Photocurable Hyperbranched Polymer Medical Glue for Water-Resistant Bonding.

Medical glue represents a suitable tool to stop wound bleeding, seal wounds, bond tissues, or implant materials. However, the development of a medical glue for durable underwater bonding remains a challenge. Herein, we developed a hydrophobic hyperbranched polymer-based medical glue with water-resistant bonding ability. Specifically, the hyperbranched polythioether (HBPTE) with abundant terminal thiol groups was first prepared through a simple one-pot thiol-Michael polyaddition reaction. Due to the hyperbranched molecular structure, HBPTE is a liquid material under room temperature, thus enabling the manufacturing of a photocurable HBPTE glue by the direct addition of poly(ethylene glycol) dimethacrylate and a photoinitiator without introduction of a solvent. This solventless HBPTE glue exhibited a maximum underwater adhesive strength of 36 kPa on porcine skin compared to only <10 kPa of the commercial fibrin glue and cyanoacrylate glue. Moreover, since the hydrophobic cross-linked network resists penetration of water, the HBPTE glue minimally swelled (2-10%) and could maintain a glass sheet structure bonded together even after 2 weeks underwater. Furthermore, an in vitro cytotoxicity test showed that the HBPTE glue did not leak any cytotoxic substances and allowed for proliferation of L929 cells on its surface. Moreover, hemocompatibility tests indicated that the HBPTE glue was nonhemolytic and did not induce thrombosis. This HBPTE glue exhibited promising characteristics to potentially find use as an underwater soft tissue adhesive or sealant.

A Temperature-Responsive Boronate Core Cross-Linked Star (CCS) Polymer for Fast and Highly Efficient Enrichment of Glycoproteins.

Fast and highly efficient enrichment and separation of glycoproteins is essential in many biological applications, but the lack of materials with high capture capacity, fast, and efficient enrichment/separation makes it a challenge. Here, a temperature-responsive core cross-linked star (CCS) polymer with boronate affinity is reported for fast and efficient enriching and separating of glycoproteins from biological samples. The temperature-responsive CCS polymers containing boronic acid in its polymeric arms and poly(N-isopropyl acrylamide) in its cross-linked core are prepared using reversible addition-fragmentation chain transfer polymerization via an "arm-first" methodology. The soluble boronate polymeric arms of the CCS polymers provide a homogeneous reaction system and facilitate interactions between boronic acid and glycoproteins, which leads to a fast binding/desorption speed and high capture capacity. Maximum binding capacity of the prepared CCS polymer for horseradish peroxidase is determined to be 210 mg g-1 , which can be achieved within 20 min. More interestingly, the temperature-responsive CCS polymers exhibit rapid reversible thermal-induced volume phase transition by increasing the temperature from 15 to 30 °C, resulting in a facile and convenient sample collection and recovery for the target glycoproteins. Finally, the temperature-responsive CCS polymer is successfully applied to enrichment of low abundant glycoproteins.

Influence of photo-cross-linking on emulsifying performance of the self-assemblies of poly(7-(4-vinylbenzyloxyl)-4-methylcoumarin-co-acrylic acid).

Polymeric micelles could be used as model polymeric particulate emulsifiers to elucidate the correlation between the micellar structure and their emulsifying performance. Photo-cross-linkable and pH-responsive micelles were prepared with amphiphilic random copolymers, poly(7-(4-vinylbenzyloxyl)-4-methylcoumarin-co-acrylic acid) (PVMAA), via the self-assembly in selective-solvent DMF/H2O and then used as polymeric particulate emulsifiers to stabilize toluene-in-water emulsions. Primary micelles, based on PVMAA with 12 mol % of hydrophobic composition, were chosen as model to investigate the influence of photo-cross-linking on the emulsifying performance. The larger shrinkage degree by photo-cross-linking (SDC) the micelles have, the lower emulsifying efficiency the micelles exhibit. Furthermore, the structural transitions of micelles with SDC of 0% and 95% in response to pH change were comparatively confirmed by a combination of electrophoresis, dynamic light scattering (DLS), and transmission electron microscopy (TEM). The micelles of various states, manipulated by photo-cross-linking and pH changes, were used as emulsifiers to stabilize toluene-in-water or styrene-in-water emulsions. For the un-cross-linked micelles, polymer chains gradually protrude from micelles with pH increasing, which benefits the increase in the emulsifying efficiency of micelles. However, as pH elevated over 8, the stability of emulsions significantly decreases due to the disintegration of micelles. On the contrary, micelles with SDC of 95% keep their structural integrity and become more rigid as pH increase, leading to lower emulsifying efficiency of micelles and worse stability of the emulsions. This paper provides a new insight into the principles governing the extremely high emulsifying efficiency of polymeric particulate emulsifiers and pH-dependent or pH-responsive properties of the formed emulsions.

