In Situ Surface-Initiated ATRP Mediated by Gallium-Based Liquid Metal Nanodroplets.

Surface-initiated atom transfer radical polymerization (SI-ATRP) is one of the most popular methods for surface modifications with functional polymer films, which has attracted significant attention in recent years. Herein, a facile method of gallium-based liquid metal (GLM) nanodroplets mediated SI-ATRP to prepare polymer brushes on GLM surfaces is reported. The ATRP initiator modified GLM (GLM-Br) nanodroplets act as a substrate for the in situ SI-ATRP and participate as a reducing agent to reduce Cu(II) deactivators to Cu(I) activators. UV-vis spectra confirm the feasibility of the in situ SI-ATRP and indicate that the thickness and density of polymer brushes play an important role in performing a successful ATRP on GLM nanodroplets surfaces. Homo- and block copolymers, poly(3-sulfopropyl methacrylate potassium salt) (PSPMA) and poly((2-dimethylamino)ethyl methacrylate-b-(3-sulfopropyl methacrylate potassium salt)) P(DMAEMA-b-SPMA) are successfully grafted to the GLM nanodroplets. Polymer brushes modified GLM nanodroplets show potential applications such as friction reduction and oil-water emulsion separation. GLM nanodroplets mediated SI-ATRP provides a novel and robust approach to preparing multifunctional GLM nanodroplets for different applications.

Tuning capsid formation dynamics in recombinant adeno-associated virus producing synthetic cell lines to enhance full particle productivity.

Recombinant adeno-associated virus (rAAV) is widely used as an in vivo delivery vector for gene therapy. It is used in a very large dose, and the large quantities required for broad applications present manufacturing challenges. We have developed a synthetic biology platform of constructing cell lines integrated with essential viral genes which can be induced to produce rAAV without plasmid transfection or virus transduction. Through iterative design-construct-characterization cycles, we have showcased the potential of this synthetic cell production system. Systems characterization of the dynamics of viral transcripts and proteins as well as virus assembly and packaging revealed that the expression level and balance of viral genome and capsid protein are keys to not only the productivity but also the full particle content, an important product quality attribute. Boosting cap gene expression by sequential transfection and integration of multiple copies of the cap gene elevated the rAAV titer to levels on a par with traditional plasmid transfection and virus infection. However, overexpression of the cap gene shifted the balance and kinetics of the genome and capsid. We independently tuned the dynamics of genome amplification and capsid protein synthesis by modulating the induction concentration as well as the time profile, and significantly enhanced full particle content while maintaining a high productivity. This strategy of constructing an inducible stable producer cell line is readily adaptable to rAAV vectors of different serotypes and payloads. It can greatly facilitate scalable production of gene therapy vectors.

Rational design of a highly effective cellulose-based macromolecular fluorescent probe for real-time recognition of palladium ion in environmental samples and its applications in plant and zebrafish.

Palladium ion (Pd2+) plays an important role in our daily life, but poses a great threat to the environment and human health. Thus, it is desirable to exploit a rapid and sensitive approach to realize the detection of Pd2+. In this study, a cellulose acetate-based macromolecular fluorescent probe CA-NA-PA was successfully prepared for tracking amounts of Pd2+. CA-NA-PA showed an obvious "on-off" fluorescence response to Pd2+, accompanied by the fluorescence color changed from bright yellow to colorless. CA-NA-PA had some outstanding detection performances such as low detection limit (26 nM), extremely short response time (1 min), good selectivity and anti-interference ability. Based on the advantages of probe mentioned above, CA-NA-PA could realize recognition of Pd2+ concentration in environmental water and soil samples. What's more, the probe CA-NA-PA was applied to image Pd2+ in zebrafish as well as in live onion tissue due to the good biocompatibility and cell membrane permeability of cellulose, suggesting its wide application prospect in biosystems.

Synthetic Cell Lines for Inducible Packaging of Influenza A Virus.

