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Over a century ago, phenolic formaldehyde (PF) resin was developed and continues to increase in yield due to its diverse applications. However, PF resin is a thermosetting plastic lacking fluidity and moldability, which are nondegradable in natural environments, leading to severe threats to fossil resources as well as global environmental crises. As a result, recycling PF resin is extremely important. In this review, we provide the recent advances in the recycling of PF resin, which includes mechanical recycling, chemical recycling, and utilization of carbon-based materials. The advantages and disadvantages of each strategy are evaluated from a green chemistry perspective. This article aims to attract interest in PF resin design, synthesizing, application and recycling, offering useful suggestions. [ABSTRACT FROM AUTHOR]

Abstract Poly(3,4-ethylenedioxythiophene) (PEDOT) has been electropolymerized on the Si wafer through a non-aqueous galvanostatic method, which is employed to fabricate the Si/organic solar cell for the first time. Surface morphology, film thickness as well as the sheet resistance of the PEDOT-coated Si wafer are investigated by controlling the polymerization time, and the best electropolymerization time for the Si/PEDOT device performance is 8 s. However, the pristine PEDOT film shows low carrier concentration, and the low work function is not suitable for the fabrication of high performance solar cells. Interestingly, after optimizing the PEDOT-coated Si wafer with hydrochloroplatinic acid (H 2 PtCl 6) solution, the work function of the PEDOT film is enhanced, which raises the barrier height (Φ SBH) as well as V bi between the Si and PEDOT interface. Additionally, the sheet resistance of the PEDOT layer is reduced. Both of them are beneficial for the better charge transfer and collection. As a result, the efficiency of 7.36% has been achieved by the Si/PEDOT devices, which is much higher than that of the control ones, ∼5.49%. More importantly, due to the stable PEDOT, the Si/PEDOT solar cell shows excellent stability. These results point out a new route to develop low-cost, high performance and high stability Si/organic hybrid solar cells. Graphical abstract Electropolymerized PEDOT is employed for the first time to Si/organic solar cells achieving a power conversation efficiency of 7.36% with much higher stability than that with traditional PEDOT:PSS. Image 1 Highlights • PEDOT is first electropolymerized on Si wafers and constructed for solar cells. • The resistance of PEDOT layer can be reduced and the work function of that can be enhanced after the H 2 PtCl 6 treatment. • Electropolymerized PEDOT solar cell displays much more excellent stability than PEDOT:PSS device. [ABSTRACT FROM AUTHOR]

Abstract: A large number of molecularly imprinted polymers (MIPs) have been investigated and reported over the last decade. Various templates have been successfully exploited and used, leading to significant advances in separation, adsorption, catalysis, sensing, and drug delivery. Among all the templates, small molecules have dominated in the synthesis of MIPs. In contrast, progress made in imprinting macromolecules has been slow, mainly due to the challenges presented by the size, structure and conformational fragility of biological macromolecules. In this review, we focus on discussing some key issues involved in the imprinting of macromolecules from recent publications. The similarity and difference between imprinting small molecules and macromolecules are highlighted. Other aspects relating to polymer design and function are also discussed. [Copyright &y& Elsevier]

Abstract: A novel electrochemical immunosensor capable of enzyme-free detection of alpha fetoprotein (AFP) is reported. This immunosensor was fabricated in a sandwich-like format where catalytic Au–Pd nanocrystals and highly conductive N-doped graphene sheets were incorporated. The significant catalysis by Au–Pd nanocrystals toward hydrogen peroxide, along with the increased electron transfer by graphene sheets, caused signal generation and increased sensitivity, which enables the enzyme-free detection of AFP. With a low detection limit at 0.005ngmL−1, this novel immunosensor worked well over the broad linear range of 0.05–30ngmL−1. Unlike previously reported enzyme-based electrochemical immunosensors, which often involve the complicated steps for enzyme loading and necessary treatments to keep the activity of enzyme, this novel immunosensor is simple in nature and employed catalytic Au–Pd nanoparticles and highly conductive graphene, which thus enables reliable and sensitive detection for clinic usage. [Copyright &y& Elsevier]

Abstract: ‘On/off’-switchable catalysis by a smart enzyme-like imprinted polymer is reported. This unique imprinted polymer was composed of poly(N-isopropylacrylamide)-containing p-nitrophenyl phosphate-imprinted networks that exhibited temperature-dependent hydrophilicity/hydrophobicity. At a relatively low temperature (such as 20°C), this polymer was capable of vigorous catalysis for the hydrolysis of p-nitrophenyl acetate due to its hydrophilic networks, which enabled access to the imprinted framework. On the contrary, at higher temperatures (such as 40°C), this polymer demonstrated poor catalysis resulting from its dramatically increased hydrophobicity, which inhibited access to the imprinted sites. Unlike previously reported imprinted polymers which lack adjustable networks, this novel imprinted polymer employed thermosensitive poly(N-isopropylacrylamide) networks, thus enabling the switchable catalysis. [Copyright &y& Elsevier]

The concept used to realize the modulation of molecular recognition in a molecularly imprinted polymer is presented. Creating a thermal phase transition within the binding framework, the imprinted material was prepared using Boc-phenylalanine as the template and pNIPAM as the sensitive unit. The results indicate that such a transition causes a clear modulation in the recognition behavior of the prepared polymer which depends on the operation temperature. At a relatively low temperature, the prepared polymer acts like a traditionally imprinted one, showing a highly specific recognition for the imprint species. However, the prepared polymer does not present any notable resolution at 40 °C. This recognition behavior is comparable to a process that can be switched on and off, thus making modulated recognition feasible. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

This article presents an original work on thermodynamically and kinetically interpreting the specific adsorption and recognition by molecularly imprinted polymer. The imprinted polymer was prepared with Bisphenol A (BPA) dimethacrylate as template monomer. The results indicate that the prepared polymer can well discriminate the template from its analogue, so as to adsorb more for BPA and less for DHBP. Kinetic analysis indicates that this specific adsorption, in nature, can be a result of preferential promotion. The imprint leads to a larger adsorption-rate in the template than in its analogue. Thermodynamic study also implies that the molecular induction of imprint toward BPA is larger than toward DHBP, which thus makes the polymer capable of specifically allowing the template to bind. [ABSTRACT FROM AUTHOR]

