Nutrient-rich hydrothermal carbon production by exogenous nutrients combined with seaweed internal water.

As a product of hydrothermal carbonization (HTC) technology, hydrothermal carbon has shown excellent application potential in soil improvement, greenhouse gas reduction and pollution remediation. Since a large amount of water and biomass are directly used as reaction media, hydrothermal carbon produced by traditional HTC possesses poor nutrient properties and accompanied by the generation of toxic and hazardous wastewater. Here, a versatile and easily scalable strategy has been demonstrated for the one-step production of industrial nutrient-rich hydrothermal carbon (NRHC) by combining the exogenous nutrients with seaweed internal water. During the reaction process, exogenous nutrients (NH4H2PO3, KNO3, CO(NH2)2) participated in the HTC reaction and were uniformly distributed on the surface of hydrothermal carbon through surface complexation precipitation, ion exchange, and electrostatic interactions. Simulations based on density functional theory revealed that NRHC produced in presence of exogenous nutrients possessed more active sites and surface charges. Moreover, the adsorbent and adsorbate were simultaneously affected by intermolecular forces, electrostatic forces, and internal energy of the system, and the thermodynamics of adsorption process was more stable. Compared with no exogenous nutrient involvement, NRHC produced by exogenous nutrients showed 2.12, 18.56, and 25.69 times increase in the N, P, and K content. The length of the seed germination root system increased by 4.3-5.9 times, which met the standards set for agricultural fertilizer. Due to increased yield per unit volume and reduced wastewater generation, the cost of NRHC production reduced by 47.83-58.23 per cent and profit enhanced by 1.56-1.68 times, as compared to traditional HTC. This low-cost streamlined process provides a new strategy for large-scale production and direct application of hydrothermal carbon.

Development and Optimal Immune Strategy of an Alum-Stabilized Pickering emulsion for Cancer Vaccines.

Therapeutic cancer vaccines are considered as one of the most cost-effective ways to eliminate cancer cells. Although many efforts have been invested into improving their therapeutic effect, transient maturation and activations of dendritic cells (DCs) cause weak responses and hamper the subsequent T cell responses. Here, we report on an alum-stabilized Pickering emulsion (APE) that can load a high number of antigens and continue to release them for extensive maturation and activations of antigen-presenting cells (APCs). After two vaccinations, APE/OVA induced both IFN-γ-secreting T cells (Th1) and IL-4-secreting T cells (Th2), generating effector CD8+ T cells against tumor growth. Additionally, although they boosted the cellular immune responses in the spleen, we found that multiple administrations of cancer vaccines (three or four times in 3-day intervals) may increase the immunosuppression with more PD-1+ CD8+ and LAG-3+ CD8+ T cells within the tumor environment, leading to the diminished overall anti-tumor efficacy. Combining this with anti-PD-1 antibodies evidently hindered the suppressive effect of multiple vaccine administrations, leading to the amplified tumor regression in B16-OVA-bearing mice.

Inside-out assembly of viral antigens for the enhanced vaccination.

Current attempts in vaccine delivery systems concentrate on replicating the natural dissemination of live pathogens, but neglect that pathogens evolve to evade the immune system rather than to provoke it. In the case of enveloped RNA viruses, it is the natural dissemination of nucleocapsid protein (NP, core antigen) and surface antigen that delays NP exposure to immune surveillance. Here, we report a multi-layered aluminum hydroxide-stabilized emulsion (MASE) to dictate the delivery sequence of the antigens. In this manner, the receptor-binding domain (RBD, surface antigen) of the spike protein was trapped inside the nanocavity, while NP was absorbed on the outside of the droplets, enabling the burst release of NP before RBD. Compared with the natural packaging strategy, the inside-out strategy induced potent type I interferon-mediated innate immune responses and triggered an immune-potentiated environment in advance, which subsequently boosted CD40+ DC activations and the engagement of the lymph nodes. In both H1N1 influenza and SARS-CoV-2 vaccines, rMASE significantly increased antigen-specific antibody secretion, memory T cell engagement, and Th1-biased immune response, which diminished viral loads after lethal challenge. By simply reversing the delivery sequence of the surface antigen and core antigen, the inside-out strategy may offer major implications for enhanced vaccinations against the enveloped RNA virus.

