Search

In this work, we successfully synthesize the core-shell structure carbon@titanium dioxide (C@TiO2) composite microspheres with wrinkled surface through a three-step method and build up the relationship between the TiO2 layer thickness and the microwave absorption property. The absorbing mechanism of the novel microsphere is revealed. Interface polymerization is applied for preparation of wrinkled poly glycidyl methacrylate/divinylbenzene polymer microspheres (PGMA/PDVB); Then, TiO2 layer is controllably coated on the surface of PGMA/PDVB microspheres by hydrolysis of tetrabutyl titanate (TBT); C@TiO2 composite microspheres are obtained by vacuum carbonization with PGMA/PDVB@TiO2 microspheres as the precursor. TiO2 layer thickness on the surface of C@TiO2 composite microspheres can be effectively adjusted by controlling the amount of TBT. When the amount of TBT is 0.75 mL, C@TiO2 composite microspheres exhibit the outstanding electromagnetic loss performance. The maximum reflection loss value (RLmax) reaches -49.21 dB at the thickness of 2 mm, corresponding effective absorption bandwidth is 5.27 GHz. The maximum effective absorption bandwidth is 5.5 GHz at 2.2 mm. The results show that the introduction of TiO2 can regulate electromagnetic parameters and enhance interface polarization ability. Meanwhile, the surface wrinkle structure offers more opportunities for multiple reflections of electromagnetic and introduces a large number of defective skeleton structure. The synergy of multiple advantages makes the absorbing performance of C@TiO2 composite microspheres significantly improved. This work plays a guiding role for the composition and the structure optimization of existing microwave absorbers.

Colloidal molecules (CMs), nonspherical clusters of a small number of particles, can be used as building blocks for self-assembly applications. Here, we propose a novel one pot method for CMs synthesis. First, poly(N-isopropylacrylamide-co-acrylic acid) (P(NIPAM-co-AA)) microgels were prepared by soap-free emulsion polymerization as seed particles, then monomer styrene and cross-linking agent divinylbenzene (DVB) were added, which could be polymerized by the remaining free radicals on the seed surface in situ. P(NIPAM-co-AA)-PS colloidal molecules with a series of morphologies such as popcorn-like, CO2-like, NH3-like, CH4-like and so on could be obtained. The effects of satellite colloid viscosity, interfacial tension, and polymer chain mobility on the number of satellite colloid have been investigated, and the formation mechanism of CMs is proposed based on morphology evolution investigation. Compared with the existing CM synthesis techniques, our method enables fabricating CMs from vinyl monomer in a facile and efficient way, and the scientific finding regarding the CMs formation will guide the CMs fabrication toward salable and reliable direction.

Levitation of pollen particles has been demonstrated in a radio frequency (RF) plasma. Pollen particles from Japanese cypress are levitated to various heights from lower electrode, where they spontaneously form quasi ordered state. Levitating pollen particles are identified from divinylbenzene particles in real-time using the polarization imaging technique.

In this work, SiBNC ceramic aerogels were prepared by the hydrosilylation reaction between precursor polyborosilazane and a cross-linking agent divinylbenzene in a highly diluted solvent, with the presence of Karstedt catalyst. The obtained SiBNC ceramic aerogels possess the characteristics of light weight, high porosity, and relatively wide pore size distribution (3–140 nm). The electromagnetic wave (EMW) absorption of the SiBNC aerogels was studied by a vector network analyzer. When the solvent fraction was 90%, the sample thickness was 3.0 mm, and the SiBNC aerogel had good absorption properties with a reflection loss of 25.05dB@16.07 GHz. These SiBNC ceramic aerogels also showed excellent temperature resistance and a unique three-dimensional network structure. They are thus expected to find application in the high-temperature absorption field.

Synthesis of sulfonated porous polymers with improved hydrophobicity and stability is of extreme importance in both academic research and industrial applications. However, there is often a trade-off between acidity and surface hydrophobicity of sulfonated polymers. In this study, we report a strategy for the synthesis of sulfonated porous organic polymers (S-PT) with improved hydrophobicity via free radical polymerization method by using a rigid and large multidentate monomer, 1,3,5-tri(4-vinylphenyl)-benzene, having a hydrophobic core. The results of vapor adsorption measurement show that S-PT has more hydrophobic properties than sulfonated poly(divinylbenzene) (S-PD), attributed to the hydrophobic core of its multidentate monomer. Furthermore, the optimization of sulfonation time established a balance between surface acidity and hydrophobicity. Under optimized conditions, S-PT afforded up to 113 mmol g-1 h-1 TOF in the esterification of oleic acid with methanol, more active than commercial Amberlyst-15 with TOF of 15 mmol g-1 h-1 and Nafion NR50 with TOF of 7 mmol g-1 h-1 . We believe that the findings of this study will provide useful insights to advance the design and synthesis of solid acid catalysts for organic transformations.

In this work, the formation of transient microporosity during the polymer-to-ceramic conversion in polymer-derived ceramics was studied using a commercially available poly(vinyl)silazane precursor which was modified with divinylbenzene (DVB) as linker molecule during crosslinking. After pyrolysis treatments between 400 and 700 °C, the resulting materials not only showed distinct changes in elemental composition and structural features upon introduction of the linker molecule, but also a shift in micropore size, e.g. shifting from 0.84 nm to 0.70 nm after pyrolysis at 600 °C. Due to hindrance of transamination reactions in the low-temperature region, the nitrogen content in linker-containing samples was significantly higher, leading to a different composition of micropore-forming entities and, in case of the system studied, to smaller pores. These findings are a first step towards the clarification of the mechanisms leading to the pore formation in PDCs during pyrolytic conversion, which is essential for their use in prospective applications.

Mimicry of nature drives the development of bionic materials. Bionic superhydrophobic materials are a kind of high-efficiency materials to handle oil spills and water pollution. However, the stability of surface coatings of the superhydrophobic materials remains a challenge. Herein, a new category of self-assembly bionic superhydrophobic surface coating was prepared via one-step condensation/copolymerization of vinyltriethoxysilane (VTES) and divinylbenzene (DVB), which realized the close combination of covalent bonds between organic (e.g. DVB) and inorganic matter (e.g. VTES), and avoided the swelling of polydivinylbenzene (PDVB) in the process of collection of oil from water. This organic-inorganic hybrid polymer could self-assembly deposit on the surface of sponge even other substrates. For example, P(VTES-DVB)-SiO2/MS obtained by assembling P(VTES-DVB)-SiO2 on the surface of Melamine Sponge (MS) exhibited superhydrophobicity with a Water Contact Angle (WCA) of 157.3°, the optimal adsorption capacity of 77 g·g−1 − 136 g·g−1 for diverse oils, and an excellent separation efficiency of 99.3%. Besides, the excellent acid and alkali resistance of P(VTES-DVB)-SiO2/MS suggested the potential value in practical oil-water separation. P(VTES-DVB)-SiO2 showed the outstanding hydrophobic performance by using as coating on different substrates. This work provided a new idea about the stable combination of organic and inorganic matter in the surface modification.