Molecular imprinting is a promising technique for the preparation of polymers with predetermined selectivity and high affinity. Normally, based on the self-assembly of functional monomers and templates (i.e., imprint molecules), the imprinted polymers are produced by crosslinking polymerizations. The templates are subsequently removed from the polymer, leaving behind binding sites complementary to the imprint species in terms of the shape and the position of functional groups. Recognition of the polymer constitutes an induced molecular memory, which makes the binding sites capable of selectively recognizing the imprint species. This article presents a limited review on molecular self-assembly and the uses of these imprinted polymers in separation, sensors, and catalysis. Other aspects including related backgrounds are also discussed. [ABSTRACT FROM AUTHOR]

Abstract: This article presents an interesting study on the adsorption of bovine serum albumin (BSA) onto electrostatic microspheres. With sulfonated poly(methyl methacrylate) microspheres as the support, the adsorption appears to be sensitive for protein concentration, pH condition and ionic strength. The electrostatic interaction from these sulfonate groups plays obviously an important role in the adsorption, not only increasing the adsorption amount but also affecting the intermolecular interaction of protein. The effect is evidenced by the changes of pH condition and ionic strength. Near the isoelectric point of BSA, the effect reaches a maximum. A higher or lower pH will result in its dramatic decrease. The dependence of protein adsorption on the ionic strength is, however, a cooperative result from the electrostatic interaction and support-protein affinity. With respect to these, further information shows that they can be related to the structure of protein. [Copyright &y& Elsevier]

Abstract: The adsorption of bovine serum albumin (BSA) onto modified PMMA microspheres was studied. The sulfonate groups on the surface of microspheres play an important role in this system. From microsphere 1 to 4, with the increase in amount of sulfonate groups on the surface of microspheres, the apparent constants increased from 2.28 to 3.18×10-2min-1. The adsorption isotherms were fitted to the Langmuir–Freundlich isotherm. With the increase of sulfonate groups on the surface of microspheres, Cm values increased and K values decreased. Close to the isoelectric point of BSA, the adsorption amount exhibits a maximum. A higher or lower pH results in the significant decrease of the adsorption amount. And with the increase of ionic strength, the adsorption of BSA onto microspheres decreased. This may be responsible for the binding of Cl- and BSA, which resulted in a degree of change in the conformation and local charge of BSA macromolecules. [Copyright &y& Elsevier]

Modified poly(methyl methacrylate) (PMMA) microspheres, about 7 μm in diameter, carrying aldehyde groups on their surfaces were synthesized and used as the support for enzyme immobilization. The immobilizing behavior as well as the properties of immobilized enzyme was studied. The amount of bound enzyme can be extended to 76.8 mg g-1 support, which is relatively much higher than other supports. The kinetic investigation derived from three typical models shows that the practical process is more complicated than the ideal condition, with one or more interactions being involved in the immobilization process. The Km value is actually larger and Vmax is smaller in the immobilized form than those in the free form. The increased resistance of the immobilized enzyme against the changes of temperature indicates that immobilizing enzyme onto the modified microspheres is useful for enzyme immobilization. [Copyright &y& Elsevier]

Effect of β-cyclodextrin (CD) on methyl methacrylate dispersion polymerization forming poly (methyl methacrylate) (PMMA) particles was investigated. The presence of CD showed obviously effects on the polymerization, so as to increase the rate of polymerization and the conversion of monomer, as well as decrease the particle size. These effects were evidenced by the more increase in the CD content. The change of free energy derived from thermodynamic investigation in the present of CD was lower than that in the absence of CD. Also the monomer reactivity in the presence of CD is actually higher than that in the absence of CD. The decrease of free energy would be thermodynamically responsible for the increase of MMA conversion. The increase of monomer reactivity may take charge of increasing the polymerization rate. The dependency of particle size on CD content may be thermodynamically responsible for the change of macromolecular conformations of stabilizer due to the interaction of CD and stabilizer. [Copyright &y& Elsevier]

In this article, a novel silicon-based electrode was designed with the facile solution methods. With the modification of highly conductive PEDOT:PSS layer on the SiNWs by the spin-coated method (SiNWs-PSS), three-dimensional (3D) porous network polyaniline nanofibers (PANI) film was uniformly electrodeposited on the silicon surface (SiNWs-PSS@PANI). The sheet resistances of the PEDOT:PSS layer with different surfactants as well as the deposition time of the PANI were investigated. After optimization, the fabricated SiNWs-PSS@PANI electrode displayed high capacitance about 301.71 mF cm−2 at the current density of 1 mA cm−2, which enhanced ~ 29 fold comparing to 10.18 mF cm−2 of electrode without the PEDOT:PSS layer between the SiNWs and PANI (SiNWs@PANI), outperforming most values of the reported silicon-based electrodes. The electrode designed in this paper provides a new idea to fabricate high-performance of silicon-based micro-supercapacitors with the simple and low-temperature method. [ABSTRACT FROM AUTHOR]

It is of interest to develop wide-temperature domain damped hydrophobic materials. In this paper, we designed incorporating bio-based phenolic resin into the IIR matrix and introducing dibenzyl fork acetone (DBA) into the main chain structure with sodium hydroxide activation to construct three-dimensional network. In this paper, we designed incorporating bio-based phenolic resin into the IIR matrix and introducing dibenzyl fork acetone (DBA) into the main chain structure with sodium hydroxide activation to construct three-dimensional network. The added bio-based phenolic resin has reticulated structure blended with butyl rubber, combined with sodium hydride activation-modified IIR. The results show that sodium hydride activated modification of DBA is introduced into the main chain structure of IIR by infrared and 1H NMR analysis. The material hydrophobic is realized by the introduction of DBA with static water contact angle of 103.5°. The addition of 10phr lignin-based phenolic resin (LPF) is compatible with IIR, and the torque can reach 7.0 N-m. The tensile elongation of the modified butyl rubber composite can reach 2400% with tensile strength up to 11.43 MPa, while the damping factor can reach 0.37 even at 70 °C. The thermal stability of the composites is enhanced with mass retention rate of 28%. The bio-based PF/NaH activation-modified butyl rubber damping material has potential applications in damping hydrophobicity with wide temperature range. [ABSTRACT FROM AUTHOR]