Biodegradable Microembolics with Nanografted Polyanions Enable High-Efficiency Drug Loading and Sustained Deep-Tumor Drug Penetration for Locoregional Chemoembolization Treatment.

Transarterial chemoembolization (TACE), the mainstay treatment of unresectable primary liver cancer that primarily employs nondegradable drug-loaded embolic agents to achieve synergistic vascular embolization and locoregional chemotherapy effects, suffers from an inferior drug burst behavior lacking long-term drug release controllability that severely limits the TACE efficacy. Here we developed gelatin-based drug-eluting microembolics grafted with nanosized poly(acrylic acid) serving as a biodegradable ion-exchange platform that leverages a counterion condensation effect to achieve high-efficiency electrostatic drug loading with electropositive drugs such as doxorubicin (i.e., drug loading capacity >34 mg/mL, encapsulation efficiency >98%, and loading time <10 min) and an enzymatic surface-erosion degradation pattern (∼2 months) to offer sustained locoregional pharmacokinetics with long-lasting deep-tumor retention capability for TACE treatment. The microembolics demonstrated facile microcatheter deliverability in a healthy porcine liver embolization model, superior tumor-killing capacity in a rabbit VX2 liver cancer embolization model, and stabilized extravascular drug penetration depth (>3 mm for 3 months) in a rabbit ear embolization model. Importantly, the microembolics finally exhibited vessel remodeling-induced permanent embolization with minimal inflammation responses after complete degradation. Such a biodegradable ion-exchange drug carrier provides an effective and versatile strategy for enhancing long-term therapeutic responses of various local chemotherapy treatments.

Combined Silver Sulfadiazine Nanosuspension with Thermosensitive Hydrogel: An Effective Antibacterial Treatment for Wound Healing in an Animal Model.

Introduction: Silver sulfadiazine (AgSD) is widely used in burn wound treatment due to its broad-spectrum antibacterial activity. However, its application in wound healing is greatly hindered by the low solubility of AgSD particles and their cellular cytotoxicity. Herein, we studied the safety and in vivo efficacy of nano-sized silver sulfadiazine loaded in poloxamer thermosensitive hydrogel (NS/Gel). Methods: In NS/Gel, silver sulfadiazine was prepared into silver sulfadiazine nanosuspension (NS) to improve the solubility and enhance its antibacterial activity, whereas the poloxamer thermosensitive hydrogel was selected as a drug carrier of NS to achieve slow drug release and reduced cytotoxicity. The acute toxicity of silver sulfadiazine nanosuspension was first evaluated in healthy mice, and its median lethal dose (LD50) was calculated by the modified Karber method. Furthermore, in vivo antibacterial effect and wound healing property of NS/Gel were evaluated on the infected deep second-degree burn wound mice model. Results: The mortality ratio of mice was concentration-dependent, and the LD50 for silver sulfadiazine nanosuspension was estimated to be 252.1 mg/kg (230.8 to 275.4 mg/kg, 95% confidence limit). The in vivo dosages used for burn wound treatment (40-50 mg/kg) were far below LD50 (252.1 mg/kg). NS/Gel significantly accelerated wound healing in the deep second wound infection mice model, achieving > 85% wound contraction on day 14. Staphylococcus aureus in the wound region was eradicated after 7 days in NS/Gel group, while the bacterial colony count was still measurable in the control group. Histological analysis and cytokines measurement confirmed that the mice treated with NS/Gel exhibited well-organized epithelium and multiple keratinized cell layers compared to control groups with the modulated expression of IL-6, VEGF, and TGF-ß. Conclusion: The combination of silver sulfadiazine nanosuspension and thermo-responsive hydrogel has great potential in clinical burn wound treatment.