Nanostructured tricontinuous block polymers allow for the preparation of single-component materials that combine multiple properties. We demonstrate the synthesis of a mesoporous material from the selective orthogonal etching of a microphase-separated tricontinuous block polymer precursor. Using the synthetic approach of polymerization-induced microphase separation (PIMS), divinylbenzene (DVB) is polymerized from a mixture of poly(isoprene) (PI) and poly(lactide) (PLA) macro-chain transfer agents. In the PIMS process in situ cross-linking by the DVB arrests structural coarsening, resulting in a disordered block polymer morphology that we posit exhibits three nonintersecting continuous domains. Selective etching of the PI domains by olefin cross metathesis and PLA domains by hydrolytic degradation produces a mesoporous polymer with two independent pore networks arising from the different etch mechanisms.

A novel type of hyper-cross-linked organic microporous polymer (HOMP) has been successfully prepared based on the radical copolymerization of bismaleimides and divinylbenzene. In comparison with the HOMPs prepared with cross-linking techniques, the new radical strategy circumvents some intractable problems, such as low atom economy, structure irregularity and corrosive byproducts. The obtained HOMPs have defined molecular structures due to the intrinsic alternating copolymerization properties of the two monomers. A maximum BET surface area of 841 m2 g–1 and high gas capture capacity (CO2, 11.22 wt %, 273 K/1.0 bar; H2, 0.82 wt %, 77.3 K/1.0 bar; benzene, 545 mg g–1, room temperature/0.6 bar; and cyclohexane, 1736 mg g–1, room temperature/0.6 bar) were achieved. In addition, the polymers also displayed good chemical and thermal stability, which is critical for the practical application.

Gel type polymers, polymers of expanded structure and macroporous polymers of styrene mostly with 6 mole% of divinylbenzene have been obtained by suspension polymerization, expanded and macroporous structures being prepared in the presence of 1.5 volumes of toluene or iso-octane, respectively. All three types of copolymers were further converted into highly porous hypercrosslinked products by their intensive post-crosslinking with monochlorodimethyl ether. For all samples obtained, the inner specific surface area, total pore volume, apparent density, and uptake of toluene, methanol and water have been measured. It was found that the swelling of macroporous and hypercrosslinked porous polymers results in an increase in the volume of the polymeric phase and decrease in the volume of large pores with insignificant rise in the total size of the polymeric beads. Swelling of porous polymers thus mainly proceeds at the expense of space of internal voids.

Novel ciprofloxacin composite imprinted materials are synthesized by using co-precipitation polymerization of dual functional monomers (methacrylic acid and 2-vinylpyridine) and polystyrene-co-divinylbenzene. The intermolecular interactions between monomers and template are evaluated by molecular modeling analysis. The physicochemical properties of the obtained polymers are characterized using FT-IR, TGA, and SEM. Batch adsorption experiments are used to investigate adsorption properties (kinetic, pH, and isotherm). These polymers are employed to prepare the solid phase extraction cartridges, and their extraction performances are analyzed by the HPLC-UV method. DFT calculations indicate that hydrogen bonding and π−π stacking are the driving forces for the formation of selective rebinding sites. The obtained polymers exhibit excellent adsorption properties, including fast kinetics and high adsorption capacity (up to 10.28 mg g−1) with an imprinted factor of 2.55. The Scatchard analysis indicates the presence of specific high-affinity adsorption sites on the imprinted polymer. These absorbents are employed to extract CIP in river water with recoveries in the range of 65.97–119.26% and the relative standard deviation of 3.59–14.01%. Furthermore, the used cartridges could be reused at least eight times without decreasing their initial adsorption capacity.

A novel porous solid amine adsorbent (PEI@polyHIPE) with a highly interconnected pore network was prepared by high inner phase emulsion (HIPE) polymerization of styrene and divinylbenzene, and was simultaneously functionalized with high molecular weight (Mw = 70 000 Da) polyethylenimine (PEI). This proposed route requires fewer chemical reagents and less energy than conventional solid amine adsorbents that were prepared by amine post-modification such as chemical grafting and wet impregnation. The SEM image shows that a PEI layer was formed on the adsorbent's surface without damaging its original structure. And the CO2 adsorption capacity and pore structure of PEI@polyHIPE could be adjusted by adding different amounts of PEI. The one-step fabricated 4.0PEI70k@polyHIPE adsorbent showed a maximum adsorption capacity of 4.18 mmol CO2 per g-adsorbent at 20 °C under humid conditions. It obviously exhibited better CO2 adsorption performance, high amino utilization efficiency, and quick adsorption kinetics compared to PEI post-modification porous polystyrene (polyHIPE-PEI). This was attributed to its well-interconnected hierarchical structure, which could remarkably reduce gas diffusion resistance. Meanwhile, owing to the high-molecular-weight of PEI, the amount of amine loss could decrease during the process of adsorption/desorption, thus the adsorbent of PEI@polyHIPE showed promising regeneration performance. This one-step synthetic route provides a novel strategy for preparing amine functionalized adsorbents with high sorption capacity, amine efficiency, and regeneration stability.

Ion-imprinted divinylbenzene and methacrylic acid copolymers for rare-earth element adsorption with crosslink ratios 60 and 40% have been synthesized. Ion imprinting has been carried out via the trapping approach. Alizarin red S has been incorporated in the polymers as a nonvinylated ligand. The obtained materials were characterized via scanning electron microscopy and Fourier transform infrared spectroscopy. Synthesized polymers exist as gel-type nonporous spherical agglomerates from 2 to 6 μm with low surface areas. The sorption properties of the synthesized polymers with respect to lanthanides in static and dynamic modes have been studied. The most efficiently synthesized materials extract rare earth elements from solutions at pH 4-7. The maximum sorption capacity of the obtained polymers with regard to Gd is around 0.5 mmol/g. According to the obtained results, the imprinted polymer with a crosslink ratio 60% is characterized by the highest values of distribution coefficients for lanthanides. The total lanthanide breakthrough capacity for this polymer is 0.861 μmol/g. The adsorption column has been constructed using the imprinted polymer with a crosslink ratio 60%. The column extraction and preconcentration procedure for the trace Eu content determination in the strontium iodide recycled material by inductively coupled plasma-atomic emission spectrometry at a level of 1 × 10-6%(mass) has been proposed.

A series of imidazolinium-based porous poly(ionic liquid)s (PILs) with different anions prepared by free-radical copolymerization of an arene-bridged tris-vinylimidazolium salt and divinylbenzene (DVB) were constructed. The as-prepared PILs were characterized by BET, SEM, TEM, TGA and Elemental Analysis (EA), and the results showed that they had plentiful ionic sites, and abundant and stable mesopores. In particular, the density of ionic sites and pore structure of PILs could be controlled by adjusting the content of DVB. Moreover, the PILs were used as efficient heterogeneous catalysts for the decarboxylation of cyclic carbonates to epoxides for the first time. Results showed that the catalytic activity of PILs was positively correlated with the nucleophilicity of the anions in PILs, and PDVB-[PhTVIM]Cl-1 with a chloride anion-enriched skeleton displayed the best catalytic performance. Without any solvent or cocatalyst, PDVB-[PhTVIM]Cl-1 achieved a TOF value of 108.1 h−1 and the yield of butylene oxide of 89.6%, which was even better than the homogeneous IL-based catalysts (TOF value: 8.7 h−1) that had been previously reported. Meanwhile, PDVB-[PhTVIM]Cl-1 also exhibited excellent recyclability and substrate compatibility.