It is of interest to develop wide-temperature domain damped hydrophobic materials. In this paper, we designed incorporating bio-based phenolic resin into the IIR matrix and introducing dibenzyl fork acetone (DBA) into the main chain structure with sodium hydroxide activation to construct three-dimensional network. In this paper, we designed incorporating bio-based phenolic resin into the IIR matrix and introducing dibenzyl fork acetone (DBA) into the main chain structure with sodium hydroxide activation to construct three-dimensional network. The added bio-based phenolic resin has reticulated structure blended with butyl rubber, combined with sodium hydride activation-modified IIR. The results show that sodium hydride activated modification of DBA is introduced into the main chain structure of IIR by infrared and 1H NMR analysis. The material hydrophobic is realized by the introduction of DBA with static water contact angle of 103.5°. The addition of 10phr lignin-based phenolic resin (LPF) is compatible with IIR, and the torque can reach 7.0 N-m. The tensile elongation of the modified butyl rubber composite can reach 2400% with tensile strength up to 11.43 MPa, while the damping factor can reach 0.37 even at 70 °C. The thermal stability of the composites is enhanced with mass retention rate of 28%. The bio-based PF/NaH activation-modified butyl rubber damping material has potential applications in damping hydrophobicity with wide temperature range. [ABSTRACT FROM AUTHOR]

Carbon materials play an important role in supercapacitors due to their structural diversity, rich surface morphology, excellent chemical stability and highly active surfaces. Currently, there are many reports on the synthesis methods for carbon-based materials. The molten salt method stands out among the many methods for its advantages of economy, environmental protection, high efficiency, and maneuverability. Here, we focus on the different roles played by molten salts as templates, sealants, reaction media, and catalysts from the point of view of their functions. The properties and selection principles of the molten salts are discussed in depth, focusing on the morphology, structure, and capacitive properties of the carbon materials prepared using the molten salt strategy. Finally, the current research status of the preparation of carbon-based materials by the molten salt method is summarized, the shortcomings of existing technology are pointed out, and the prospects for its development are envisioned. It is hoped that this review can provide some basic knowledge for the preparation of carbon-based materials by the molten salt method and promote further research on molten salt technology. [ABSTRACT FROM AUTHOR]

The poly[N,N-(dimethylamino) ethyl methacrylate] (PDMAEMA) macro-RAFT agent mediated dispersion polymerization of photo-responsive nitrobenzene-based monomer of o-nitrobenzyl methacrylate (NBMA) was performed and the polymerization kinetics and evolution of the block copolymer nanoparticles morphology during the RAFT dispersion copolymerization were investigated in detail. This dispersion RAFT polymerization underwent initial homogeneous polymerization at initial stage and then a subsequent stage of slowed heterogeneous polymerization occurred until the monomer conversion of the polymerization reaction is basically unchanged at about 50% at 24 h. The reason of deceleration of the second stage that is different from the second stage of acceleration for common monomer is discussed. The PDMAEMA-b-PNBMA nanoparticles were prepared by PDMAMEA-mediated RAFT dispersion polymerization, and the photo-response of PDMAEMA-b-PNBMA nanoparticles was also studied. [ABSTRACT FROM AUTHOR]

Low toxicity, environmentally friendly and sustainable bio-based phenol–formaldehyde (PF) resins are the primary factors and health goals that researchers need to consider when modifying PF resins. Two novel biomass-modified PF resins were synthesized using two flavonoid phenols of daidzein and naringenin with rigid backbone structures. The results show that compared with ordinary PF, the introduction of daidzein and naringenin during the synthesis of N-PF and D-PF can delay the curing reaction and results in higher curing peak temperatures. The appropriate substitution rate of daidzein and naringenin can improve the crosslinking degree, resulting in N-PF and D-PF with higher thermal stability, ablation resistance and mechanical properties. The highest carbon yield YC800 for N-PF is 59.81% (56.85%for PF-1), and the highest YC800 for D-PF is 64.39% (PF-2 with 58.15%). The maximum tensile strength and flexural strengths of N-PF are respective 33.86 MPa and 110.42 MPa (28.77 and 79.89 MPa for PF-1), and the maximum tensile strength and flexural strengths of D-PF are respective 35.61 MPa and 103.17 MPa (24.48 and 55.79 MPa for PF-2). The D-PF and N-PF resins modified and enhanced by daidzein and naringenin have lower friction coefficient and more excellent wear resistance than pure PF. [ABSTRACT FROM AUTHOR]

In this study, we report the preparation of a lotus-leaf-like coating with robust super-hydrophobicity and anti-ultraviolet ability. As theoretically decoded from quantum mechanics, the combination of ceria-modified roughness with a substrate layer with low surface energy may help narrow the water-"hit" moiety on the surface and accordingly enhance the super-hydrophobicity, along with the intrinsic ultraviolet-resistant ability of ceria. To the end, this coating was fabricated by spraying a ceria emulsion and a perfluorosilane emulsion of the substrate layer onto a glass slide that helped form the lotus-leaf-like rough surface. Depending on the content of ceria, the prepared coating demonstrated the desired and excellent superhydrophobic properties in which the contact angle can be up to 155.7° and the rolling angle can be up to 4.8°. The presence of ceria in the prepared lotus-leaf-like coating not only enhanced the super-hydrophobicity but also dictated the anti-ultraviolet ability. In conjunction with the sturdy wear resistance, the successful preparation of this coating suggests a promising prospect for practical applications and particularly outdoor applications. [ABSTRACT FROM AUTHOR]

