Photoresponsive heparin ionic complexes toward controllable therapeutic efficacy of anticoagulation.

Controllable heparin-release is of great importance and necessity for the precise anticoagulant regulation. Efforts have been made on designing heparin-releasing systems, while, it remains a great challenge for gaining the external-stimuli responsive heparin-release in either intravenous or catheter delivery. In this study, an azobenzene-containing ammonium surfactant is designed and synthesized for the fabrication of photoresponsive heparin ionic complexes through the electrostatic complexation with heparin. Under the assistance of photoinduced trans-cis isomerization of azobenzene, the obtained heparin materials perform reversible athermal phase transition between ordered crystalline and isotropic liquid state at room temperature. Compared to the ordered state, the formation of isotropic state can effectively improve the dissolving of heparin from ionic materials in aqueous condition, which realizes the photo-modulation on the concentration of free heparin molecules. With good biocompatibility, such a heparin-releasing system addresses photoresponsive anticoagulation in both in vitro and in vivo biological studies, confirming its great potential clinical values. This work provides a new designing strategy for gaining anticoagulant regulation by light, also opening new opportunities for the development of photoresponsive drugs and biomedical materials based on biomolecules.

α-Fe2O3 based nanotherapeutics for near-infrared/dihydroartemisinin dual-augmented chemodynamic antibacterial therapy.

Due to the negligible bacterial resistance, chemodynamic therapy (CDT) is a promising treatment for bacterial infection. However, it is severely impeded by the constant body temperature, shortage of Fe(Ⅱ) ions and insufficient H2O2 level in infected tissue. To enhance the therapeutic efficiency of CDT, improved strategies are urgently needed to tackle these problems. Herein, we exploited an infection microenvironment-responsive nanotherapeutics for near-infrared (NIR)/dihydroartemisinin (DHA) dual-augmented antibacterial CDT. The convenient encapsulation of DHA-loaded α-Fe2O3 nanorods with metal-polyphenol networks (MPN) led to the generation of an antibacterial nanoagent Fe2O3@DHA@MPN (FDM). Afterwards, its photothermal and peroxidase-like activities were intensively studied. Furthermore, the bactericidal efficacy of FDM was evaluated through both in vitro and in vivo antibacterial assays. Firstly, FDM showed both satisfactory photothermal and NIR/DHA dual-augmented peroxidase-like activities. Besides, it exhibited a pH-responsive release behavior of both Fe(Ⅱ) ions and DHA. Moreover, it presented tannic acid-mediated bacterial adhesion effect. In vitro experiments demonstrated that FDM could achieve a satisfactory efficiency against both planktonic bacteria and biofilms. In vivo assays illustrated both the extraordinary synergistic antibacterial effect and efficient anti-inflammatory ability of FDM. The outcomes indicated that the exploited antibacterial agent could offer new insight on developing intelligent nanotherapeutics for clinical use in the future. STATEMENT OF SIGNIFICANCE: The antibacterial efficiency of chemodynamic therapy (CDT) is seriously limited by the constant body temperature, shortage of Fe(Ⅱ) ions and insufficient H2O2 level at the mildly acidic inflammatory microenvironment. To address these issues, we have developed a pH-responsive nanoagent (Fe2O3@DHA@MPN) for near-infrared (NIR)/dihydroartemisinin (DHA) dual-augmented CDT. Through the NIR-induced photothermal effect of exterior Fe(Ⅲ)/tannic acid complex, the increased local temperature led to a photothermal enhanced CDT. Besides, a continuous supply of Fe(Ⅱ) ions could be achieved by tannic acid-mediated Fe(Ⅲ) reduction. Moreover, DHA was adopted as a substitute for H2O2 to initiate DHA-mediated CDT. Both in vitro and in vivo assays demonstrated its outstanding bactericidal efficiency. Therefore, the developed nanotherapeutics could be a promising candidate for clinical trials.

Alginate-based aerogels as wound dressings for efficient bacterial capture and enhanced antibacterial photodynamic therapy.

The development of novel wound dressings, such as aerogels, with rapid hemostasis and bactericidal capacities for pre-hospital care is necessary. To prevent the occurrence of bacterial resistance, antibacterial photodynamic therapy (aPDT) with broad-spectrum antibacterial ability and negligible bacterial resistance has been intensively studied. However, photosensitizers often suffer from poor water solubility, short singlet oxygen (1O2) half-life and restricted 1O2 diffusion distance. Herein, sodium alginate was covalently modified by photosensitizers and phenylboronic acid, and cross-linked by Ca(II) ions to generate SA@TPAPP@PBA aerogel after lyophilization as an antibacterial photodynamic wound dressing. Afterwards, its photodynamic and bacterial capture activities were intensively evaluated. Furthermore, its hemostasis and bactericidal efficiency against Staphylococcus aureus were assessed via in vitro and in vivo assays. First, chemical immobilization of photosensitizers led to an enhancement of its solubility. Moreover, it showed an excellent hemostasis capacity. Due to the formation of reversible covalent bonds between phenylboronic acid and diol groups on bacterial cell surface, the aerogel could capture S. aureus tightly and dramatically enhance aPDT. To sum up, the prepared aerogel illustrated excellent hemostasis capacity and antibacterial ability against S. aureus. Therefore, they have great potential to be utilized as wound dressing in clinical trials.