Liquid-solid ratio during hydrothermal carbonization affects hydrochar application potential in soil: Based on characteristics comparison and economic benefit analysis.

Returning straw-like agricultural waste to the field by converting it into hydrochar through hydrothermal carbonization (HTC) is an important way to realize resource utilization of waste, soil improvement, and carbon sequestration. However, the large-scale HTC is highly limited by the large water consumption and waste liquid pollution. Here, we propose strategies to optimize the liquid-solid ratio (LSR) of HTC, and comprehensively evaluate the stability, soil application potential, and economic benefits of corn stover-based hydrochar under different LSRs. The results showed that the total amount of dissolved organic carbon of hydrochars increased by 55.0% as LSR reducing from 10:1 to 2:1, while the element content, thermal stability, carbon fixation potential, specific surface area, pore volume, and functional group type were not obviously affected. The specific surface area and pore volume of hydrochar decreased by 61.8% and 70.9% as LSR reduced to 1:1, due to incomplete carbonization. According to the gray relation, hydrochar derived at LSR of 10:1 and followed by 2:1 showed greatest relation degree of 0.80 and 0.70, respectively, indicating better soil application potential. However, reducing LSR from 10:1 to 2:1 made the income of single process production increased from -388 to 968 ¥, and the wastewater generation decreased by 80%. Considering the large-scale application of HTC in fields for farmland improvement and environmental remediation, the comprehensive advantages of optimized LSR will be further highlighted.

Cellular Affinity of Particle-Stabilized Emulsion to Boost Antigen Internalization.

The cellular affinity of micro-/nanoparticles is the precondition for cellular recognition, cellular uptake, and activation, which are essential for drug delivery and immune response. The present study stemmed from the observation that the effects of charge, size, and shape of solid particles on cell affinity are usually considered, but we seldom realize the essential role of softness, dynamic restructuring phenomenon, and complex interface interaction in cellular affinity. Here, we developed poly-lactic-co-glycolic acid (PLGA) nanoparticle-stabilized Pickering emulsion (PNPE) that overcame the shortcomings of rigid forms and simulated the flexibility and fluidity of pathogens. A method was set up to test the affinity of PNPE to cell surfaces and elaborate on the subsequent internalization by immune cells. The affinity of PNPE to bio-mimetic extracellular vesicles (bEVs)-the replacement for bone marrow dendritic cells (BMDCs)-was determined using a quartz crystal microbalance with dissipation monitoring (QCM-D), which allowed real-time monitoring of cell-emulsion adhesion. Subsequently, the PNPE was used to deliver the antigen (ovalbumin, OVA) and the uptake of the antigens by BMDCs was observed using confocal laser scanning microscope (CLSM). Representative results showed that the PNPE immediately decreased frequency (ΔF) when it encountered the bEVs, indicating rapid adhesion and high affinity of the PNPE to the BMDCs. PNPE showed significantly stronger binding to the cell membrane than PLGA microparticles (PMPs) and AddaVax adjuvant (denoted as surfactant-stabilized nano-emulsion [SSE]). Furthermore, owing to the enhanced cellular affinity to the immunocytes through dynamic curvature changes and lateral diffusions, antigen uptake was subsequently boosted compared with PMPs and SSE. This protocol provides insights for designing novel formulations with high cell affinity and efficient antigen internalization, providing a platform for the development of efficient vaccines.

Orally administered covalently-assembled antioxidative peptide nanoparticles for inflammatory bowel disease therapy.