The present endeavor is to develop a highly-intelligent catalytic reactor prototype which is able to autonomously adapt to the environment and provides an in-situ double-shift catalytic ability. By seeking inspiration from nature, this objective is achieved by developing a self-adaptive hydrogel catalytic reactor which held a catalytic trilaminar structure capable of reverse thermosensitive properties. With increasing temperatures, the catalytic tri-layers of this catalytic reactor would function in a sequential way (i.e., one negative temperature response layer, one support layer and one positive temperature response layer) and as a result, led to the single-tandem double-shift catalytic ability. This catalytic reactor individually presented single/tandem catalytic process at relatively low temperatures or high temperatures through the cooperative work of the three layers. In this way, this catalytic reactor showed the single-tandem controllable catalytic ability. The novel protocol not only provides a new solution to complicated catalytic processes but also inspires the further application of smart polymers in a broader spectrum of areas. [ABSTRACT FROM AUTHOR]

The inflammability of polystyrene (PS) limited its application. In order to improve the flame retardancy of PS, developing reactive-type flame retardants is a promising approach. In this work, a novel N-arylpiperazine phosphoramidate monomer, 2-((phenoxy(4-phenylpiperazin-1-yl)phosphoryl)oxy)ethyl methacrylate (PPPEM), was facilely synthesized and used as a reactive-type flame retardant. The obtained monomer was then copolymerized with styrene through the free radical bulk polymerization. The thermal stability of copolymers was measured by the thermogravimetric analysis. The addition of the PPPEM units increased decomposition temperature of the copolymers, indicating the improvement of the thermal stability. The glass transition temperature of the copolymers remained little changed with varied amount of the PPPEM, implying that the introduction of PPPEM units did not evidently affect the mobility of the PS main chain. The flammability of the copolymers was evaluated by microscale combustion calorimeter (MCC) and limiting oxygen index (LOI). According to the MCC and LOI results, PPPEM unites can contribute to the decrease of the peak heat release rate, the increase of LOI and improvement of the flame retardancy. The novel N-arylpiperazine phosphoramidate monomer show a great potential for application in reactive-type flame retardants. [ABSTRACT FROM AUTHOR]

As an attractive electrode material of supercapacitors, metal organic frameworks (MOFs) have been greatly exploited. However, the nearly exclusive microporous structure prevented their advantages from being fully utilized, restraining their electrochemical performance. In this work, a hierarchical porous Zr-MOF (HP-Zr-MOF) was prepared via ligand thermolysis method, and its electrochemical performance was investigated. HP-Zr-MOF exhibits a high specific capacitance (492.7 F g−1, 1 A g−1), and good rate performance (362.5 F g−1, 10 A g−1). An asymmetric supercapacitor based on HP-Zr-MOF and activated carbon electrodes was assembled, which delivers a specific capacitance of 107.5 F g−1, and an energy density of 38 Wh kg−1 with a power density of 1341 W kg−1 at 1 A g−1, showing prospective prospect of hierarchical porous MOFs-based electrodes in energy storage application. [ABSTRACT FROM AUTHOR]

This study is aimed at booming intelligent catalysts, suggesting a bio-inspired polymer catalyst with catalytic substrate-sieving ability. By mimicking the hierarchical multi-level structures in biopolymers, this polymer catalyst was fabricated with metal nanoparticles and double "zipper" conformations individually made of polymeric hydrogen bonds and complexing interactions. Owing to the discrepant strength of both interactions against temperature, the double zipper conformations led to a hierarchical disruption of the two interactions and the stepwise disaggregation of the polymeric networks and as a result the substrate-sieving ability. This catalyst didn't present effective catalysis at low temperatures because of the blocked networks. With the increasing temperatures, this catalyst would first present catalysis towards small molecules of substrate and then further towards bigger molecules of substrate, by virtue of the hierarchical disruption of the weaker hydrogen bonds and the stronger complexing interactions. In this way, this catalyst assumed the substrate-sieving ability. The protocol of this catalyst suggests a prospect to modulate the catalytic proceedings, particularly for complicated processes. [ABSTRACT FROM AUTHOR]

Developing high-performance, low-cost and large-scale absorbent materials is crucial for the treatment of water pollution caused by pollutants leakage and emission. Herein, superelastic and superhydrophobic thermoplastic polymeric nanofibrous aerogels (NFAs) were created for removal pollutants from water by using a facile and effective method. Poly(vinyl alcohol-co-ethylene) (EVOH) nanofibers fabricated by mass-production techniques were used to construct three-dimensional NFAs through combing freeze-drying process and cross-linking treatment. The optimal parameters for creating EVOH NFAs with good formability and resilience, including composition and ratio of dispersion, dosage of cross-linking agent were obtained through experiments. EVOH nanofibers bonded with each other by glutaraldehyde under acidic conditions to from fibrous network structure in EVOH NFAs. The silane-coated EVOH NFAs were prepared through further modification with vapor-phase methyltrichlorosilane. The deposition of siloxane improved mechanical strength and decreased plastic deformation after 500 cyclic compressions. An asperate fibrous and granular siloxane coating was deposited on the surface of EVOH NFAs. The surface water contact angle increased from 104.4° ± 4.0° to 152.7° ± 1.9°, wettability of NFAs transitioned to being superhydrophobic. Silane-coated EVOH NFAs exhibited superior absorption capacity (40–92 g/g) for a variety of organic pollutants. The organic pollutants would be collected and the sorbents could be reused after distillation or squeezing. A successful scale-up of such materials open up a new insight into design polymeric aerogels in low-cost and large-scale with substantial industrial water purification applications. [ABSTRACT FROM AUTHOR]

Here, we developed a lotus-leaf-resembling superhydrophobic coating with sturdy abrasion and weather resistance. By taking the sturdiness of the superhydrophobicity into account, this coating was created by incorporating a zinc-mediated superhydrophobic surface that was rough and ultraviolet-resistant into a polyurethane layer capable of strong wear resistance. By spraying the zinc-mediated perfluorosilane and a polyurethane suspension onto an aluminum flake, the lotus-leaf-resembling superhydrophobic coating was thus prepared. The resulting coating displayed the natural superhydrophobic phenomena with a contact angle of up to 157.1° and a rolling angle of 4.2°, greater or smaller by depending on the dosage of zinc. The adoption of zinc to the prepared coating not only mediated the rough surface texture but also extra granted the ultraviolet resistance. In couple with the strong wear resistance of the substrate layer, the proposed superhydrophobic coating provided the expected sturdy abrasion and weather resistance. The development of the superhydrophobic coating shares a prospect with practical applications, especially outdoor applications. [ABSTRACT FROM AUTHOR]