Influenza A virus (IAV) is a negative-sense RNA virus that causes seasonal infections and periodic pandemics, inflicting huge economic and human costs on society. The current production of influenza virus for vaccines is initiated by generating a seed virus through the transfection of multiple plasmids in HEK293 cells followed by the infection of seed viruses into embryonated chicken eggs or cultured mammalian cells. We took a system design and synthetic biology approach to engineer cell lines that can be induced to produce all viral components except hemagglutinin (HA) and neuraminidase (NA), which are the antigens that specify the variants of IAV. Upon the transfection of HA and NA, the cell line can produce infectious IAV particles. RNA-Seq transcriptome analysis revealed inefficient synthesis of viral RNA and upregulated expression of genes involved in host response to viral infection as potential limiting factors and offered possible targets for enhancing the productivity of the synthetic cell line. Overall, we showed for the first time that it was possible to create packaging cell lines for the production of a cytopathic negative-sense RNA virus. The approach allows for the exploitation of altered kinetics of the synthesis of viral components and offers a new method for manufacturing viral vaccines.

Removal of polystyrene nanoplastics from water by CuNi carbon material: The role of adsorption.

Nanoplastics have attracted wide attention worldwide as a new potentially threatening pollutant, and they can cause harm to the organisms and pose threat to the water environment. Therefore, efficient removal techniques for nanoplastics are urgently needed. In this study, CuNi carbon material (CuNi@C) was prepared by hydrothermal method for the removal of polystyrene (PS) nanoplastics from water. CuNi@C was effectively adsorbed on PS nanoplastics. When the CuNi@C dosage increased from 0.1 g/L to 0.3 g/L, the removal efficiency of PS nanoplastics (10 mg/L) elevated from 32.72% to 99.18%. The images of the scanning electron microscope (SEM) and the Fourier transform infrared spectroscopy (FTIR) spectra of CuNi@C confirmed the adsorption of PS nanoplastics on the CuNi@C. The fitting results of adsorption kinetic models and isotherms equations demonstrated that physical adsorption and monolayer coverage were the predominant mechanisms of the PS nanoplastics adsorption on CuNi@C. Thermodynamics analysis illustrated the adsorption of PS nanoplastics on CuNi@C was a spontaneous and endothermic process. The electrostatic attraction occurred in adsorption progress, and the removal efficiency of PS nanoplastics in the acidic system was generally higher than that in the alkaline system. CuNi@C can be recycled via washing and drying treatment and these CuNi@C comparable PS nanoplastics removal performance to the original ones. After four times cycles, CuNi@C can still remove ~75% of total PS nanoplastics from water. This study reveals that CuNi@C can be used as promising techniques for the removal of PS nanoplastics from the aqueous environment.

[The effects of different herbal compound and extracts from different extraction methods on hypoxia tolerance in mice].