We report a sulfonated hydrophobic mesoporous organic polymer (MOP-SO3H) as a highly efficient heterogeneous catalyst for one-pot 5-ethoxymethylfurfural (EMF) production from fructose in ethanol solvent. MOP-SO3H was fabricated by co-polymerization of divinylbenzene (DVB) and sodium p-styrene sulfonate (SPSS) followed by ion exchange with dilute H2SO4, and its pore structure and acid density could be tuned easily by varying the mole ratio of SPSS to DVB. 31P MAS NMR analysis using trimethylphosphine oxide as a base probe molecule indicated that MOP-SO3H possessed a weaker Bronsted acid site than conventional cation-exchange resins. The superhydrophobic properties of MOP-SO3H were retained even after incorporating a greater number of sulfonic acid groups into the polymer framework, while conventional solid acid resins exhibited hydrophilic properties. MOP-SO3H exhibited a superior catalytic performance in comparison with conventional acid resins, a mesoporous acid catalyst, and homogeneous acid catalysts in EMF production from fructose. After optimization of various reaction conditions using MOP-SO3H, a high EMF yield of 72.2% at 99.3% fructose conversion was achieved at 100 °C in a very short reaction time of 5 h. Notably, MOP-SO3H showed a much higher EMF formation rate than the Amberlyst-15 catalyst (53.5 vs. 6.1 μmol g−1 min−1). This superior performance of the MOP-SO3H catalyst was attributed to its unique feature of large surface area containing a large quantity of readily accessible acid sites distributed throughout the hydrophobic polymer framework. In addition to its high catalytic activity, the notable stability of the MOP-SO3H catalyst was also confirmed by leaching and recyclability tests. Thus, owing to its excellent catalytic performance and easy scalability, MOP-SO3H can potentially be used as an industrial heterogeneous catalyst to produce EMF from various fructose-containing biomass.

Highly porous polymer materials with preset pore sizes and porosities can be prepared via polymerization of dispersion media of highly concentrated water-in-oil emulsions. In this work, the effect of divinylbenzene concentration in styrene–divinylbenzene mixed dispersion media of highly concentrated emulsions on the emulsion stability and the structure of resulting polymer materials has been investigated. It has been found that the emulsion stability at 25 and 65°C decreases with an increase in divinylbenzene concentration. Therewith, the pore size in the polymer material slightly grows from 4.0 to 4.5 μm. Emulsion stability expectedly rises with the concentration of a surfactant (Span 80). It has been shown that concentrations of divinylbenzene and Span 80 equal to 10 vol % are optimal for obtaining highly porous polymers from emulsions containing ammonium peroxodisulfate as a polymerization initiator. When emulsions containing benzoyl peroxide as a polymerization initiator are used to obtain highly porous polymers, NaCl (0.02–0.03 wt %) should be added to the dispersed phase of the emulsions. In this case, emulsion stability increases due to a decrease in the Ostwald ripening rate. Accordingly, highly porous polymers with smaller pores are obtained.

Dissolved organic matter (DOM) is an important component in marine and freshwater environments and plays a fundamental role in global biogeochemical cycles. In the past, optical and molecular-level analytical techniques evolved and improved our mechanistic understanding about DOM fluxes. For most molecular chemical techniques, sample desalting and enrichment is a prerequisite. Solid-phase extraction (SPE) has been widely applied for concentrating and desalting DOM. The major aim of this study was to constrain the influence of sorbent loading on the composition of DOM extracts. Here we show that increased loading resulted in reduced extraction efficiencies of dissolved organic carbon (DOC), fluorescence and absorbance, and polar organic substances. Loading-dependent optical and chemical fractionation induced by altered adsorption characteristics of the sorbent surface (PPL) and increased multilayer adsorption (DOM self-assembly) can fundamentally affect biogeochemical interpretations, such as the source of organic matter. Online fluorescence monitoring of the permeate flow allowed to empirically model the extraction process, and to assess the degree of variability introduced by changing the sorbent loading in the extraction procedure. Our study emphasizes that it is crucial for sample comparison to keep the relative DOC loading (DOCload [wt%]) on the sorbent always similar to avoid chemical fractionation.

A tricyclazole selective chitosan/Fe3O4 magnetic molecularly imprinted polymer (MMIP) was synthesized using non-covalent binding polymerization involving methacrylic acid (MAA) as functional monomer, divinylbenzene (DVB-80) as crosslinker, 2,2'-azobisisobutyronitrile as initiator, acetonitrile/toluene (75:25, v/v) as porogenic solvent and tricyclazole as template. Surface morphology and magnetic characterization of the prepared imprinted and non-imprinted polymers were done using scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectrometry and vibrating sample magnetometry, respectively. The adsorption kinetic data fitted best in pseudo-second-order model. The adsorption equilibrium was achieved in 30 min and the maximum binding capacity was 4579.9 µg/g. The Freundlich isotherm model was found suitable for explaining the binding isotherm data (R2 > 0.99). Negative values of thermodynamic parameters ∆G (Gibb’s free energy), ∆H (enthalpy), and ∆S (entropy) revealed exothermic and spontaneous nature of adsorption processes. It also revealed decreased randomness at the solid–liquid interface during sorption. The scatchard plot analysis suggested heterogeneity of binding sites on MMIPs. The molecular recognition selectivity of MMIPs towards tricyclazole was much higher, as compared to its structural analogues, tebuconazole (α = 28.58) and hexaconazole (α = 37.16). The MMIPs were successfully applied to separate and enrich tricyclazole from fortified samples of rice and water, with a recovery percentage of 89.4% and 90.9%, respectively. These reusable imprinted polymers possessing high selectivity and specificity can be utilized as an adsorbent for solid-phase extraction in sample preparation for tricyclazole residue analysis in complex environmental matrices.

In this work, graphene oxide-hybridized high internal emulsion polymers with crosslinking and open-cell structure was prepared and applied for separation and enrichment of estrogens. The prepared graphene oxide-hybridized high internal emulsion polymer monoliths had hydrophobicity, porosity and stability, which were just obtained by one step in-situ emulsion polymerization of 2-ethylhexyl acrylate, glycidyl methacrylate, and divinylbenzene after doping with graphene oxide. Benefit from the advantages of its unique character, the graphene oxide-hybridized high internal emulsion polymers monolith with low background pressure (85 kPa) and high mechanical strength could be applied for efficient separation for trace estrogens in urine. Under the optimized condition, trace estrogens, including estrone, estradiol, and diethylstilbestrol in urine, were detected by high-performance liquid chromatography, all the sample preparation process were carried out in 15 min, the recovery rate was ranged from 85.0 to 106.0% and the relative standard deviation was less than 4.

This work reports a superhydrophobic divinylbenzene polymer with hierarchical porous structure as sensing material to modify the quartz crystal microbalance (QCM) to detect benzene, toluene, ethylbenzene, and xylene (BTEX) vapor. Notably, sensing results toward toluene vapor in different relative humidities indicates that this superhydrophobic polymer has favorable toluene/water selective detection performance. Besides, the limit of detection toward toluene is lower than 1 ppm.