[Display omitted] More attention has been paid on the preparation of hybrid nanomaterials consisting of a polymeric phase and an organic/biological/inorganic component. This hybrid nanomaterials combine the attractive properties of their constituents, which are expected to produce materials with synergistic properties. Recently, a new self-assembly method, polymerization-induced self-assembly (PISA), has shown great promise in the production of nanoparticles using a straightforward one-pot approach. To date, various hybrid nanomaterials loading organic, biological or inorganic components have been designed and constructed via PISA. The aim of this review is to summarize the current approaches to prepare hybrid nanomaterials via PISA as well as their potential applications. [ABSTRACT FROM AUTHOR]

The hydrothermal method was used to synthesize carbon sphere, and the hard template synthesis method was used to prepared C-doped hollow TiO2 sphere (CHTS). Bismuth nitrate was used as bismuth source to modify CHTS. The composite material was oxidized in air atmosphere at 450℃ to obtain Bi2O3 modified C-doped TiO2 hollow spheres(BCHTS). The morphology, elemental composition and photocatalytic degradation efficiency of tetracyclines (TC) by BCHTS hollow spheres were characterized by various measurements. Additionally, the possible transformation pathways and degradation mechanism of tetracycline were revealed via LC–MS and trapping experiments. The experimental results show that the Bi nanoparticles are uniformly dispersed in the CHTS. The photocatalyst exhibits enhanced degradation rate of TC (98.4% under visible-light within 180 min and 99.4% under natural light within 50 min) for its structure and narrow bandgap (2.87 eV). After five degradation cycles, the photocatalyst still remains high removal rate of 96.4% for TC. The results indicate that the photocatalyst may be promising for degrading antibiotic residuals remains. According to the trapping experiment, OH and h+ have a certain role on the photodegradation process, while·O2− is the main active species for degrading TC. [ABSTRACT FROM AUTHOR]

This study is aimed at booming intelligent polymers and their applications in catalysis, presenting an intelligent polymer catalyst with photo-mediated catalytic ability. This catalyst was fabricated with polymeric 2-acrylamide-2-methylpropylsulfonic acid (acidic moieties capable of catalytic hydrolysis) and photo-sensitive acrylamide-azobenzene prepared from the synthesis of 4-aminoazobenzene with acryloyl chloride. Under the radiation of ultraviolet light, this catalyst would undergo a change of cis/trans-conformation of azobenzene, causing alterable accessibility to the internal catalytic sites and as a result mediated catalytic ability. This catalyst presented significant catalytic ability at ambient conditions due to the trans-conformation of azobenzene which endorsed accessibility to the internal catalytic sites. Conversely, this catalyst showed limited catalytic ability under ultraviolet light, in response to the isomerization of the cis-conformation of azobenzene which inhibited the accessibility. In this way, this catalyst showed the photo-mediated catalytic ability. The suggestion of this polymer catalyst provides a prospect to optically modulate the catalytic proceedings, particularly for complicated processes. [ABSTRACT FROM AUTHOR]

This study aimed at the present dilemma in selective catalysis, about how to furnish metal-nanoparticle catalysts with predictable selectivity. This issue was addressed by developing a 'key-vs.-lock'-like polymer reactor made of an elaborate molecularly imprinted polymer containing metal nanoparticles, which was capable of predictably and selectively catalyzing its specified substrate. Unlike reported polymer reactors and enzyme-like imprinted polymer catalysts, which lack either predictable selectivity or reactive metal nanoparticles, this polymer reactor has incorporated both of the molecular recognition ability of the polymer carrier and the catalytic sites of metal nanoparticles into one entire entity and thereby dictated selective catalysis. This study highlighted how this polymer reactor works in a selective way in contrast to reported catalytic polymers or polymer reactors, which thus opens opportunities of tailoring selective catalysts for controlled chemical processes. [ABSTRACT FROM AUTHOR]

The present endeavor is to develop a highly-intelligent catalyst prototype which is able to autonomously adapt to the environment and provide an in-situ triple-shift catalytic function. By searching strategies from the nature, this objective is gained by developing a self-adaptive polymer reactor which held Venus flytrap-inspired catalytic bi-layers capable of reverse thermo-responsive properties. The first layer was fabricated with a negatively-thermo-responsive imprinted polymer and embedded metal nanoparticles which were responsible for catalytic reduction. In contrast, the second layer was made of a positively-thermo-responsive polymer containing acidic groups, which were capable of catalytic hydrolysis. This reactor presented individually one single catalytic process at relatively low temperatures and high temperatures because one of the simple layers validated. This reactor presented nevertheless the tandem catalytic ability due to the simultaneous work of the two layers at modest temperatures. With increasing temperatures, the catalytic bi-layers of this reactor would function in a sequential way (i.e., one simple layer, both layers and then another simple layer) and as a result led to the single-tandem-single triple-shift catalytic ability. The protocol of this reactor shares a prospect with developing manipulatable catalytic paradigms. [ABSTRACT FROM AUTHOR]

To address the rising challenges in self-controlled tandem processes, a catalytic reactor with two reversely-responsive layers was fabricated, for which the two layers acted as the carriers of two different-type active sites so as to achieve the adjustable catalytic ability. This first layer was a shape-memory copolymer consisting of 2-acrylamido-2-methylpropane sulfonic acid and 1-heptene. Given the "frozen" domains in the copolymer at low temperatures, the channel of the substrate became closed. At middle temperatures, the channel of the substrate became open as a result of the activation of the copolymer. The second layer was a copolymer embedding Ag nanoparticles made of polymeric 2-(trifluoromethyl) acrylic acid and 2-vinylpyridine. This layer showed the "closed" channel at low temperatures due to the electrostatic interactions between the two polymeric components, which inhibited the entry of reactants. At higher temperatures, as the polymeric interactions at this layer were broken, the channel in this layer became open for the reactants. In combination with the contained acidic sites and catalytic Ag nanoparticles sites in the two layers, which were individually responsible for catalytic hydrolysis and reduction, the reactor did not show substantive catalytic ability at low temperatures due to the closed channels in both the two layers. At middle temperatures, the reactor ran with simple hydrolysis due to the open channel in the first layer which contained acidic sites. At higher temperatures, the reactor ran with tandem catalytic processes because of the open channels in the two layers. Hence, the design of the dual-responsive catalytic reactor acquired the non-tandem/tandem self-controlled catalytic ability. [ABSTRACT FROM AUTHOR]