Objective: To investigate the effects of different prescription compositions of traditional Chinese medicine and its different extraction methods of compound formula extracts on hypoxia tolerance in mice, in order to preferably select their prescription compositions and preparation extraction methods. Methods: Male BALB/c mice were randomly divided into 6 groups: blank control group, compound danshen group, compound Rhodiola Rosea alcohol-water extract group (Rhodiola rosea, Astragali Radix, Polygonati Rhizoma, Lycii Fructus), compound Rhodiola Rosea water extract group, compound Astragalus alcohol-water extract group (Astragali Radix, Polygonati Rhizoma, Lycii Fructus) and compound Astragalus water extract group, 30 mice in each group. Each group was administered continuously by gavage for 10 d. The blank group was gavaged with sterilized injection water. The mice in the other groups were treated with 0.15 g/kg of compound danshen, 3 g/kg of compound Rhodiola Rosea alcohol-water extract or water extract, and 1.7 g/kg of compound Astragalus alcohol-water extract or water extract, respectively. Each group was subjected to normobaric hypoxia tolerance test, sodium nitrite toxicity survival test and acute cerebral ischemia-hypoxia test 1 h after the last gavage, and the mice brain tissues were used to determine the activity of antioxidant enzymes and metabolites related to oxidative stress. Results: Compared with the blank control group, in normobaric hypoxia tolerance test, the survival time of mice in the compound danshen group and the compound Astragalus alcohol-water extract group and water extraction group was prolonged significantly (P＜0.01), and the number of open-mouth gasping after cerebral ischemia and hypoxia was increased significantly (P＜0.05). There was no statistical difference in survival time after sodium nitrite injection in each group. Compared with the blank control group, the activities of T-AOC, SOD, GSH and CAT were increased significantly (P＜0.05, P＜0.01) and the content of MDA was decreased significantly (P＜0.01) in the compound Astragalus water extract group. Compared with the compound danshen group, the activities of SOD, CAT and GSH were increased significantly (P＜0.01, P＜0.05) and the content of MDA was decreased significantly (P＜0.05). Conclusion: Compound Astragalus water extraction has the best effect of hypoxia tolerance, compound Rhodiola Rosea can eliminate Rhodiola rosea and consists of Astragali Radix, Polygonati Rhizoma, Lycii Fructus and its extraction method is water extraction.

Biomaterials-Based Delivery of Therapeutic Antibodies for Cancer Therapy.

Considerable breakthroughs in the treatment of malignant tumors using antibody drugs, especially immunomodulating monoclonal antibodies (mAbs), have been made in the past decade. Despite technological advancements in antibody design and manufacture, multiple challenges face antibody-mediated cancer therapy, such as instability in vivo, poor tumor penetration, limited response rate, and undesirable off-target cytotoxicity. In recent years, an increasing number of biomaterials-based delivery systems have been reported to enhance the antitumor efficacy of antibody drugs. This review summarizes the advances and breakthroughs in integrating biomaterials with therapeutic antibodies for enhanced cancer therapy. A brief introduction to the principal mechanism of antibody-based cancer therapy is first established, and then various antibody immobilization strategies are provided. Finally, the current state-of-the-art in biomaterials-based antibody delivery systems and their applications in cancer treatment are summarized, highlighting how the delivery systems augment the therapeutic efficacy of antibody drugs. The outlook and perspective on biomaterials-based delivery of antitumor antibodies are also discussed.

Switching water droplet adhesion using responsive polymer brushes.

Two stimuli-responsive polymers, poly(N-isopropylacrylamide) (PNIPAM) and poly(dimethylamino)ethyl methacrylate (PDMAEMA), were grafted from initiator-modified anodized alumina substrates with irregular micro/nanoscale surface topography. The resulting polymer-coated surfaces exhibited highly unusual wettability properties, as spherical water/acid/alkali/salt droplets could be reversibly switched between pinned states and rolling states due to the changes of temperature, pH, and electrolytes. The key to this effect is the combination of a mixed monolayer which provides initiator points for brush growth as well as a permanently hydrophobic substrate and a surface roughness.

Mechanistic aspects of the copolymerization of CO2 with epoxides using a thermally stable single-site cobalt(III) catalyst.

