPO causes browning of grains in cereals. In this study, genetic mapping of sorghum grain for phenol color reaction (PHR) was performed using a recombinant inbred line population. Only one locus was detected between SSR markers SM06072 and Xtxp176 on chromosome 6. Two linked orthologous genes (Sb06PPO1 and Sb06PPO2) within the mapped region were discovered and cloned. Transformation experiments using Nipponbare (a PHR negative rice cultivar) showed that Sb06PPO1 from LTR108 and two Sb06PPO2 alleles from both varieties could complement Nipponbare, whereas Sb06PPO1 from 654 could not. Subsequent quantitative real-time PCR (qPCR) experiments showed that Sb06PPO1 and Sb06PPO2 functioned diversely, Sb06PPO1 was mainly expressed in young panicles before flowering. Sb06PPO2 was strongly expressed in flowering panicles, especially in hulls and branches at filling stage. Moreover, the expression of Sb06PPO1 was found to be significantly up-regulated by exogenous ABA and salt, whereas Sb06PPO2 was not changed significantly, further demonstrating functional differentiation between the two genes.

Association of BAFF and IL-17A with subphenotypes of primary Sjögren's syndrome.

AIM: Primary Sjögren's syndrome (pSS) is an autoimmune disease affecting exocrine glands. Both autoreactive T cells and B cells are involved in the development of pSS, but their exact contribution to the pathogenesis is not clear. Here, we aimed to investigate the association of B-cell activating factor (BAFF) and interleukin (IL)-17A with subphenotypes of pSS. METHODS: Peripheral blood samples were collected from 31 pSS patients and 28 healthy controls. The serum levels of BAFF and IL-17A were quantified by sandwich ELISA. RESULTS: The increased circulating BAFF levels are associated with higher immunoglobulin G (IgG) levels (P = 0.0167) and anti-Ro/SS antigen A autoantibody (P = 0.032), while the elevated circulating levels of IL-17A are associated with lower C3 levels (P = 0.0213) and higher focus score of salivary gland tissue (P = 0.002). CONCLUSION: Our results show that BAFF and IL-17A are associated with different subphenotypes of pSS, suggesting both humoral and cellular immune response are involved in the pathogenesis of pSS.

Superior Antifouling Performance of a Zwitterionic Peptide Compared to an Amphiphilic, Non-Ionic Peptide.

The aim of this study was to explore the influence of amphiphilic and zwitterionic structures on the resistance of protein adsorption to peptide self-assembled monolayers (SAMs) and gain insight into the associated antifouling mechanism. Two kinds of cysteine-terminated heptapeptides were studied. One peptide had alternating hydrophobic and hydrophilic residues with an amphiphilic sequence of CYSYSYS. The other peptide (CRERERE) was zwitterionic. Both peptides were covalently attached onto gold substrates via gold-thiol bond formation. Surface plasmon resonance analysis results showed that both peptide SAMs had ultralow or low protein adsorption amounts of 1.97-11.78 ng/cm2 in the presence of single proteins. The zwitterionic peptide showed relatively higher antifouling ability with single proteins and natural complex protein media. We performed molecular dynamics simulations to understand their respective antifouling behaviors. The results indicated that strong surface hydration of peptide SAMs contributes to fouling resistance by impeding interactions with proteins. Compared to the CYSYSYS peptide, more water molecules were predicted to form hydrogen-bonding interactions with the zwitterionic CRERERE peptide, which is in agreement with the antifouling test results. These findings reveal a clear relation between peptide structures and resistance to protein adsorption, facilitating the development of novel peptide-containing antifouling materials.

Deciphering the binding patterns and conformation changes upon the bovine serum albumin-rosmarinic acid complex.