HYPOTHESIS: Inflammatory bowel disease (IBD) is a chronic inflammation disease and still faces many therapeutic challenges, such as ineffective treatments, antibiotic resistance, and systematic toxicity. In order to improve the therapeutic efficacy of IBD, it is thus urgent to develop efficient, non-toxic and conveniently-administrated nanoagents to replace the currently used medicines. Casein phosphopeptide (CPP) has been found capable of chelating transition metal ions to suppress reactive oxygen species (ROS) generation, showing the potential for the treatment of IBD. However, CPP easily suffers from hydrolysis and enzymatic degradation, which limits its further clinical application. Covalent assembly of CPP to form nanoparticles (GCPP NPs) may be an efficient way to enhance the CPP stability in physiological environment and finally improve its capability of in vivo antioxidation and IBD treatment. EXPERIMENTS: We synthesized GCPP NPs through covalent assembly of Genipin and CPP, followed by characterizing their physicochemical properties. GCPP NPs were incubated under different physiological conditions including phosphate buffered saline, cell culture media, simulated gastrointestinal fluid for evaluation of stability. Cytotoxicity and antioxidation activities of GCPP NPs were tested in vitro under the 3T3 cell line using the ABTS and MTT assays, respectively. Finally, a DSS-induced mouse colitis model was established to assess specific accumulation and good therapeutic efficacy of GCPP NPs via an oral administration strategy. FINDINGS: GCPP NPs are robust and stable to overcome easy degradation of CPP even under the harsh gastrointestinal environments, which are adapted for oral administration. As-prepared GCPP NPs show benign antioxidant activity to scavenge ROS. Meanwhile, nanoscale GCPP NPs can passively accumulate and maintain at inflamed sites. The body weight and colon length of DSS-induced colitis mice treated by GCPP NPs perform a rehabilitation trend. These results indicate that GCPP NPs, as peptide-based therapeutic nanoagents, have great potential in the anti-inflammatory treatment of IBD by oral administration.

Correction: Coordination-assembled myricetin nanoarchitectonics for sustainably scavenging free radicals.

[This corrects the article DOI: 10.3762/bjnano.13.23.].

The effect of biochar on the migration theory of nutrient ions.

As the acidification of arable soils increases, the utilization of nutrient ions such as N, P, and K decreases substantially. It causes environmental pollution and reduces crop yields. Through previous studies, acidified soil amendments have problems such as easy-retrograde and unclear mechanism. Therefore, in this study, biochar prepared by pyrolysis using peanut shells was used as a green amendment for acidified soil. Biochar with 0, 5 and 10 % biochar ratios were applied to the acidified soil, and the improvement and mechanism were investigated via experiments and software simulations. Analysis of the software simulation results revealed that biochar had the highest unit adsorption of K+ through physical adsorption at 820.38 mg/g. This was followed by PO43-, NO3-, and NH4+ as 270.51, 235.65 and 130.93 mg/g, respectively. These ions were controlled by both electrostatic and ion-exchange adsorption processes. During the improvement, the 10 % biochar ratio group performed the best with a 65.32 % reduction in the outlet volume, and the accumulated levels of nutrient ions in the leachate dropped by 48.40-68.28 % and increased by 437.80-913.87 % in the surface soil. Nutrient ion levels decreased gradually with the increase of soil depth, which agreed with the software simulation results. This study found that applying biochar to acidified soils can provide a solution to low nutrient utilization efficiency and unclear improvement mechanism of acidified soils, and provide a partial theoretical basis for the large-scale application of biochar. Future research on biochar for soil carbon sink and microbial expansion can be strengthened to contribute to environmental protection and multi-level utilization of energy.

Coordination-assembled myricetin nanoarchitectonics for sustainably scavenging free radicals.