Ecological interception effect of mangroves on microplastics.

As the last barrier preventing river pollutants from entering the ocean, mangroves have strong absorption and purification abilities, and strong tolerance. We collected mangrove surface water and sediment samples from the Xixi Estuary of Xiamen city. The results showed that the abundance of microplastics in seawater ranged from 620 to 13,100 n/m3, the abundance of microplastics in sediment ranged from 143 to 488 n/kg, the distribution of microplastics was uneven, and the abundance of microplastics in the Xixi Estuary mangrove was significantly higher than that in the non-mangrove area. The sediment column sample results also showed that microplastics were detected in each layer of the sediments, indicating that microplastics were trapped in each layer of mangrove sediments. Therefore, we believe that mangrove forests have an ecological interception effect on microplastics. After entering mangroves, microplastics are affected by tidal reciprocating current scouring, river runoff, sunlight, wind erosion and other factors and gradually break into increasingly smaller particles through physical, chemical and biological effects. Microplastics accumulate in the sediments and experience sedimentation, suspension and reprecipitation processes together with the surface sediments. Mangroves should be widely planted in estuaries to reduce microplastic entry into the ocean.

Hyperbranched epoxy resin-grafted graphene oxide for efficient and all-purpose epoxy resin modification.

Despite great efforts have been made on epoxy resins modification, development of additives that can be used to efficiently and universally modify epoxy composites remains a challenging task. Herein, graphene oxide (GO) sheets were covalently linked with hyperbranched epoxy resin (HBPEE-epoxy) to form HBPEE-epoxy functionalized GO (HPE-GO), which was then incorporated into epoxy resin (EP) matrix to achieve efficient and all-purpose enhancement of the properties of EPs. Compared with unmodified GO sheets, the functionalized HPE-GO sheets were better dispersed and exhibited better interfacial compatibility with the epoxy matrix, and consequently, the mechanical and thermal properties of HPE-GO/EP composites improved significantly compared to unmodified GO/EP composites. The tensile strength, flexural strength, impact strength, and fracture toughness (KIC) of EP composites containing 0.5 wt% HPE-GO increased by 65.0%, 36.2%, 259.1%, and 178.9%, respectively, compared with those for the neat EP. The storage modulus (E'), glass transition temperature (Tg), and thermal stability (T5%) also showed modest improvements. Furthermore, the HPE-GO/EP composites exhibited optimal thermal conductivities and thermal expansion properties, while maintaining higher volume resistivities compared with GO/EP composites. The results of this study support that HPE-GO is a promising, all-purpose modifier for EPs.

Universal platform for accurately damage-free mapping of sEVs cargo information.

SEVs (small extracellular vesicles) contents signatures appear to mirror pathological changes of diseases, and mapping sEVs contents profile is a promising approach for non-invasive diagnosis of the disease. Herein, we propose a universal system for accurately and damage-freely mapping of sEVs content profile using dual-recognition triggered CHA (catalytic hairpin assembly) and DNAzyme based signal amplification strategy. After immunoassay based capture of CD63 positive sEVs by anti-CD63 lgG coated on the surface of polystyrene plates, probes are incubated with fixed sEVs to penetrate sEVs membrane and act to sense sEVs contents. In detection step, integrated CHA and DNAzyme based strategy is initiated by released initiator from capture probe after recognizing targets, forming a dual circle signal recycling process, realizing signal amplification for high sensitivity. Given the attractive analytical features that i) a universal platform for indistinctive sEVs nucleic acids and protein molecules detection; ii) high sensitivity derived from dual circle signal recycling process; iii) enzyme-free characteristic of integrated CHA and DNAzyme minimizes the interference to sEVs biological activity; iv) mapping of sEVs contents profiles indicates a brand-new strategy for non-invasive diagnosis of the disease, the present approach shows great promise for analyzing additional different analytes in clinical and experimental researches.

Zinc Ion-crosslinked polycarbonate/heparin composite coatings for biodegradable Zn-alloy stent applications.