In this paper, we report a novel three-layer polymer reactor capable of simple/tandem self-controlled catalysis. The top and bottom layers were composed of two different molecularly imprinted polymers respectively containing two catalytic sites (an acidic site catalyzing hydrolysis and metal nanoparticles catalyzing reduction), performing two selective tandem reactions without interference between each other. The middle layer was composed of a copolymer of poly- N -isopropylacrylamide (PNIPAM) and polyacrylamide (PAm) in different ratios, acting as a temperature-responsive switch for the tandem catalysis process. In an aqueous environment, when the temperature is lower than the Lower Critical Solution Temperature (LCST) of the copolymer, the reactor exhibited an open middle access (hydrophilic condition) of intermediate, allowing the tandem processes from hydrolysis to reduction. When the temperature is higher than the LCST, the channels of the middle layer were closed (hydrophobic condition), which obstructed the access of reactants. As a result, the reactor could only conduct simple hydrolysis processes. Therefore, with the three-layer structure, the polymer reactor has led to a self-controlled catalysis. This new multi-layer polymeric reaction concept can expand the practical use of functional catalysts by permitting the control of processes in large temperature ranges. The switchable mechanism of the three-layer polymer reactor. [Display omitted] • A three-layer polymer reactor with non-tandem/tandem self-controlled catalytic abilities was prepared. • The middle layer made of PNIPAM-PAM acts as a molecular switch to control the tandem catalysis. • Tandem catalysis without interference was obtained by using molecularly imprinted polymers as carriers. • A temperature controlled and stable smart tandem catalysis was achieved. [ABSTRACT FROM AUTHOR]

In this study, the photoresponsive monomer of 2-nitrobenzyl methacrylate (NBMA) was introduced into the dispersion polymerization of benzyl methacrylate (BzMA) monomer mediated by poly[N,N-(dimethylamino) ethyl methacrylate] (PDMAEMA) macro-RAFT agent, and the PDMAEMA-b-P(BzMA-co-NBMA) block copolymer nanoparticles were prepared. The effects of the introduction of NBMA on the polymerization kinetics and the morphology of formed copolymer nanoassemblies were studied in detail. Then, the light response of PDMAEMA-b-P(BzMA-co-NBMA) block copolymer nanoparticles was verified. Moreover, the copolymer nanoparticles after irradiation could be used as the templates for loading silver nanoparticles, and it is proved that the template has advantage of regulating the amount of loaded silver by changing the UV light irradiation time.Graphical Abstract: In this study, the photoresponsive monomer of 2-nitrobenzyl methacrylate (NBMA) was introduced into the dispersion polymerization of benzyl methacrylate (BzMA) monomer mediated by poly[N,N-(dimethylamino) ethyl methacrylate] (PDMAEMA) macro-RAFT agent, and the PDMAEMA-b-P(BzMA-co-NBMA) block copolymer nanoparticles were prepared. The effects of the introduction of NBMA on the polymerization kinetics and the morphology of formed copolymer nanoassemblies were studied in detail. Then, the light response of PDMAEMA-b-P(BzMA-co-NBMA) block copolymer nanoparticles was verified. Moreover, the copolymer nanoparticles after irradiation could be used as the templates for loading silver nanoparticles, and it is proved that the template has advantage of regulating the amount of loaded silver by changing the UV light irradiation time. [ABSTRACT FROM AUTHOR]

This study is aimed to develop a selectivity-steerable catalyst prototype, expounding how to acquire selectivity-online/offline catalytic ability. By searching strategies from nature's toolbox, this goal is met by reporting a "living" imprinted reactor which held sea cucumber-inspired domains capable of alterable recognition properties. By depending on the temperature, this reactor was able to dynamically bring up the selectivity-online/offline catalytic ability because of the unique bio-inspired domains. This reactor presented selective catalytic behaviors at low temperatures by virtue of the "frozen" domains which admitted recognition behaviors towards the imprinted species (i.e., the selectivity's "online" state). This reactor presented, however, non-selective catalytic ability at relatively higher temperatures, resulting from the "thawed" domains which demolished the recognition properties (i.e., the selectivity's "offline" status). In this manner, this reactor showed the selectivity-online/offline catalytic function. The protocol of the reactor suggests a prospect for the development of manipulatable catalytic paradigms. [ABSTRACT FROM AUTHOR]

Abstract: Highly sensitive and label-free detection of the biomarker carbohydrate antigen 15-3 (CA 15-3) remains a challenge in the diagnosis of breast cancer. Here, a novel electrochemical immunosensor capable of sensitive and label-free detection of CA 15-3 is reported. This unique immunosensor, equipped with a highly conductive graphene (i.e., N-doped graphene sheets)-modified electrode, exhibited significantly increased electron transfer and high sensitivity toward CA 15-3. This novel immunosensor, with a low detection limit of 0.012U/mL, worked well over a broad linear range of 0.1–20U/mL. Unlike conventional immunosensors, which usually involve complicated label processing and time-consuming separations, the use of highly conductive graphene avoids the need for labels and is simple in nature. The strategy developed for this immunosensor provides a promising approach for clinical research and diagnostic applications. [Copyright &y& Elsevier]