Oxidative stress can lead to permanent and irreversible damage to cellular components and even cause cancer and other diseases. Therefore, the development of antioxidative reagents is an important strategy to alleviate chronic diseases and maintain the redox balance in cells. Small-molecule bioactive compounds have exhibited huge therapeutic potential as antioxidants and anti-inflammatory agents. Myricetin (Myr), a well-known natural flavonoid, has drawn wide attention because of its high antioxidant, anti-inflammatory, antimicrobial, and anticancer efficacy. Especially regarding antioxidation, Myr is capable of not only chelating intracellular transition metal ions for removing reactive oxygen species, but also of activating antioxidant enzymes and related signal pathways and, thus, of sustainably scavenging radicals. However, Myr is poorly soluble in water, which limits its bioavailability for biomedical applications, and even its clinical therapeutic potential. The antioxidant peptide glutathione (GSH) plays a role as antioxidant in cells and possesses good hydrophilicity and biocompatibility. However, it is easily metabolized by enzymes. To take advantages of their antioxidation activity and to overcome the abovementioned limitations, GSH, Zn2+, and Myr were selected to co-assemble into Myr-Zn2+-GSH nanoparticles or nanoarchitectonics. This study offers a new design to harness stable, sustainable antioxidant nanoparticles with high loading capacity, high bioavailability, and good biocompatibility as antioxidants.

Self-Assembly of Triphenylamine Macrocycles and Co-assembly with Guest Molecules at the Liquid-Solid Interface Studied by STM: Influence of Different Side Chains on Host-Guest Interaction.

The side chains of macrocyclic molecules have a non-negligible effect on the two-dimensional (2D) supramolecular networks at the liquid-solid interface. In this study, we investigate the self-assembly behaviors of two conjugated triphenylamine macrocycles modified with different alkyl chains and construct the host-guest supramolecular nanopatterns on the highly oriented pyrolytic graphite with a scanning tunneling microscope. In combination with density functional theory calculations, how different side chains affect the host-guest interaction is discussed. This work provides insights into constructing a 2D host-guest dynamic co-assembly on the surface.

Evaluating the addition of xylooligosaccharides into alginate-gelatin hydrogels.

Xylooligosaccharides (XOS) are emerging prebiotic that may improve structural features of biopolymer blends. The investigation around the conformation of XOS into the matrix of alginate and gelatin clarifies the potential applications of this formulation in the food industry as texture modifiers or encapsulation systems. Structural properties verified by flow behavior, SEM, XRD, and FT-IR demonstrated that the add up to 3% XOS into the alginate-gelatin blend formed a cohesive matrix, with smaller pores and crystalline structure, confirming the potential of xylooligosaccharides hydrogels for the development of functional and synbiotic foods.

Novel insights on the encapsulation mechanism of PLGA terminal groups on ropivacaine.

Currently, the influences of free terminal groups (hydroxyl, carboxyl and ester) of PLGA on encapsulating active pharmaceutical ingredient are relatively ambiguous even though PLGA types were defined as critical quality attributes in vast majority of design of experiment process. In this study, emulsion method combined with premix membrane emulsification technique has been used to encapsulate ropivacaine (RVC), a small molecule local anesthetic in clinical. Based on the narrow particle size distribution, the influences and mechanisms of the terminal groups on properties of ropivacaine loaded microspheres have been investigated in detail. It was found that microspheres prepared by PLGA with hydroxyl or ester groups exhibited lower encapsulation efficiency but faster in vitro release rate than that of carboxyl groups. In the meanwhile, on microcosmic level analysis by quartz crystal microbalance with dissipation, atomic force microscope and confocal laser scanning microscopy, we attributed this distinction to the specific interaction between ropivacaine and different terminal groups. Subsequently, the reaction activation centers were verified by density functional simulation calculation and frontier molecular orbital theory at molecular level. Additionally, pharmacokinetics and pharmacodynamic research of infiltration anesthesia model were performed to compare sustained release ability, duration and intensity of the anesthetic effect in vivo. Finally, potential safety and toxicity were evaluated by the biochemical analysis. This study not only provides a novel mechanism of drug encapsulation process but also potential flexible selections in terms of various anesthesia indications in clinical.

One-pot synthesis of conjugated triphenylamine macrocycles and their complexation with fullerenes.