Zinc and its alloys are the best candidates for biodegradable cardiovascular stents due to their good corrosion rate and biocompatibility in vasculature. However, the cytotoxicity caused by the rapid release of zinc ions during the initial degradation stage and the lack of an anticoagulant function are huge challenges for their practical clinical applications. In this work, we developed a zinc ion-crosslinked polycarbonate/heparin composite coating via electrophoretic deposition (EPD) to improve the biocompatibility and provide anticoagulant functions for Zn-alloy stents. Both electrochemical tests and in vitro immersion tests demonstrated an enhanced corrosion resistance and lower Zn ion release rate of the coated Zn alloys. Enhanced adhesion and proliferation of endothelial cells on coated Zn alloys were also observed, indicating faster reendothelialization than that on bare Zn alloys. Moreover, the surface erosion of the composite coating led to the uniform and long-term release of heparin, which remarkably inhibited the adhesion and activation of platelets, and may have endowed the coated Zn-alloy stents with long-term anticoagulant functions.

Spatial and temporal distributions of microplastics and their macroscopic relationship with algal blooms in Chaohu Lake, China.

Microplastics are emerging pollutants with sizes less than 5 mm, and they are ubiquitous. The occurrence of algal blooms has become a major problem affecting water quality in Chaohu Lake. To understand the relationship between the microplastic distribution and algal bloom density from a macroscopic point of view in Chaohu Lake, we collected microplastic samples from water and sediments during the wet and dry seasons and collected satellite remote sensing images of the algae density in recent years. The research results showed that the spatial and temporal distributions of microplastics were uneven and varied greatly. The average abundances of microplastics in the water samples were 2133 ± 1534 n•m-3 in the dry season and 1679 ± 1577 n•m-3 in the wet season, and the average abundance of microplastics in sediments was 308 ± 231 n•kg-1. The abundance of microplastics in the estuaries was higher than those in other locations, and it was higher in the western part of the lake than in the eastern part. The microplastics in water and sediments presented different sizes, colors, shapes and compositions. The abundance, distribution and migration of microplastics were mainly affected by population density, rainfall, runoff, hydrodynamic force and wind direction. At a more macroscopic level, the distribution of microplastics was similar to that of algal blooms, TN and TP to some extent, especially in the early stage of algal bloom outbreaks, and the algal density was significantly positively correlated with the flux of microplastics into the lake. Microplastics, as carriers of algae, could promote the growth of algae blooms in the early stage, while in the later stage, microplastics and algal blooms could aggregate and coprecipitate through adsorption or adhesion and then inhibit the growth of algae.

[Pollution Characteristics of Microplastics in Sediments of Xiamen Bay Beach].

Microplastics widely exist in various environmental media and have become a global environmental problem. To investigate the pollution characteristics, deposition patterns, and influencing factors of microplastics in the sediments of bay beach, five typical beaches were selected in Xiamen Bay. According to the tidal variation, 0-10 cm, 10-20 cm, and 20-30 cm sediment column samples were collected in layers at the high tide line, middle tide line, and low tide line at the same time, and the characteristics of the horizontal and vertical distribution of microplastics in the beach sediments were studied. The results showed that the abundance of microplastics in 45 sediment samples in Xiamen Bay beach ranged from 39 to 260 n·kg-1, with an average abundance of (114±26) n·kg-1. The shapes of microplastics were mainly fibers, fragments, granules, and foams, with fibers making up the largest proportion. The main components were polyethylene terephthalate (PET), cellophane, and polyethylene (PE). The colors of microplastics included transparent, yellow, blue, black, white, etc. The average abundance of microplastics showed a certain pattern depending on the beach location, intertidal zone, and sampling depth. Moreover, the abundance and distribution of microplastics on the beach were affected by various natural and human factors such as waves, tides, shoreline shape, the number of tourists, and the cleaning of marine floating debris. These results aid the understanding of the distribution characteristics and sources of microplastics in beach sediments, provide a basis for the transport of microplastics from land to sea, and provide data support for the collection of sea floating garbage and shoreline garbage.

Facile fabrication of biodegradable endothelium-mimicking coatings on bioabsorbable zinc-alloy stents by one-step electrophoretic deposition.