Hypothesis The CO2-sensitive dispersion/precipitation transition of polymer latexes fabricated based on a responsive emulsifier is a promising way to conveniently acquire bulk polymer materials. Nevertheless, the tedious synthesis procedures for switchable surfactants and the harsh operating requirements for the sensitive latexes constrain the applicability of the approach for latex preparation. Therefore, a new strategy for generating latexes with tunable CO2 responsiveness in a maneuverable way is urgently needed. Experiments In this work, a CO2-switchable electrostatic interaction is introduced to construct responsive latexes. A series of lightly crosslinked poly(diethylaminoethyl methacrylate-styrene) [P(DEA-St)] latexes with different PDEA contents were fabricated via one-pot emulsion copolymerization, with divinylbenzene and sodium dodecylsulfate (SDS) used as the crosslinker and anionic emulsifier, respectively. The influence of the DEA feeding ratio on the resulting P(DEA-St) colloids was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. Then, a cyclic CO2/N2 input was introduced to verify the response transitions of polymer latexes. Findings Accompanied by the stepwise decrease of DEA feeding ratio, the morphology of the resulting copolymerized nanoparticles changed from an ambiguous bulge to the typical spherical pattern. In addition, the P(DEA-St) latexes treated by cyclic CO2/N2 exhibit four different types of response modes, namely (i) CO2-switchable swelling/deswelling transition, (ii) CO2-reversible dispersion/coagulation transition, (iii) CO2-induced irreversible destabilisation and (iv) CO2-insensitive latexes. The CO2-responsive destabilisation is highly applicable in the separation and transportation fields of commercial latex products, such as poly(methyl methacrylate), poly(n-butyl acrylate) and poly(butyl methacrylate) colloids.

Bridged polysilsesquioxanes are promising materials for reverse osmosis membranes because they exhibit robust properties. To investigate the effects of the polarity and rigidity of organic components of the polymer on the water permeability of the membrane, two alkoxysilane monomers, 2,5-bis[2-(triethoxysilyl)vinyl]pyridine (BTES-VP) and 1,4-bis[2-(triethoxysilyl)vinyl]benzene (BTES-VB), were synthesized to compare their hydrophilicity and water desalination properties. Water contact angle experiments on the film surfaces revealed that the BTES-VP-derived film was more hydrophilic than the BTES-VB-derived film. Density functional theory calculations of the monomer structures also suggested that BTES-VP is more polar and has a larger dipole moment than BTES-VB. Both membranes prepared from BTES-VP and BTES-VB rejected 95–97% of aqueous sodium chloride and displayed water permeances of 1.1 × 10−13 and 8.5 × 10−14 m3/(m2 Pa s), respectively. Bridged polysilsesquioxanes are promising materials for reverse osmosis membranes because they exhibit robust properties. To investigate the effects of the polarity and rigidity of organic components of the polymer on the water permeability of the membrane, two alkoxysilane monomers, 2,5-bis[2-(triethoxysilyl)vinyl]pyridine (BTES-VP) and 1,4-bis[2-(triethoxysilyl)vinyl]benzene (BTES-VB), were synthesized. Both membranes prepared from BTES-VP and BTES-VB rejected 95–97% of aqueous sodium chloride and displayed water permeances of 1.1 × 10−13 and 8.5 × 10−14 m3/(m2· Pa· s), respectively.

The molecularly imprinted polymers (MIPs) were prepared by using the non-covalent approach. In the polymerization process, xylenol orange was used as a template (T), acrylic acid as a functional monomer (M), divinylbenzene as a cross-linker (CL) and 2,2’-azobisisobutyronitrile (AIBN) as an initiator and microemulsion as a solvent. The synthesized polymers were characterized by using FTIR and SEM micrograph. The batch binding analysis was used to evaluate the rebinding efficiency of imprinted polymers. The highest rebinding efficiency was obtained from the MIP-R2 (0.1:0.6:2, T:M:CL). The selected MIP-R2 was used for the removal of xylenol orange from the water sample and have shown removal efficiency of about 80%.

The synergistic effect of divinylbenzene and triallyl cyanurate on the properties and structure of the thermoplastic vulcanizate prepared from a blend of polypropylene and hydrogenated styrene–butadiene–styrene triblock copolymer by vulcanization under dynamic conditions with 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane was revealed. The synergism consists in the enhancement of the strength, increase in the relative elongation, and decrease in the compression set to a greater extent then when using divinylbenzene or triallyl cyanurate separately. The synergism is caused by the increased gel fraction content and vulcanization network thickness, with preservation of the higher molecular mass of the polypropylene matrix.

Polystyrene crosslinked microspheres were prepared by soap-free emulsion polymerization using styrene (St) and divinylbenzene (DVB) as monomers; then, the microporous structure was knitted by the Friedel-Crafts alkylation reaction, and the Au nanoparticles (AuNPs) were loaded into the pores through thermal reduction, to obtain AuNPs/hyper-crosslinked microporous polymer composite microspheres. SEM and particle-size test results show that the microspheres show good monodispersity. The micropore analysis indicates that the specific surface area and the pore volume of the microporous polymer microspheres decrease with increasing DVB content, and when the DVB content is 0.1%, the specific surface area reaches a maximum of 1 174.6 m2/g. After loading AuNPs, the specific surface area and the amount of micropores of the composite microspheres decrease obviously. The results of XRD and XPS analyses suggest that HAuCl4 is reduced to AuNPs. The composite microspheres show a good catalytic performance for the reduction catalyst of 4-nitrophenol.

Polymerized high internal phase emulsion (polyHIPE) monoliths have attracted much attention because of their ease of preparation, precise control of porous structure and useful properties. For many applications, such as chromatographic separation media, reactivity or absorptivity, post-modification of surface functional groups is required to achieve the desired functionality. However, for fluoro-polymers, it has been a challenge to fabricate high-performance foams with uniform porous structures using HIPE due to the lack of suitable surfactants to stabilize the fluorinated emulsions. In our work, we proposed a bottom-up approach where the same surfactant that stabilized the water droplets within the oil phase was used to control the solid foam surface chemistry. We employed reversible addition–fragmentation chain transfer living radical polymerization to synthesize amphiphilic-fluorinated macrosurfactant (mPEG5K-PHFBMA) to stabilize water-in-oil (W/O) HIPE. Using hexafluorobutyl methacrylate as the oil-phase monomer and divinylbenzene as the cross-linking agent, we achieved a one-pot preparation of polyHIPEs based upon poly(ethylene glycol) (PEG) with biocompatible pore surfaces and potential use in tissue engineering. The effects of amphiphilic macromolecular surfactant concentration, PHFBMA block length and initiator oil/water solubility on the emulsion droplet size, pore morphology, porous surface performance and mechanical properties were studied. The PEG modification on porous surface in the polyHIPE was also confirmed by a contact angle test and water uptake experiment. It was found that short-chain fluorinated materials demonstrated very little bioaccumulation potential and consequently better environmental safety attributes. The addition of PEG gave good biocompatibility, and the properties of these porous materials may have great potential in cell tissue engineering applications.