The mechanism of the copolymerization of CO(2) and epoxides to afford the corresponding polycarbonates catalyzed by a highly active and thermally stable cobalt(III) complex with 1,5,7-triabicyclo[4,4,0] dec-5-ene (designated as TBD, a sterically hindered organic base) anchored on the ligand framework has been studied by means of electrospray ionization mass spectrometry (ESI-MS) and Fourier transform infrared spectroscopy (FTIR). The single-site, cobalt-based catalyst exhibited excellent activity and selectivity for polymer formation during CO(2)/propylene oxide (PO) copolymerization even at temperatures up to 100 degrees C and high [epoxide]/[catalyst] ratios, and/or low CO(2) pressures. The anchored TBD on the ligand framework plays an important role in maintaining thermal stability and high activity of the catalyst. ESI-MS and FTIR studies, in combination with some control experiments, confirmed the formation of the carboxylate intermediate with regard to the anchored TBD on the catalyst ligand framework. This analysis demonstrated that the formed carboxylate intermediate helped to stabilize the active Co(III) species against decomposition to inactive Co(II) by reversibly intramolecular Co-O bond formation and dissociation. Previous studies of binary catalyst systems based on Co(III)-Salen complexes did not address the role of these nucleophilic cocatalysts in stabilizing active Co(III) species during the copolymerization. The present study provides a new mechanistic understanding of these binary catalyst systems in which alternating chain-growth and dissociation of propagating carboxylate species derived from the nucleophilic axial anion and the nucleophilic cocatalyst take turns at both sides of the Co(III)-Salen center. This significantly increases the reaction rate and also helps to stabilize the active SalenCo(III) against decomposition to inactive SalenCo(II) even at low CO(2) pressures and/or relatively high temperatures.

Grafting Robust Thick Zwitterionic Polymer Brushes via Subsurface-Initiated Ring-Opening Metathesis Polymerization for Antimicrobial and Anti-Biofouling.

In the present work, high-thickness zwitterionic polymer brushes based on imidazolium salts were successfully grafted via a novel subsurface-initiated ring-opening metathesis polymerization (subsurface-initiated ROMP) from polydimethylsiloxane (PDMS), and their antifouling performance was evaluated in detail. First, an initiator-embedded PDMS was prepared via copolymerization of PDMS prepolymer and ROMP initiator, and then zwitterionic polymer brushes were grafted via subsurface-initiated ROMP from surface to subsurface of the PDMS due to the implanted ROMP initiator. Results from a series of characterization methods such as infrared spectroscopy, X-ray photoelectron spectroscopy, contact angle, and atomic force microscopy proved the zwitterionic polymer brushes' successful grafting. The grafting thickness of zwitterionic polymer brushes via subsurface-initiated ROMP can reach the micron scale, and the as-prepared zwitterionic polymer based surfaces showed good lubricating properties compared to traditional surface-initiated ROMP, which hints that polymer brushes can be grafted not only on the surface but also on the subsurface of PDMS. The protein adhesion test and biofouling assay of zwitterionic polymer brushes were tested in the laboratory, and the results indicated that the zwitterionic polymer-functionalized PDMS can effectively resist the adhesion of bovine serum albumin and algae (Porphyridium and Dunaliella) and has good anti-bacterial activity against both Escherichia coli and Staphylococcus aureus.

Polymer brushes on structural surfaces: a novel synergistic strategy for perfectly resisting algae settlement.

The current paper reports a novel model of a marine antibiofouling surface based on polymer brushes on a wrinkled silicone elastomer. Polymer brushes (POEGMA and PSPMA) were grafted via surface-initiated atom transfer radical polymerization (SI-ATRP). Successful grafting was verified with various characterization techniques including infrared spectroscopy, X-ray photoelectron spectroscopy and contact angle measurements. A series of laboratory static and dynamic bioassays as well as field immersion tests were carried out to systematically investigate the relationship between surface chemistry, surface topography and antifouling properties. The results indicated that the adhesion of marine organisms was strongly influenced by the surface chemistry composition and surface topography structure. The synergistic effect of the surface chemistry, surface topography and bulk properties of the substrates endowed the new marine coatings with excellent antifouling properties.

Self-assembling anticaries mucosal vaccine containing ferritin cage nanostructure and glucan-binding region of S. mutans glucosyltransferase effectively prevents caries formation in rodents.