The zinc-alloy stent is one of the best potential candidates for bioabsorbable metal stents because of its appropriate corrosion rate aligned to the duration of the healing process of the surrounding vessel tissues. However, excessive release of zinc ions, causing cytotoxicity of endothelial cells, and insufficient surface bio-functions of Zn-alloy stents lead to considerable challenge in their application. Herein, one-step electrophoretic deposition was employed to apply a hybrid coating of polycarbonate, tannic acid, and copper ions with tailored functions on Zn-alloy stents to enhance their corrosion resistance and provide an endothelium-mimicking surface. Specifically, the synthesized amino-functionalized aliphatic polycarbonates endowed the hybrid coating with specific surface-erosion properties, resulting in superior corrosion resistance and long-term stability in degradation tests both in vitro and in vivo. The immobilized copper ions enabled the catalytic generation of nitric oxide and promoted the adhesion and proliferation of endothelial cells on zinc alloy. The added tannic acid firmly chelated the copper ions and formed durable phenolic-copper-amine crosslinked networks by electrostatic interaction, resulting in long-term stability of the hybrid coating during the 21 day dynamic immersion test. Tannic acid exerted a synergistic antibacterial effect with copper ions as well as a reduction in the inflammatory response to the zinc substrate. In addition, the hybrid coating improved the in vitro hemocompatibility of zinc alloys. By adjusting the amount of chelated copper in the coating system, the biological function of the corresponding coatings can be controlled, providing a facile surface treatment strategy to promote the progress of zinc-alloy stents in clinical applications.

Shape-Anisotropic Microembolics Generated by Microfluidic Synthesis for Transarterial Embolization Treatment.

Particulate embolic agents with calibrated sizes, which employ interventional procedures to achieve endovascular embolization, have recently attracted tremendous interest in therapeutic embolotherapies for a wide plethora of diseases. However, the particulate shape effect, which may play a critical role in embolization performances, has been rarely investigated. Here, polyvinyl alcohol (PVA)-based shape-anisotropic microembolics are developed using a facile droplet-based microfluidic fabrication method via heat-accelerated PVA-glutaraldehyde crosslinking reaction at a mild temperature of 38 ° C. Precise geometrical controls of the microembolics are achieved with a nearly capsule shape through regulating surfactant concentration and flow rate ratio between dispersed phase and continuous phase in the microfluidics. Two specific models are employed, i.e., in vitro decellularized rabbit liver embolization model and in vivo rabbit ear embolization model, to systematically evaluate the embolization behaviors of the nonspherical microembolics. Compared to microspheres of the same volume, the elongated microembolics demonstrated advantageous endovascular navigation capability, penetration depth and embolization stability due to their comparatively smaller radial diameter and their central cylindrical part providing larger contact area with distal vessels. Such nonspherical microembolics present a promising platform to apply shape anisotropy to achieve distinctive therapeutic effects for endovascular treatments.

A Strong Dual-Component Bioadhesive Based on Solventless Thiol-isocyanate Click Chemistry.

Isocyanate is an efficient tissue anchor for engineering of strong bioadhesives. However, isocyanate-containing adhesives were seldom manufactured due to their requirement of water-free administration and time-consuming moisture-induced solidification. To address this issue, here, a solventless dual-component bioadhesive based on thiol-isocyanate cross-linking chemistry is reported. This dual-component bioadhesive consists of a hyperbranched polymer with thiol groups (HBPTE) and an isocyanate-modified polyethylene glycol (PEGNCO). HBPTE and PEGNCO are low-viscosity fluids at room temperature and hence could be used directly as adhesive components, in the absence of a catalyst and a solvent. The thiol-isocyanate click chemistry of components provides the HBPTE-PEGNCO mixture with a gelation time of 1.8-3 min, which makes it acceptable for practical applications. The abundance of isocyanate groups in the adhesive molecule provides strong bonding strength through formation of chemical linkages with reactive groups on the tissue. Moreover, in vitro and in vivo evaluations showed excellent biocompatibility of the HBPTE-PEGNCO adhesive. This dual-component bioadhesive based on solventless thiol-isocyanate click chemistry displayed a fast gelation time and excellent bonding performance, providing a pioneering idea for engineering isocyanate-containing bioadhesives.