Pre-concentrators are used to improve the detection of analytes that are at low concentration, particularly in air. Polymeric materials are the basis for most pre-concentrators and a strategy to enhance the pre-concentration capability is to add moieties that enhance the polymer matrix–analyte interaction. In this study, the sorption capability of poly(dimethylsiloxane) (PDMS)-based pre-concentrator films towards nitro-based explosives was improved by incorporating a 1,4-divinylbenzene (DVB) derived component. It was found that the mode of DVB incorporation strongly influenced the structure and pre-concentration properties of the resulting film. Films formed from blends of PDMS and DVB (PDMS:DVB) were found to have similar sorption properties as PDMS. The copolymerised (PDMS-co-DVB) film was found to be comprised of voids and spheroidal features, which were retained even after thermal treatment. The copolymer film offered the greatest sorption and retention of analyte vapor, which we attribute to increased material surface area and π–π interactions between the DVB-derived units and the nitroaromatic analytes. The copolymerised film was able to increase the effective concentration of TNT vapor by 3 orders of magnitude relative to the headspace vapor concentration.

Based on the electron-transfer mechanism between the template and quantum dots (QDs), an optical sensor was structured. It is a phenol sensor, which has the room-temperature phosphorescence (RTP) property of Mn-doped ZnS QDs and high selectivity of molecular imprinted polymers (MIPs). On the surface of the silane modified Mn-doped ZnS QDs, the phenol sensor was prepared by double cross-linker precipitation polymerization in the absence of any stabilizer and additive. Double cross-linkers, divinylbenzene (DVB) and ethyleneglycol dimethacrylate (EGDMA), make a great contribution to the imprinted polymerization with hydrogen-bonding interaction. Then, as a result of the functional monomer, methacrylic acid (MAA), a carboxylic acid was grafted onto the surface of ZnS QDs:Mn@MIPs. Under optimal conditions, the phenol determination experiment had a linear range of 5.0 to 55 μmol L−1 with a correlation coefficient of 0.9984, and a high imprinting factor (IF) of 3.43. In addition, the prepared ZnS QDs:Mn@MIPs were successfully used to detect phenol in real water samples. Therefore, this work provided a highly selective and sensitive RTP probe for phenol determination.

High-refractive-index sulfur-rich polymers with significantly improved thermal properties are prepared using divinylbenzene (DVB) as a comonomer in a modified, low-temperature inverse vulcanization with elemental sulfur. Differential scanning calorimetry and Fourier transform infrared studies reveal that under the modified inverse vulcanization conditions, homopolymerized DVB segments form, leading to high glass-transition temperatures (

The possibility of creating monolithic plates containing functional groups capable of performing therole of MALDI matrices is shown, and the first results on desorption / ionization of compounds with massesof the order of 400 Da are demonstrated. Monolithic plates were prepared based on (co)polymers of glycidylmethacrylate and ethylene glycol dimethacrylate with the content of the first from 0 to 29% and styrene anddivinylbenzene with the content of styrene from 0 to 35%. The best results were obtained for TLC plates withglycidyl methacrylate content from 19 to 29% and with a styrene content of 5 to 20%. It is noted that the absence of a monofunctional monomer in the polymerization mixture resulted in the suppression of analyteionization and the impossibility of using such TLC plates in the MALDI-MS mode. Another factor affecting the possibility of desorption / ionization of compounds is the quality of the surface. The presence of roughness,uneven surface dramatically affect the ability to work in the mode of MALDI-MS, and the monoliths,containing less than 19% of the GMA, were mechanically fragile, and manipulation with them easily led tosurface damage. Similar results were obtained for monolithic sorbents based on (co)polymers of styrene anddivinylbenzene with styrene percentage lower than 10%. In order to obtain information on the surface relief,monolithic layers were prepared on glass substrates (18 × 18 mm, 0.13–0.17 mm thick) with various contentsof monofunctional monomers and using various porogens and were studied by scanning electron microscopy.According to the height distribution histograms, it was found that for a sample of St-DVB copolymer containing 30% styrene and 10% divinylbenzene in the initial polymerization mixture (undecanol-toluene solvent 52: 8) the highest density corresponded to an average roughness value of 150 nm, whereas for sample composition (14% GMA + 26% DMEG, 60% cyclohexanol), the highest density corresponded to an average roughness value of 50-60 nm. The proposed method for obtaining MALDI-MS-TLC spectra eliminates one of the most labor-intensive stages of the process associated with the preparation and application of theMALDI matrix on a TLC plate

Microfluidic techniques allow for the tailored construction of specific microparticles, which are becoming increasingly interesting and relevant. Here, using a microfluidic hole-plate-device and thermal-initiated free radical polymerization, submicrometer polymer particles with a highly textured surface were synthesized. Two types of monomers were applied: (1) methylmethacrylate (MMA) combined with crosslinkers and (2) divinylbenzene (DVB). Surface texture and morphology can be influenced by a series of parameters such as the monomer–crosslinker–solvent composition, surfactants, and additives. Generally, the most structured surfaces with the simultaneously most uniform particles were obtained in the DVB–toluene–nonionic-tensides system. In a second approach, poly-MMA (PMMA) particles were used to build aggregates with bigger polymer particles. For this purpose, tripropyleneglycolediacrylate (TPGDA) particles were synthesized in a microfluidic co-flow arrangement and polymerized by light- irradiation. Then, PMMA particles were assembled at their surface. In a third step, these composites were dispersed in an aqueous acrylamide–methylenebisacrylamide solution, which again was run through a co-flow-device and photopolymerized. As such, entities consisting of particles of three different size ranges—typically 0.7/30/600 µm—were obtained. The particles synthesized by both approaches are potentially suitable for loading with or incorporation of analytic probes or catalysts such as dyes or metals.

This work presents the results of the synthesis of granular copolymers of acrylonitrile with hexahydro-1,3,5-triacrylyltriazine and their modification with organic amines, in particular diethylamine, as well as a study of the physicochemical characteristics and sorption properties of the obtained ion exchangers. The result of the study was the synthesis of granular ion exchangers with the necessary physicochemical properties based on acrylonitrile and divinylbenzene, N,N´-methylene-bis-acrylamide and hexahydro-1,3,5-triacrylyltriazine, the kinetics of this process was studied. The synthesized copolymers were modified with diethylamine, the physicochemical and ion-exchange properties of the obtained polymers were studied. It has been shown that acrylonitrile, its copolymers coated with divinylbenzene, N,N´-methylene-bis-acrylamide and hexahydro-1,3,5-triacrylyltriazine, as well as granular ion exchangers based on them, can be obtained. For the first time, copolymers of acrylonitrile and hexahydro-1,3,5-triacrylyltriazine with the necessary physicochemical characteristics were synthesized and, on their basis, conditions for obtaining weak anion-exchange resins on a complex basis were developed. The synthesized anion exchangers have complexing properties and can be used in the hydrometallurgy of non-ferrous and heavy metals, purification of waste water from toxic ions, separation and concentration of metal ions.