Anticaries protein vaccines that induce a mucosal immune response are not effective. Therefore, development of effective and convenient anticaries vaccines is a priority of dental research. Here we generated self-assembling nanoparticles by linking the glucan-binding region of Streptococcus mutans glucosyltransferase (GLU) to the N-terminal domain of ferritin to determine whether these novel nanoparticles enhanced the immunogenicity of an anticaries protein vaccine against GLU in rodents. We constructed the expression plasmid pET28a-GLU-FTH and purified the proteins from bacteria using size-exclusion chromatography. BALB/c mice were used to evaluate the ability of GLU-ferritin (GLU-FTH) nanoparticles to induce GLU-specific mucosal and systemic responses. The protective efficiency of GLU-FTH nanoparticles was compared with that of GLU alone or a mixture of GLU and poly(I:C) after administering an intranasal infusion to Wistar rats. The phagocytosis and maturation of dendritic cells (DCs) exposed in vitro to the nanoparticles were assessed using flow cytometry. The GLU-FTH nanoparticle vaccine elicited significantly higher levels of GLU-specific antibodies compared with GLU or a mixture of GLU and poly(I:C). Immunization with GLU-FTH achieved lower caries scores compared with those of the other vaccines. Administration of GLU-FTH nanoparticles enhanced phagocytosis by DCs and their maturation. Thus, self-assembling GLU-FTH is a highly effective anticaries mucosal vaccine that enhanced antibody production and inhibited S. mutans infection in rodents.

CdS/CdSe quantum dot co-sensitized graphene nanocomposites via polymer brush templated synthesis for potential photovoltaic applications.

CdS/CdSe quantum dot (QDs) co-sensitized graphene sheets have been obtained via polymer brush templated synthesis. Firstly, the anionic functional polymer (polymethacrylate cadmium) was grafted via the surface initiated atomic transfer radical polymerization (ATRP) using a macromolecular initiator, which contains polymerized pyrene units for chemical anchoring on graphene surface and alkyl bromines to initiate ATRP. Then, the coordinated cadmium in the polymer chains can act as a source precursor for QDs. After reaction, polymer brushes can be recovered and act as the nanoreactor via the absorption of cadmium ions by carboxylate groups. So, high density QDs can be multiply uploaded onto the graphene surface by repeated steps. The as-prepared composite materials exhibited significantly enhanced visible light response compared to plain graphene, and have potential applications as the platform to build solar cell assembles.

Grafting polymer brushes on biomimetic structural surfaces for anti-algae fouling and foul release.

Sylgard-184 silicone elastomer negative replica and resorcinol-formaldehyde (RF) positive replica were made by biomimicking the patterns of natural Trifolium and three other kinds of leaves using the micromolding lithography. An effective antifouling (AF) polymer, poly(3-sulfopropyl methacrylate) (PSPMA), was then grafted on these replica surfaces via the surface-initiated atom transfer radical polymerization (SI-ATRP). The AF property of the modified biomimetic surfaces was tested via the settlement assay with two microalgae in different sizes, and their fouling-release (FR) property was evaluated by the removal assay. The results indicate that the structure of microspines on Trifolium leaf can inhibit settlement of microalgae and facilitate the cell release. The AF property was improved by modification with PSPMA brushes.

Low surface energy surfaces from self-assembly of perfluoropolymer with sticky functional groups.

Fluorinated methacrylic copolymer containing catechol and perfluoroalkyl pendant side groups is synthesized by the free radical polymerization of a catechol-containing methacrylate monomer N-(3,4-dihydroxyphenyl)ethyl methacrylamide and 1H,1H-perfluorooctyl methacrylate using alpha,alpha'-azobisisobutyronitrile (AIBN) as initiator. The fluorinated copolymer can assemble onto surfaces of a wide variety of materials including Ti, Al, Cu, steel, silicon, glass, mica, polyimide, polystyrene, and polymethylmethacrylate using catechol groups as multivalent H-bonding anchors. X-ray photoelectron spectroscopy and contact-angle data provide solid evidence of the formation of the assembly films that exhibit the surface free energy as low as 8.0 mJ m(-2).