Hyperbranched polymer with dynamic thiol-aldehyde crosslinking and its application as a self-healable bioadhesive.

Bioadhesives crosslinked with dynamic bonds exhibit shear-thinning, self-healing, and on-demand detachment properties, but generally show a weak bonding performance due to their poor bulk strength. Obtaining a strong bioadhesive with reversible crosslinking remains a challenge. To address this issue, herein we engineered a dynamic thiol-aldehyde crosslinked solvent-free adhesive based on hyperbranched polymer. The adhesive was obtained by directly mixing a liquid hyperbranched polymer with thiol end groups (HBPTE) and benzaldehyde-terminated polyethylene glycol (PEGCHO) without any additional catalyst or solvent. The solvent-free strategy yielded a dense crosslinking structure with many aldehyde groups, so this HBPTE-PEGCHO adhesive can strongly bond to tissue and various non-biological substrates. In addition, the HBPTE-PEGCHO adhesive has self-healing and thermo-reversible bonding properties due to the dynamic thiol-aldehyde crosslinking matrix. In vivo wound healing experiments show that this HBPTE-PEGCHO adhesive is tissue-benign, suggesting it can be applied in clinical practice. Combining the hyperbranched polymer-based solvent-free strategy and dynamic thiol-aldehyde crosslinking chemistry provides a simple but effective way to engineer a multifunctional bioadhesive with the desired bonding performance.

Photoinduced morphology switching of polymer nanoaggregates in aqueous solution.

A novel photosensitive C-PNIPAAm comprising hydrophilic PNIPAAm conjugated with a relatively short but very hydrophobic coumarin part was designed and prepared using a coumarin-containing disulfide derivative (C-S-S-C) as transfer agent in the presence of Bu(3)P and water. It was found that C-PNIPAAm can form polymer micelles in aqueous solution. And the micellar morphology in aqueous solution can be photoswitched into hollow spheres according to the photodimerization of coumarin end groups upon 365 nm irradiation and reform the micellar morphology after the subsequent photoscission of dimers upon 254 nm. This instant morphology changing phenomenon was successfully monitored by dynamic light scattering (DLS) and transmission electron microscopy (TEM) measurements. TEM observations showed the small spherical shape of micelles with diameter at 30-50 nm before photo-cross-linking, the big vesicles with diameter at 200-350 nm after photo-cross-linking, and the small micelles with diameter at 30-50 nm after the subsequent photo-de-cross-linking in the first irradiation cycle. The reason for this significant morphology switching can be attributed to the reversible photoinduced amphiphilic structure transformation between the telechelic "hydrophobic end-hydrophilic chain" structure and the ABA type of "hydrophilic chain-hydrophobic center-hydrophilic chain" one upon alternating irradiation.

Fluorescent molecularly imprinted nanoparticles with boronate affinity for selective glycoprotein detection.

Specific recognition and sensing of glycoproteins are of great importance in clinical diagnostics considering their frequent utilization as biomarkers and therapeutic targets. In this work, a biomimetic fluorescent sensor for the selective and sensitive detection of glycoprotein was developed, which was based on late-model boronate fluorescent molecularly imprinted nanoparticles (B-FMIP NPs). The B-FMIP NPs were fabricated via the macromolecular assembly of a fluorescent photo-crosslinkable amphiphilic copolymer containing boronic acid with glycoprotein in aqueous solution and in situ photo-crosslinking. Due to the synergism of boronate affinity and the molecular imprinting effect, the resultant B-FMIP NPs demonstrated specific recognition and remarkable selectivity toward the template glycoprotein (ovalbumin, OVA) with a high imprinted factor (α) of 6.0 and gave rise to obvious fluorescence quenching after binding with OVA in water. Under optimized experimental conditions, the as-prepared B-FMIP NPs exhibited linearity over the OVA concentration range of 10-13 to 10-3 mg mL-1 with a detection limit of 3.3 × 10-14 mg mL-1, as well as a rapid response time (about 10 min), which was superior to that of other previously reported OVA sensors. Finally, these B-FMIP NPs have been applied for the determination of OVA in real samples.

A fabrication strategy for protein sensors based on an electroactive molecularly imprinted polymer: Cases of bovine serum albumin and trypsin sensing.