The article presents thermodynamic and kinetic surveys on the specific recognition and catalysis by molecularly imprinted polymer catalysts. Using p-nitrophenyl phosphate as templates and 1-allylimidazole as functional monomers, the imprinted material was prepared. The prepared polymer catalyst shows a highly specific recognition and catalysis toward the imprint species. Kinetic analysis indicates that this specific behavior, in nature, can be a result of a preferential promotion. The specific imprint leads to a larger hydrolysis rate in the imprint species than in its analogue. Thermodynamic study also implies that the molecular induction generating from the imprint to NPA is larger than to its analogue, which thus makes the polymer capable of specifically alluring the imprint species to bind. [ABSTRACT FROM AUTHOR]

Abstract: Micron-grade monodisperse PMMA microspheres, whose surfaces were modified with functional groups by co-polymerisation using functional monomer, were prepared via dispersion polymerisation. Characterized by their large specific surface area, high adsorption ability, favourable biocompatibility, these monodisperse micron-sized PMMA microspheres were employed as the supporting material in the enzyme immobilization in present work. The influential factors on the activity of immobilized enzyme including pH, temperature, time etc were preliminarily investigated. The results concluded from the experiments indicated that the immobilization procedure could promote the resistance of enzyme against temperature, pH shift and some other tough reaction conditions meanwhile prolong the enzymatic lifetime for storage. [Copyright &y& Elsevier]

Here, we aimed to develop manipulatable catalytic paradigms, expounding how to endue the catalysts with on/off-selective catalytic ability. Inspired from the nature, this target was hit by reporting a polymer catalyst prepared by imprinting substrate molecules in a metal-nanoparticle- encapsulated smart polymer that held mobile molecular chains in the polymeric networks. These mobile functional chains, by being "frozen" or "thawed", allowed the smart polymer carrier to function with either recognition or misrecognition properties for the imprinted substrate, resulting in on/off-selective catalytic ability. This catalyst exhibited selective catalytic behaviors towards the imprinted substrate at relatively low temperatures, due to the "frozen" functional chains which admitted recognition properties. In contrast, this catalyst did not provide selective catalytic behaviors at relatively high temperatures, arising from the growing mobility of these functional chains which dismantled the recognition system. In this way, this catalyst showed the on/off- selective catalytic ability. The formulation of this catalyst shares an attractive prospect with the development of programmable catalytic processes. [ABSTRACT FROM AUTHOR]

Summary: Solid polymer electrolytes have the merits of high safety and energy density and lightweight. Therefore, they gradually become the key for commercial applications of solid batteries. In this study, a new type of solid composite electrolyte (SCE) is prepared by adding Li0.33La0.557TiO3 (LLTO) nanorods into poly(vinylidene fluoride‐co‐hexafluoropropylene (PVDF‐HFP) matrix. This SCE displays excellent thermal stability and mechanical properties. Moreover, it has been proven to sufficiently suppress the growth of lithium dendrites. When the content of the LLTO nanorods reaches 10 wt%, the SCE delivers a high ionic conductivity of 1.21 × 10−4 S cm−1 at 25°C and the electrochemical stability window of 4.7 V (vs Li+/Li). The NCM622/SCE/Li solid‐state lithium‐ion battery delivers a discharge specific capacity of 129.1 mAh g−1 at 0.5 C after 100 cycles, and the coulombic efficiency reaches 99%. These results demonstrate that the SCE is expected to become one of the most hopeful candidates for the coming generation of solid‐state lithium‐ion batteries. [ABSTRACT FROM AUTHOR]

Polyurethane (PU) belongs to a class of special polymeric materials with hydrogen bonds, which has the potential for self-healing ability. In the present work, by introducing polypropylene glycol (PPG) blocks with high segment mobility and different block lengths on the ends of PU chains, the PUs with adjustable self-healing ability were successfully obtained. The self-healing ability of the PUs firstly increases with the increase of the PPG block lengths, but then decreases. This phenomenon can be attributed to the combined effects of the density of hydrogen bonds and the mobility of PPG segments. At first, the increase of the PPG block length leads to the improvement of mobility of PU chains, which is beneficial for the enhancement of the self-healing. However, the further increase of the PPG block length results in the reduction in the hydrogen bond density, finally leading to the decrease of the self-healing ability of the PUs. [ABSTRACT FROM AUTHOR]

Natural antifreeze proteins are known for their excellent control of ice formation and growth, while synthetic molecules seldom have the similar effects. Here we report a series of protein mimetic peptoids with different side chains exhibiting significant ice recrystallization inhibition activity, and their structure–property relationships are also studied. The presence of peptoid can clearly slow down ice growth and decrease ice crystal grain size, but shows no thermal hysteresis, which make peptoids great antifreeze agent candidates in cryopreservation. Peptoids with methyl, ethyl and amino groups on side chains can modulate ice crystal shape, while peptoids bearing hydroxyl and ethyl groups decrease ice growth rate the most. All peptoids can reduce ice crystal grain size and the one with hydroxyl groups give the smallest grain size. This study reveals peptoid structure effects on ice growth and points to the design rules for biomimetic antifreeze agents. [ABSTRACT FROM AUTHOR]

The Stöber method was used to synthesize silicon sphere carriers with uniform size. The surface of the silicon sphere carrier was treated with 3-aminopropyltrimethoxysilane and 2-bromopropionyl bromide as atom transfer radical polymerization (ATRP) initiator and grafted with polyhydroxyethyl methacrylate (PHEMA) by ATRP. Bismuth nitrate was used as bismuth source to form polymer-metal complex with PHEMA. Sodium borohydride was used to reduce the bismuth ions in the composite material to metallic bismuth, and the metal bismuth on the surface of the composite material was oxidized in air atmosphere at 450 °C to obtain the inorganic–organic bismuth oxide composite. The morphology, elemental composition and photocatalytic degradation efficiency of Rhodamine B by bismuth oxide composite were characterized by various measurements. The TG and TEM results show that the composite material has good thermal stability, and Bi2O3 has very good dispersibility and stability in the prepared Bi2O3 composite. When the pH value is 4 with a catalyst dosage of 1.2 g/L, the degradation efficiency of Rhodamine B can reach 99.3% after 4 h of light irradiation, which is 24.2% higher than that of pure bismuth oxide. After 5 cycles, Bi2O3 composites still have a strong degradation effect with a degradation rate of 90.1% for Rhodamine B dye solution, which illuminates that the prepared Bi2O3 composite has good cyclic degradation performance. [ABSTRACT FROM AUTHOR]