Triphenylamine derivates have been utilized as building blocks in hole-transporting materials. Herein, we describe the synthesis of three octyl-derived conjugated triphenylamine macrocycles with different sizes, and a 4-(2-ethylhexyloxy)-substituted cyclic triphenylamine hexamer using a palladium-catalyzed C-N coupling reaction. These conjugated triphenylamine macrocycles not only have interesting structures, but also are capable of complexing with C60, C70 and PC61BM. Their binding stoichiometries with fullerenes were all determined to be 1 : 1 by an emission titration method. The association constants of these complexes were measured to be in the range of 0.115-1.53 × 105 M-1 depending on the cavity size of the triphenylamine macrocycles and the volume of the fullerenes. The space-charge-limited current properties of the complexes were further investigated using the fabricated ITO/PEDOT:PSS/active layer/Au devices.

Single-Component Polycondensation of Bis(alkoxycarbonyldiazomethyl)aromatic Compounds To Afford Poly(arylene vinylene)s with an Alkoxycarbonyl Group on Each Vinylene Carbon Atom.

The original synthetic strategy for a new type of poly(arylene vinylene) (PAV) is presented, where the C=C-bond-forming coupling of bis(alkoxycarbonyldiazomethyl)aromatic compounds is utilized as propagation. The strategy is unique in that the resulting PAVs have an alkoxycarbonyl group as an electron-withdrawing substituent on each vinylene carbon atom in the polymer main chain. Among the transition-metal catalysts examined in this study, RuCl(cod)Cp* (cod = 1,5-cyclooctadiene, Cp* = pentamethylcyclopentadienyl) is the most efficient, affording PAVs from a series of bis(alkoxycarbonyldiazomethyl)aromatic compounds with a high trans-C=C-forming selectivity of up to 90%. A PAV sample with a fluorenylene framework as an arylene moiety prepared by the Ru catalyst exhibited a hole mobility of 4 × 10-6 cm2 V-1 s-1.

Synthesis of acrylic resins for high-solids traffic marking paint by solution polymerization.

Fast-drying traffic marking paint comprising a solvent-borne resin, a filler, a pigment and a solvent that is especially suitable for colder ambient (temperatures near freezing) applications, where waterborne traffic paint cannot be used. Acrylic resins based on methyl methacrylate, butyl acrylate, acrylic acid, and styrene were synthesized in different solvents using organic peroxide initiators such as peroxyester, peroxyketal, dialkylperoxide and azo. After polymerization, the molecular weight (Mw), polydispersity index = PDI (Mw/Mn), viscosity, total residual monomer and APHA color were evaluated and results of organic peroxide initiators (t-butyl and t-amyl derivatives) were compared with the azo initiator. The Mw, PDI, viscosity, mass conversation and APHA color of resins with t-amyl derivatives of organic peroxide initiators are very proper.

Preparation of Conductive Polyester Fibers Using Continuous Two-Step Plating Silver.

Polyester fibers are used in various fields, due to their excellent mechanical and chemical stability. However, the lack of conductivity limits their application potential. In order to prepare conductive polyester fibers, silver is one of the most widely used materials to coat the surface of the fibers. This work aimed to prepare silver-coated polyester fibers by a continuous two-step method, which combined the operations of continuous electroless plating and electroplating. Meanwhile, we designed specialized equipment for the continuous plating of silver on the polyester fibers under a dynamic condition. The mechanical property, washability, electrical resistivity, and electrical conductivity of the resultant conductive polyester fibers obtained from different silver-plating conditions were also characterized. The results demonstrated that the conductive fibers prepared by continuous two-step silver plating equipment, had good electrical conductivity with better mechanical properties and washability.

Laser-Induced Silver Seeding on Filter Paper for Selective Electroless Copper Plating.

The generation of a flexible printed circuit board on polymer fabrics has been a challenge over the last decade. In this work, a copper pattern was obtained on a soft substrate of filter paper/polyacrylonitrile (FP/PAN) film, where the filter paper was commercially available. The pattern of Ag particles was first produced on an Ag⁺-doped FP/PAN composite film, followed by electroless plating of copper using the metal silver particles as seeds. The in situ reduction of silver particles and the formation of the silver agglomeration pattern were induced by laser irradiation technology on the FP/PAN/AgNO3 composite film. A variety of characterizations indicated that the resultant copper deposition was uniform, with good conductivity properties.