Στην παρούσα διδακτορική διατριβή επιδιώκεται η σύνθεση και ο χαρακτηρισμός πολυμερικών νανοδομών ελεγχόμενης μορφολογίας, με την τεχνική του πολυμερισμού μέσω ελευθέρων ριζών (FRP) σε οργανωμένα υδατικά διαλύματα, καθώς και η διερεύνηση δυνητικών εφαρμογών των υλικών αυτών. Για το σκοπό αυτό, ο πολυμερισμός των υλικών πραγματοποιείται παρουσία οργανωμένων υπερμοριακών δομών, οι οποίες αναμένεται να λειτουργήσουν ως εκμαγεία (templates). Τα εκμαγεία αυτά οργανώνονται από κατάλληλες επιφανειοδραστικές ενώσεις μέσω υδρόφιλων/υδρόφοβων ή/και ηλεκτροστατικών αλληλεπιδράσεων σε υδατικό περιβάλλον. Οι κατηγορίες εκμαγείων που αξιοποιήθηκαν σε αυτή τη μελέτη είναι: οι δομές αυτοοργάνωσης των επιφανειοδραστικών ενώσεων σε φυλλώδη (Lamellar) ή σπογγώδη (sponge) φάση, η ανάπτυξη σκωληκοειδών μικκυλίων και η ικανότητα των επιφανειοδραστικών ενώσεων να δημιουργούν γαλακτώματα παρουσία κάποιας οργανικής φάσης.Τα μονομερή που επιλέχθηκαν για τον πολυμερισμό στο επιθυμητό εκμαγείο είναι το στυρόλιο (St), το 4-βινυλοβενζυλοχλωρίδιο (VBC), ο οξικός βινυλεστέρας (VAc) και το στυρενοσουλφονικό νάτριο (SSNa), ενώ οι επιφανειοδραστικές ενώσεις που χρησιμοποιήθηκαν για το σχηματισμό των εκμαγείων ήταν το δωδεκυλο θειικό νάτριο (SDS), το βρωμιούχο δεκαεξυλτριμεθυλαμμώνιο (CTAB) και ο πολυαιθυλενο-γλυκολ-δωδεκυλ-αιθυλαιθέρας (Brij-30). Για τη σταθεροποίηση της μορφολογίας, όλοι οι πολυμερισμοί πραγματοποιήθηκαν παρουσία του διασταυρωτή διβινυλοβενζόλιο (DVB). Μέσω ηλεκτρονικής μικροσκοπίας σάρωσης (SEM) ή/και διαπερατότητας (TEM) επιβεβαιώθηκε, η σύνθεση νανοσφαιρών (PSt), πλακόμορφων νανοδομών (PSt, PVAc και PVBC) και δικτύου νανοράβδων (PSt και PVBC). Η επιτυχία των συνθέσεων καθώς και η διατήρηση της μορφολογίας έπειτα από θερμική καταπόνηση ή χημικές τροποποιήσεις, όπως θα παρουσιαστούν στη συνέχεια, πιστοποιήθηκε με φασματοσκοπία υπερύθρου ATR-IR, θερμοσταθμική ανάλυση TGA και ηλεκτρονική μικροσκοπία σάρωσης SEM. Η ειδική επιφάνεια των δειγμάτων προσδιορίστηκε με τη μέθοδο Brunauer-Emmet-Teller (BET).Η αναζήτηση πρωτότυπων δυνητικών εφαρμογών των συντεθέντων υλικών αποτέλεσε το αντικείμενο ενασχόλησης των επόμενων σταδίων της παρούσας διδακτορικής διατριβής. Έτσι, διερευνήθηκε η εφαρμογή τους ως εν δυνάμει προσροφητές χρωστικών ουσιών από υδατικά απόβλητα ή προσροφητές μοριακού οξυγόνου από υδατικά συστήματα ή αέρα. Όσον αφορά την πρώτη εφαρμογή, αξιοποιήθηκαν τα δίκτυα νανοράβδων διασταυρωμένου PVBC τα οποία τροποποιήθηκαν κατάλληλα με φορτισμένες ομάδες ή φορτισμένα πολυμερή. Διαπιστώθηκε πως η προσροφητική ικανότητα των υλικών αυτών έναντι των αντίθετα φορτισμένων χρωστικών ουσιών Orange II και Methylene blue είναι σημαντική, 175mg/g – 500 mg/g και 160 mg/g για τις δύο χρωστικές αντίστοιχα.Η εναλλακτική λειτουργικότητα των νεοσυντεθέντων υλικών που μας απασχόλησε ήταν η προσρόφηση μοριακού οξυγόνου από υδατικά συστήματα ή αέρα. Για το σκοπό αυτό αξιοποιήθηκαν τόσο υδατοδιαλυτά πολυμερή όσο και σφαιρικά νανοσωματίδια PSt ή PVBC, στα οποία ενσωματώθηκε κατά τον πολυμερισμό η δραστική ομάδα της ανθρακινόνης (AQ), η οποία αντιδρά με το οξυγόνο έπειτα από κατάλληλη ενεργοποίηση με UV ακτινοβολία. Ανάλογα με την περίπτωση τα νέα υλικά μελετήθηκαν σε διαλύματα, διασπορές ή ενσωματωμένα σε πολυμερικές μήτρες. Διαπιστώθηκε πως έπειτα από κατάλληλη ενεργοποίηση με UV ακτινοβολία απομακρύνουν αποτελεσματικά το διαλυμένο οξυγόνο από υδατικά συστήματα, με τελική τιμή ~1ppm, ενώ λειτουργούν ικανοποιητικά για τη δέσμευση οξυγόνου του αέρα. Στην περίπτωση του υδατοδιαλυτού συμπολυμερούς, αυτή η λειτουργία συνοδεύεται με αλλαγές στα φάσματα απορρόφησης UV-vis αμέσως μετά την ακτινοβόληση με UV ακτινοβολία, ως ένδειξη σχηματισμού νέων ειδών AQ, καθώς και με σημαντική εκπομπή φωτός από τα φωτο-διεγερμένα είδη της.

The preparation of nanofibers with finer diameters is of great importance to meet the needs of nanomaterials in fabricating nano-devices. The diameter of polydivinylbenzene nanofibers can be reduced from 200 nm to 20–50 nm by adding a very small amount of oleic acid-capped Fe3O4 nanoparticles during the polymerization of divinylbenzene. Through ultrasonic disruption and magnetic separation of the nanofiber composites, we can obtain purified ultrafine nanofibers without Fe3O4 nanoparticles. The ultrafine nanofibers have widespread potential applications in nanomaterials and nano-devices with smaller requirements.

In this study, we used amines electrolyte solution with layer-by-layer (LbL) technique to modify and increase the CO2 adsorption capacity of highly porous polymer from high internal phase emulsion template polymer. This perspective presents the extraordinary versatility of emulsion templating polymerization, which has emerged with the growing numbers of HIPE systems and modification. In this study, we used polyHIPE prepared from styrene (S) and divinylbenzene (DVB) with varying ratios, 80:20, 20:80, and 0:100 to improve the surface area, thermal properties, and mechanical properties of the materials. Furthermore, the surface of the polyHIPE was modified by LbL technique to increase the adsorption efficiency. This technique consisted of two main layers, the primary layer of poly(diallyldimethylammonium chloride) (PDADMAC) and polystyrene sulfonate (PSS) and the secondary layer, which was the CO2 adsorbing layer, of polyethylene imine (PEI) or tetraethylene pentamine (TEPA). Poly(S/DVB)HIPE modified by PEI terminated as the secondary coating showed the highest CO2 adsorption capacity, with up to 42% (from 0.71 to 1.01 mmol/g). The amine-multilayered modified material still possessed an open cell structure, since the solution did not block the pore structure of the poly(S/DVB)HIPE and was suitable for being used as an adsorbent in adsorption technology.