A high-performance molecularly imprinted sensing platform inspired by natural recognition mechanisms was fabricated to detect protein by employing a linear electro-polymerizable molecularly imprinted polymer as macromonomer. This was achieved via the combination of a biosensor fabrication with a self-assembly imprinting technique without the use of chemical labels. An amphipathic electroactive copolymer was designed as macro-monomer to maintain structural integrity of the protein template via self-assembly, resulting in generation of a 3D construction around the protein molecule to form imprinted sites. Electro-polymerization was utilized not only to anchor imprinted sites but also to enhance electron transfer. The adaptable sensing platform was based on a strengthened recognition reaction between the MIP layer and template protein after the generation of an electroactive network. Bovine serum albumin (BSA) and trypsin were used as model proteins to investigate the method's generality, which gave broad detection ranges of 10-14-10-5 mg mL-1 for BSA and 10-13-10-8 mg mL-1 for trypsin. These results indicate that the proposed fabrication offers an effective and versatile strategy for protein recognition.

Synthesis of Temperature/pH Dual-Stimuli-Response Multicompartmental Microcapsules via Pickering Emulsion for Preprogrammable Payload Release.

Stimuli-responsive microcapsules, which can release the encapsulated payload under various environmental stimuli, have attracted great interests of the food, pharmaceutical, cosmetics, and agricultural fields in recent years. However, most reported responsive microcapsules normally have a single storage area and thus load/release only one type of payload under one stimulus. In this work, we fabricated a novel kind of multicompartmental intelligent microcapsule with two storage areas and independently controlled (preprogrammable) releasing behavior under different stimuli via rapid photopolymerization of Pickering emulsions. In our strategy, a temperature-sensitive polymeric (N-isopropyl acrylamide, pNIPAM) particle was prepared and loaded with Nile Red (NR), which was then employed as a Pickering emulsifier to stabilize oil-in-water droplets. The oil was composed of pH-responsive monomers and oil-soluble fluorescent green (OG). Upon exposure to photoirradiation, pH-responsive monomers were polymerized along the interior of the droplets and converted into microcapsules. With NR in the temperature-sensitive pNIPAM@NR particles and OG in the interior of the microcapsules, the as-prepared microcapsules possess dual-carrier capability with two payloads encapsulated dependently in two different compartments. In addition, the microcapsules could respond to two different external stimuli (temperature and pH) and realize the selective and independent release of encapsulated molecules (NR and OG) from the shell and core without any mutual interference. More importantly, the release of NR and OG can be programmed by preprogramming the order of the stimulus responses, which can be altered. Our work develops a simple and effective strategy to fabricate responsive multicompartment microcapsules with preprogrammable release of different molecules.

Electrochemical protein recognition based on macromolecular self-assembly of molecularly imprinted polymer: a new strategy to mimic antibody for label-free biosensing.

A versatile strategy, based on the use of an amphiphilic copolymer as a macromonomer, was developed for the preparation of a fully synthetic MIP (molecularly imprinted polymer) sensor for protein recognition. A UV-crosslinkable copolymer poly(DMA-co-HEA-co-St) (UPDHS) was designed and synthesized to assemble with the template protein in aqueous solution, resulting in the fabrication of protein imprinted polymeric nanoparticles. Linear macromolecular chains were used to protect the structural integrity of the protein, through which a 3D structure was formed around the protein molecule to generate recognition cavities. Then the nanoparticles were immobilized on the cleaned surface of a transducer as an MIP sensing platform. The resultant MIP coating was then irradiated via ultraviolet light to ensure that the recognition cavities were stable after UV curing. After protein extraction, recognition cavities complementary to the protein molecule in shape, size and chemical functionality were formed in the platform, which could then selectively rebind to the template in a mixture of closely related compounds. The sensor exhibited satisfactory selectivity, a wide linear range from 10-14 to 10-9 mg mL-1, and a comparatively lower detection limit for protein detection. This strategy offers a new and straightforward method for the synthesis of receptors for label-free and cost-efficient protein recognition. This is one of the most effective and versatile strategies for the preparation of high-performance protein recognition devices based on a fully synthetic MIP.