A smart catalytic reactor capable of simple/tandem-commutative catalytic ability was reported here. By borrowing the natural soft morphology and segregated zones in biosystems, this reactor was constructed with polymeric bilayer composites where each constituted a catalytic zone. The combination of the two catalytic zones with a catalytically-coupled process would dictate the reactor sequential catalytic behaviors and accordingly simple/tandem-commutative catalytic ability. To that end, one of the layers in this reactor was fabricated with acidic architectures capable of catalytic hydrolysis whereas the other layer was made of a thermo-sensitive antibody-like imprinted hydrogel which acted as a switch to provide access for the succeeding reaction. In this way, this reactor demonstrated the simple/tandem-commutative catalytic ability. This suggested design shares a promising prospect with developing functional catalysts and programmable catalytic processes. [ABSTRACT FROM AUTHOR]

Summary: A promising solid polymer blend electrolyte is prepared by blending of poly(ethylene oxide) (PEO) with different content of amorphous poly(propylene carbonate) (PPC), in which the amorphous property of PPC is utilized to enhance the amorphous/free phase of solid polymer electrolyte, so as to achieve the purpose of modifying PEO‐based solid polymer electrolyte. It indicates that the blending of PEO with PPC can effectively reduce the crystallization and increase the ion conductivity and electrochemical stability window of solid polymer electrolyte. When the content of PPC reaches 50%, the ionic conductivity reaches the maximum, which is 2.04 × 10−5 S cm−1 and 2.82 × 10−4 S cm−1 at 25°C and 60°C, respectively. The electrochemical stability window increases from 4.25 to 4.9 V and the interfacial stability of lithium metal anode is also greatly improved. The solid‐state LiFePO4//Li battery with the PEO/50%PPC blend solid polymer electrolyte has good cycling stability, which the maximum discharge specific capacity is up to 125 mAh g−1 at a charge/discharge current density of 0.5 C at 60°C. [ABSTRACT FROM AUTHOR]

Si nanostructures have drawn considerable attention in the field of Micro-supercapacitors. In this work, a hybrid electrode based on poly(3,4-ethylenedioxythiophene) (PEDOT) coated silicon nanowire arrays (SiNWs) is prepared via a two-step process. The SiNWs are synthesized by metal-assisted electroless etching method and treated by the tetramethylammonium hydroxide (TMAH) solution. Then, the porous PEDOT film is electrodeposited from the ionic liquid electrolyte. The influence of SiNWs and the oligomers in the electrolyte on the morphology of the hybrid electrode and/or on the contact/adhesin between PEDOT and SiNWs are systematically investigated for the first time. Additionally, the storage mechanism of the hybrid electrode is also investigated. After optimization, the hybrid electrode delivers a specific capacitance as high as 115 mF/cm2 at the current density of 0.5 mA/cm2, comparing to the top values of previously reported Si nanostructure electrodes. These preliminary results demonstrate that each component provides unique and crucial function to achieve optimized electrochemical properties, benefiting to fabricate high capacitive performance of Si nanostructure Micro-supercapacitors with simple and low-cost approaches. [ABSTRACT FROM AUTHOR]

Summary: To seek a solid polymer electrolyte (SPE) with excellent performance, a novel poly(ethylene oxide) (PEO) based SPE is prepared by blending an appropriate amount of microcrystalline poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) with PEO using a universal solution casting method. Field emission scanning electron microscopy (FESEM), X‐ray diffraction (XRD) and differential scanning calorimetry (DSC) are utilized to analyse the samples. The crystallinity of the blend solid polymer electrolyte is significantly lower than that of the neat PEO‐based SPE. The addition of the PVDF‐HFP disrupts the segment structure of the PEO crystal region and increases the proportion of the amorphous region, thus boosting the migration of lithium ions. The results show that the electrochemical stability window of the blend solid polymer electrolyte reaches as high as 4.8 V. The initial discharge specific capacity of the solid‐state LiFePO4/SPE/Li battery is 131 mAh g−1 at 0.5 C and 60°C, and the discharge specific capacity is still 110.5 mAh g−1 after 100 cycles. On the basis of the results, the novel SPE has a widespread application prospects in solid‐state lithium‐ion batteries. [ABSTRACT FROM AUTHOR]

This study is aimed at the present challenge in self-controlled catalysts, addressing how to furnish the catalysts with cascade/non-cascade-switchable catalytic ability. By borrowing the "soft" properties and autonomous ability from nature, this objective was met by reporting an artificial polymer reactor that was composite of tri-layer architectures made of two inversely-thermosensitive outward layers and a non-responsive middle layer. With the middle layer containing catalytic metal nanoparticles, the two thermosensitive outward layers consisted separately of a negatively-temperature responsive polymer and a positively-temperature responsive composite. The opposite responsiveness at the two thermosensitive outward layers induced convex/flat/concave-switchable shapes in this reactor, leading to cascade/non-cascade-alterable substrate channeling to the reactive middle layer. In this way, this polymer reactor led to the occurrence of cascade/non-cascade-switchable catalytic ability. This design shares a promising prospect with the struggling field of self-controlled catalysts, which allows opportunities to finely control catalytic processes. [ABSTRACT FROM AUTHOR]

Inspired by the polymeric "soft" properties and divisional isolation of tandem processes in natural systems, an artificial reactor with self‐screened catalytic ability was fabricated with a polymeric tri‐layer architecture. The non‐responsive middle layer encapsulated catalytic metal nanoparticles, while the two outer layers consisted of a negatively and a positively thermosensitive imprinted polymer. The inverse responsiveness of the outer layers induced switchable shapes, which led to alterable tandem channeling to the reactive middle layer and, as a result, the divisional admission of different substrates. This way, the reactor led to the formation of self‐screened catalytic ability. The design for this artificial reactor offers promising prospects for struggling tandem catalysts, suggesting opportunities to develop schedulable tandem processes. [ABSTRACT FROM AUTHOR]