In this study, a special poly solid-phase extraction (in-tube SPE) column consisting of poly (POSS-octavinyl-co-N-methylacetamide-co-divinylbenzene) [poly (POSS-OS-co-DVB-co-NMA)] was prepared based on the chemical structure of the preservatives, and was used as medium for extraction analysis in combination with UPLC. The composition of polymer SPE was optimized and characterized; good scanning electron microscopy (SEM) properties and satisfactory porosity were obtained with 30% monomer (POSS-OS:DVB:NMA = 2 wt%:13 wt%:15 wt%) and 70 wt% porogenic solvent (PEG20000:DMSO:ACN = 10 wt%:50 wt%:10 wt%). The experimental parameters of the in-tube SPE-UPLC analysis were optimized systematically. Then, the in-tube SPE-UPLC method was applied for analyzing the beverage sample, and correlation coefficients (R2) > 0.99 were obtained for the linear relationship within limits of 0.1~5.0 μg mL−1. Excellent extraction efficiency, good precision, and satisfactory limit of detection sensitivity between 0.03 and 0.10 μg mL−1 were obtained. The recovery ranged from 71.5 to 88.0%, with RSD ≤ 6.1%. Furthermore, the proposed method has the features of simple sample pretreatment, high throughput, rapid analysis, cost-effectiveness, and satisfactory sensitivity. Hence, the developed in-tube SPE-UPLC method based on the poly (POSS-OS-co-DVB-co-NMA) SPE column can be potentially used for simple and sensitive detection of preservatives.

A new method for the synthesis of highly crosslinked and in situ alkyne functionalized microspheres, by combining type II photoinitiation with precipitation polymerization, is reported. Using a benzophenone-tertiary amine initiation system, the method allows the preparation of functional microspheres at room temperature by UV irradiation in the absence of stabilizers or surfactants of any kind. To demonstrate the presence and accessibility of the alkyne moiety on the polymer particles, fluorescent pyrene groups are attached to the microspheres by copper(I)-catalyzed alkyne-azide cycloaddition click reaction, using 1-azidomethyl pyrene as a model compound. FT-IR, fluorescence spectroscopy, fluorescence microscopy, and scanning electron microscopy are used for characterization of the particles and to monitor the click reaction.

The development of heterogeneous catalytic processes is crucial for the synthesis of chiral compounds for both academic and industrial applications. However, thus far, such achievements have remained elusive. Herein, we report the heterogeneous asymmetric hydrogenation of 2-methylquinoline over solid chiral catalysts, which were prepared by the one-pot polymerization of (1R,2R)-N-(4-vinyl-benzenesulfonyl)-1,2-diphenylethane-1,2-diamine (VDPEN) and divinylbenzene (DVB) in the presence or absence of activated carbon (C) or carbon nanotubes (CNTs), followed by Ru coordination and anion exchange. The solid chiral catalysts were fully characterized by N2 sorption analysis, elemental analysis, TEM, FT-IR spectroscopy, and13C CP-MAS NMR. All the solid chiral catalysts could efficiently catalyze the asymmetric hydrogenation of 2-methylquinoline to afford 2-methyl-1,2,3,4-tetrahydroquinoline with 90% ee. Studies have shown that polymer/C and polymer/CNTs composites are more active than pure polymers. The polymer/CNTs composite exhibited the highest activity among all the solid chiral catalysts under identical conditions, owing to the unique morphology of CNTs. The recycling stabilities of the solid chiral catalysts were greatly improved when ionic liquids (ILs) were employed as solvents; this is mainly attributed to the decreased leaching amount of anions owing to the confinement effect of ILs on ionic compounds.

Novel organic/inorganic hybrid star polymer was prepared dually crosslinked within inner-core via divinylbenzene (DVB) and outer-surface via octafunctional polyhedral oligomeric silsesquioxane (POSS). Core cross-linked star polymers bearing dialkynyl-terminated polystyrene arms, (dialkynyl-PS)n-CCL, were synthesized at first by the atom transfer radical polymerization (ATRP) of DVB using α,α-dialkynyl-terminated PS macroinitiator, followed by the subsequent fractionation. Under high dilution conditions, (dialkynyl-PS)n-CCL was subjected to surface cross-linking with octa(3-azidopropyl) polyhedral oligomeric silsesquioxane, POSS-(N3)8, via click reaction, affording POSS-functionalized hybrid polymer doubly cross-linked within core and surface regions, SCL-(PS)n-CCL. FT-IR, 1H NMR, GPC, and elemental analysis results revealed that on average, the obtained hybrid polymer possesses a cross-linked PDVB inner core, ∼14 linear PS arms (the Mw per arm of 5.1 kDa), and ∼4-5 POSS moieties at outer surface. Differential scanning calorimetry (DSC) thermograms and thermogravimetric analysis (TGA) revealed that after surface cross-linking the thermal stability of SCL-(PS)n-CCL is considerably improved. This work provides a proof-of-concept example for the preparation of dually cross-linked hybrid star polymer, which represents a novel category of organic/inorganic composite materials with unique chain architectures.

The influence of the concentration of an external solution, the nature of the polar groups, and the amount of cross-linking in the resins on the degree of swelling of the ionites synthesized based on the polystyrene cross-linked by divinylbenzene is investigated. It is shown that the share of the volume of the external solution in an ionite depends only on the amount of cross-linking and is independent of the nature of the polar groups and the composition of the external solution. The dependence of the share of the volume occupied by the external solution in the swollen ionite on the percentage of divinylbenzene is determined. The model of the polymer matrix in which the concentration of the external solution affects the degree of polymer swelling but does not affect the volume of the external solution in the granule is proposed. It is shown that the “sandwich” model of the polymer matrix is most convenient for describing the properties of polymer gels in which the concentration of the external solution affects the degree of swelling of the polymer but does not affect the volume of the phase of the external solution in the granule.

Hydrophilic divinylbenzene (DVB) (Bakerbond) has surfaced as a promising sorbent for active sampling of analytes from aqueous matrices over a very broad polarity range. Given this, hydrophilic DVB may likewise offer potential for passive sampling, if sorbent/water partitioning coefficients (Ksw) were to be available. In this work, static exposure batch experiments were performed to quantitatively study the equilibrium sorption of 131 environmentally relevant organic contaminants (P values ranging from -1.30 to 9.85) on hydrophilic DVB. The superior affinity of hydrophilic DVB, as compared to Oasis HLB, for compounds with a broad polarity range was confirmed by functional Fourier-transform infrared spectroscopy and Raman characterization, demonstrating the presence of carboxyl moieties. Concentration effects were studied by increasing compound concentrations in mixture experiments and resulted in the steroidal endocrine disrupting compounds in higher Ksw, while lower Ksw were obtained for the (alkyl)phenols, personal care products, pesticides, pharmaceuticals, and phthalates. Nevertheless, Ksw remained constant in the said design for equilibrium water concentrations at environmentally relevant seawater levels. An independent analysis of thermodynamic parameters (change in enthalpy, entropy, and Gibbs free energy) revealed the nature of the main partitioning processes. While polar (log P 4) compounds also exhibited binding by multiple hydrogen bonding. In conclusion, this research facilitates the future application of hydrophilic DVB for active as well as passive sampling in the analysis of organic contaminants for monitoring purposes and for toxicity testing.