Rosmarinic acid (RA) is an importantly and naturally occurring polyphenol from plants of the mint family with potent biological activities. Here, the in vitro interaction of RA with bovine serum albumin (BSA) has been investigated using various biophysical approaches as well as molecular modeling methods, to ascertain its binding mechanism and conformational changes. The fluorescence results demonstrated that the fluorescence quenching of BSA by RA was mainly the result of the formation of a ground state BSA-RA complex, and BSA had one high affinity RA binding site with a binding constant of 4.18 × 10(4) mol L(-1) at 298 K. Analysis of thermodynamic parameters revealed that hydrophobic and hydrogen bond interactions were the dominant intermolecular force in the complex formation. The primary binding site of RA in BSA (site I) had been identified by site marker competitive experiments. The distance between RA and the tryptophan residue of BSA was evaluated at 3.12 nm based on Förster's theory of non-radiation energy transfer. The UV-vis absorption, synchronous fluorescence, three-dimensional fluorescence, 8-anilino-1-naphthalenesulfonic acid (ANS) fluorescence, circular dichroism (CD), and Fourier transform infrared (FT-IR) spectra confirmed that the conformation and structure of BSA were altered in the presence of RA. Moreover, the nuclear magnetic spectroscopy showed that the aromatic groups of RA took part in the binding reaction during the BSA-RA complexation. In addition, the molecular picture of the interaction mechanism between BSA and RA at the atomic level was well examined by molecular docking and dynamics studies. In brief, RA can bind to BSA with noncovalent bonds in a relatively stable way, and these findings will be beneficial to the functional food research of RA.

Interfacial Polymerization of Dopamine in a Pickering Emulsion: Synthesis of Cross-Linkable Colloidosomes and Enzyme Immobilization at Oil/Water Interfaces.

Colloidosomes are promising carriers for immobilizing enzyme for catalytic purposes in aqueous/organic media. However, they often suffer from one or more problems regarding catalytic performance, stability, and recyclability. Here, we report a novel approach for the synthesis of cross-linkable colloidosomes by the selective polymerization of dopamine at oil/water interfaces in a Pickering emulsion. An efficient enzyme immobilization method was further developed by covalently bonding enzymes to the polydopamine (PDA) layer along with the formation of such colloidosomes with lipase as a model enzyme. In this enzyme system, the PDA layer served as a cross-linking layer and enzyme support for simultaneously enhancing the colloidosomes' stability and improving surface availability of the enzymes for catalytic reaction. It was found that the specific activity of lipases immobilized on the colloidosome shells was 8 and 1.4 times higher than that of free lipase and encapsulated lipase positioned in the aqueous cores of colloidosomes, respectively. Moreover, the immobilized lipases demonstrated excellent operational stability and recyclability, retaining 86.6% of enzyme activity after 15 cycles. It is therefore reasonable to expect that this novel approach for enzyme immobilization has great potential to serve as an important technique for the construction of biocatalytic systems.

Capillary Force-Driven, Hierarchical Co-Assembly of Dandelion-Like Peptide Microstructures.

The wetting and drying of drops on flexible fibers occurs ubiquitously in nature, and the capillary force underlying this phenomenon has motivated our great interest in learning how to direct supramolecular self-assembly. Here, the hierarchical co-assembly of two aromatic peptides, diphenylalanine (FF) and ferrocene-diphenylalanine (Fc-FF), is reported via sequential, combinatorial assembly. The resulting dandelion-like microstructures have highly complex architectures, where FF microtube arrays serve as the scapes and the Fc-FF nanofibers serve as the flower heads. Homogeneous FF microtubes with diameters tailored between 1 and 9 µm and wall thickness ranging from 70 to 950 nm are initially formed by controlling the degree of supersaturation of the FF and the water content. Once the FF microtubes are formed, the growth of the dandelion-like microstructures is then driven by the capillary force, derived from the wetting and drying of the Fc-FF solution on the FF microtubes. This simple and ingenious strategy offers many opportunities to develop new and creative methods for controlling the hierarchical self-assembly of peptides and thus building highly complex nano and microstructures.