Ultrafiltration concentrated biogas slurry can reduce the organic pollution of groundwater in fertigation.

Biogas slurry has the problems of having a low concentration, having a large production volume, and containing many small-molecule organic pollutants. During the fertigation process of biogas slurry, many small-molecule organic pollutants may pose potential pollution risks to groundwater. In this study, the ultrafiltration membrane technology was used to separate small-molecule organics in the biogas slurry to prepare ultrafiltration concentrated biogas slurry (UCBS). To research the impact of UCBS and raw biogas slurry (RBS) on the small-molecule organic pollution of groundwater, a laboratory soil column simulation leaching device was used to conduct leaching experiments with 4 types of UCBS and RBS in acric ferralsols and hydragric anthrosols for two quarters (8 fertilization periods). The results of the study show that both UCBS and RBS caused nitrate pollution to groundwater. UCBS has a lower risk of organic pollution to groundwater than RBS. Irrigating UCBS in hydragric anthrosols has a higher risk of organic pollution of groundwater than that in acric ferralsols. Analysis of the molecular weight distribution of dissolved organic matter (DOM) in the leaching solution showed that the organic pollutants were mainly small molecules <10 kDa. According to 3D excitation-emission matrix (3D-EEM) analysis, the main organic pollutants in the leaching solution were fulvic acid, microbial protein metabolites and humic acid organic compounds. The research results show that the pretreatment of biogas slurry by ultrafiltration can reduce the risk of small-molecule organic pollution of groundwater in land application, which can provide a new scientific basis to standardize biogas slurry land application technical guidelines and reduce groundwater pollution.

Removal of refractory organics from piggery bio-treatment effluent by the catalytic ozonation process with piggery biogas residue biochar as the catalyst.

After anaerobic-oxic (A/O) treatment, there are often high chromaticity levels in piggery bio-treatment effluents, which still contain a high concentration of refractory organics. This paper describes the use of piggery biogas residue biochar (BioC) to support MnO2 to prepare a catalyst (MnO2/BioC) and examines the effects of catalyst addition, pH and ozone dosage on chromaticity and organic matter degradation in the ozonation process. Three-dimensional fluorescence spectroscopy (3D-EEM) and GC-MS were used to analyse changes in the organic component of the effluent before and after ozonation. The results indicate that the decolorization percentages reached 91.29% and that the UV254 and CODcr removal percentages reached 81.64% and 61.07%, respectively, when the MnO2/BioC catalyst addition amount was 1.0 g·L-1, the pH was 9.0, and the ozone dosage was 0.45 g·L-1. The 3D-EEM analysis results showed that the macromolecular organics mainly consisted of humic acids before treatment, and the removal of humic acid organic matter after treatment had an obvious effect. The GC-MS analysis results showed that the refractory organics were mainly phenols, esters, alcohols and hydrocarbons, and most of the refractory organics were oxidatively degraded after treatment. These results show that ozone catalytic oxidation treatment of piggery bio-treatment effluent can reduce chromaticity and refractory organics.

Influence of reflux ratio on the anaerobic digestion of pig manure in leach beds coupled with continuous stirred tank reactors.

The effect of reflux ratio on the anaerobic mono-digestion of pig manure (PM) in leach beds coupled with continuous stirred tank reactors (CSTRs) has been studied in this work, and contents of volatile fatty acids (VFAs) and biogas yields were determined for three groups of leach bed reactor (LBR) - CSTR systems. The obtained results indicated that the reflux of biogas slurry increased both the pH of the acid-producing phase and acetic acid yield and repeatedly degraded the refractory organic matter in the biogas slurry. The larger reflux ratio increased the inoculation volume and substantially enhanced the mass transfer process. The maximum values of the biogas and methane yields equal to 259.49 and 167.44 mL/g volatile solids, respectively, were achieved at a reflux ratio of 100%. Moreover, the weight of the PM leachate residue was reduced by 94.14%, and the total nutrient content (N + P2O5 + K2O) was relatively high (1.48%), which was suitable for vegetable seedling substrates. In conclusion, during the treatment of PM in LBR-CSTRs, the solid phase remains on the leach bed, and the leachate is supplied to a biogas tank, which effectively increases its stability of operation.