Mimicking the structures and functions of biological systems is considered as a promising approach to construct artificial materials, which have great potential in energy, the environment, and health. Here, we demonstrate a conceptually distinct design by synergistically combining a kidney-inspired porous membrane and natural sponge-inspired heterostructured nanoporous particles to fabricate a bioinspired biomolecule cleaning device, achieving highly efficient biomolecule cleaning spanning from small molecules to macromolecules. The bioinspired biomolecule cleaning device is a two-layer microfluidic device that integrates a polyamide porous membrane and heterostructured nanoporous poly(acrylic acid)-poly(styrene divinylbenzene) particles. The former as a filtration membrane isolates the upper sample liquid and the latter fixed onto the bottom of the underlying channel acts as an active sorbent, particularly enhancing the clearance of macromolecules. As a proof-of-concept, we demonstrate that typical molecules, including urea, creatinine, lysozyme, and β2-microglobulin, can be efficiently cleaned from simulant liquid and even whole blood. This study provides a method to fabricate a bioinspired biomolecule cleaning device for highly efficient biomolecule cleaning. We believe that our bioinspired synergistic design may expand to other fields for the fabrication of integrated functional devices, creating opportunities in a wide variety of applications.

The catalytic activity of imidazolium-based SILLPs stabilised onto DVB/CMS catalyst supports is evaluated to develop “Union Carbide” process catalytic systems. Under similar conditions, SILLPs based on 4-Methyl Imidazole behave as more active catalysts in trichlorosilane disproportionation in part of silane yield. In these systems, the polymer support is not only an inert matrix. The polymer is designed to play an important role. Firstly controlling the easy accessibility of the reagents to the active sites and providing specific micro-environments for a transition state complex. The structure of these supports can be tuned to adjust the catalytic efficiency SILLPs for different reactions. For this purpose, the meticulous physico-chemistry characterisation was carry out. Based on the experimental data obtained, a reaction mechanism is proposed.

Most applications of nanoparticles require robust stabilization, for example, by surface-bound ligands or the encapsulation within polymer shells. Furthermore, for biomedical applications, the particles must be dispersible in a complex biological environment. Thus, high-quality nanoparticles synthesized in organic solvents must be transferred into aqueous media. Here, we present a novel scalable method enabling the robust hydrophilic encapsulation of non-agglomerated nanoparticles by growing polystyrene shells via AGET-ATRP in microemulsion. To demonstrate this approach, we encapsulate iron oxide nanoparticles (diameter: 13.7 ± 0.6 nm). Because the ATRP initiator is grafted onto the nanoparticles' surface, the shells are covalently attached to the iron oxide cores. By varying the amount of monomers, the shell thickness can be adjusted precisely, as indicated by the increasing hydrodynamic size from ∼22 to 26 nm (DLS, number mean) with an increasing amount of added monomers. Moreover, the degree of cross-linking can be controlled by the amount of added divinylbenzene (DVB). To evaluate the robustness of the polymer shells against ion infusion, we introduce a novel colorimetric method, which is based on the formation of the red iron thiocyanate complex. After addition of HCl, the increase in absorbance at 468 nm indicates leaching of iron ions from the polymer-encapsulated core particles. These measurements confirm that with increasing shell thickness, significantly improved shielding is achieved. Furthermore, high concentrations of added DVB [33-50% (v/v) in a monomer mixture] improve the shielding effect. However, when smaller amounts of DVB were added [10-25% (v/v)], the shielding effect was diminished, even in comparison to non-cross-linked polymer shells. This finding suggests a higher porosity of shells with a low degree of cross-linking.

α-FeOOH nanocrystals were grown on the surface of polymeric spheres through in situ hydrothermal synthesis. The polymer with the surface amine groups was composed of styrene, divinylbenzene and 2-(dimethylamino)ethyl methacrylate via emulsion polymerization, which abbreviated it as PSDM. The structure and component of PSDM@α-FeOOH composites were investigated by Fourier transform infrared, thermogravimetric analysis, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscope and transmission electron microscopy. It was observed that the crystal structure, morphology and dispersion of α-FeOOH depended on different factors, i.e., temperature, reactant concentration and ferric salt types. A plausible formation mechanism of PSDM@α-FeOOH composites was revealed based on the systematic investigations of the assembly process. Additionally, it was possible for this method to be extended to synthesis the composite particles for other metal ions. The photocatalytic activity of the composites had been discussed by testing the degradation of rhodamine B as well as methylene blue and neutral red in the presence of H2O2. The measurements demonstrated that PSDM@α-FeOOH composites catalyst exhibited excellent photocatalytic ability and superior stability.

Catalyst performance is highly relevant to its mass transport performance. In the present study, seven styrene-co-divinylbenzene polymer samples were synthesized by varying the amounts of crosslinker and porogen, so as to elucidate mass transport mechanism in poly (styrene-co-divinylbenzene) microspheres with hierarchical pore structure. Correspondingly, pore structure parameters of seven samples were characterized by BET and MIP. By choosing toluene as probe molecule, surface diffusion coefficient and pore diffusion coefficient of toluene inside the microspheres were measured. The experimental results indicated that both surface diffusion coefficient and pore diffusion coefficient increase with the rise of the ratio of average mesopore diameter to average macropore diameter under a certain porosity. Moreover, the rise of porosity results in greater enhancement of pore diffusion coefficient than surface diffusion coefficient. Finally, sulfonic acid groups were anchored onto polymer microspheres to investigate the relative importance of mass transport performance and catalytic performance by virtue of methyl acetate hydrolysis.

A well-defined molecularly imprinted polymer (Fe3O4@CS@MIP) was synthesized via reversible addition-fragmentation chain transfer polymerization for magnetic solid-phase extraction coupled with high-performance liquid chromatography-diode array detector to detect carbamazepine (CBZ) in biological samples. The composition of Fe3O4@CS@MIP was selected by a two-step screening method. 4-vinyl pyridine, divinylbenzene and dimethylformamide were chosen as the functional monomer, cross-linker and porogen, respectively. The imprinted layer was coated on the surface of the chain transfer agent-modified magnetic chitosan nanoparticles. The prepared Fe3O4@CS@MIP was characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller measurement and vibrating sample magnetometer. The results indicated that Fe3O4@CS@MIP had a large surface area (265.8 m2/g), high saturation magnetization (19.88 emu/g) and uniform structure. Besides, the binding property of the Fe3O4@CS@MIP was studied in detail. The Fe3O4@CS@MIP showed high imprinting factor (IF = 4.83) and desirable adsorption capacity (323.10 μmol/g) to CBZ. Under the optimum conditions, the developed method exhibited excellent linearity (R2>0.999) in the range of 0.01–0.5 mg/L and 1.0–30.0 mg/L, and the limits of detection were 1.0 μg/L and 9.6 μg/L for the urine and serum samples, respectively. Good recoveries (88.22%–101.18%) were obtained with relative standard deviations less than 4.83%. This work provided a practical approach for the selective extraction and detection of CBZ in real samples.