Microfluidic Fabrication of Morphology-Controlled Polymeric Microspheres of Blends of Poly(4-butyltriphenylamine) and Poly(methyl methacrylate).

Multicomponent polymer particles with specific morphology are promising materials exhibiting novel functionality which cannot be obtained with single-component polymer particles. Particularly, the preparation of such kinds of polymer particles involving electrically or optically active conjugated polymers with uniform size is a challenging subject due to their intense demands. Here, microspheres of binary polymer blend consisting of poly(4-butyltriphenylamine) (PBTPA)/poly(methyl methacrylate) (PMMA) (1:1 in weight) were produced via a microfluidic emulsification with a Y-shaped microreactor, and a subsequent solvent evaporation method. The flow rate of the dispersed phase (polymer solution) was fixed to 7 µL/min, and 140 or 700 µL/min of the flow rate of the continuous phase (aqueous 0.6 wt % of poly(vinyl alcohol) (PVA) solution) was utilized to produce the dispersion with different diameter. The concentration of dispersed phase was adjusted to 0.1 or 1.0 w/v%. Core-shell, Janus and dumbbell type microspheres were obtained dependent on the flow rate of continuous phase. Incomplete core-shell type microspheres were produced for the blend involving low molecular weight PMMA. Complex Janus and core-shell type microspheres were fabricated by the addition of sodium dodecyl sulfate (SDS) to continuous phase. It is found that final morphologies are strongly dependent on the initial conditions of dispersion including the particle size suggesting that the morphologies are governed by the kinetical factors together with the conventionally accepted thermodynamic ones.

Fabrication of Completely Polymer-Based Solar Cells with p- and n-Type Semiconducting Block Copolymers with Electrically Inert Polystyrene.

It is widely recognized that fullerene derivatives show several advantages as n-type materials in photovoltaic applications. However, conventional [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) exhibits weak absorption in the visible region, and poor morphological stability, due to the facile aggregation. For further improvement of the device performance and durability, utilization of n-type polymeric materials instead of PCBM is considered to be a good way to solve the problems. In this study, we fabricated completely polymer-based solar cells utilizing p- and n-type block copolymers consisting of poly(3-hexylthiophene) (P3HT) and poly{[N,N'-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(NDI2OD-T2)], respectively, containing common polystyrene (PSt) inert blocks, which decreased the size of phase separated structures. Electron mobility in synthesized P(NDI2OD-T2)-b-PSt film enhanced by a factor of 8 compared with homopolymer. The root mean square roughness of the blend film of two block copolymers (12.2 nm) was decreased, compared with that of the simple homopolymers blend (18.8 nm). From the current density-voltage characteristics, it was confirmed that the introduction of PSt into both P3HT and P(NDI2OD-T2) improves short-circuit current density (1.16 to 1.73 mA cm-2) and power-conversion efficiency (0.24% to 0.32%). Better performance is probably due to the uniformity of the phase separation, and the enhancement of charge mobility.

Color Change of Sudan III against Concentrated Sulfuric Acid in Acetonitrile and Quantification for a Small Amount of Concentrated Sulfuric Acid.

The color-changing phenomenon of hydrophobic bisazo dye, Sudan III in an acetonitrile solution against the addition of concentrated sulfuric acid has been discovered and the chromic properties investigated. Based on observations, a novel quantification method of concentrated sulfuric acid has been developed. Sudan III changes its color from orange to blue against a small volume of sulfuric acid, and the acetonitrile solution of Sudan III is the most suitable for observing the color-change phenomenon. (1)H-NMR and UV-Vis spectroscopic studies showed that the color-change mechanism of Sudan III against sulfuric acid is due to the protonation of the dye by sulfuric acid. This phenomenon is applicable to the quantification of concentrated sulfuric acid by introducing the Hammett acidity function. The proposed method requires only a small amount of the sample, 0.04 mL, and enables rapid quantification.