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Block copolymers (BCPs) have been intensively used as structure-directing agents for the synthesis of mesostructured materials because of their rich microphase separation and excellent thermal stab...

Nanoporous membranes prepared by supramolecular assembly of block copolymers have attracted increasing attention for their well-defined nanostructure, adjustable pore size, and large-scale manufact...

H4SiW12O40 (SiW12)/cellulose acetate (CA) composite nanofibrous membrane was prepared by electrospinning in which CA was employed as the support of SiW12. Characterization with Fourier transformation infrared spectroscopy (FT-IR), Energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) indicated that SiW12 has been successfully loaded into the CA membrane and its Keggin structure remained intact. The as-prepared composite membrane exhibited enhanced photocatalytic activity in the decomposition of tetracycline (TC) and methyl orange (MO) compared with pure SiW12 under ultraviolet irradiation. The optimal mass ratio of SiW12 to CA was 1:4, and the corresponding degradation efficiency for TC and MO was 63.8% and 94.6%, respectively. It is noteworthy that the degradation rate of MO increased more evidently than that of TC under the same conditions, which may be attributed to the different role that CA nanofibrous membrane played in the TC and MO photodegradation process. Besides providing more contact area between SiW12 and the pollutant in TC photodegradation, CA membrane played an additional role that donated electron to SiW12 in the MO degradation process, leading to a different photocatalytic mechanism with greatly enhanced degradation rate. Moreover, the composite membrane presented an excellent reusability, which was mainly ascribed to the water-insolubility of CA and the hydrogen bonds between CA and SiW12. This work will be useful for the design of biopolymer-based membrane photocatalysts applied to antibiotics and dyes wastewater treatment.

Herein, the Zr-MOF UiO-66-NH2 was synthesized in a facile method. When the as-synthesized UiO-66-NH2 is served as an adsorbent for 2,4,6-trinitrophenol (PA), styphnic acid (TNR), 2,4-dinitrophenol (2,4-DNP), 2,4,6-trinitrotoluene (TNT), and 2,4-dinitrotoluene (2,4-DNT) in water, the absorption capacities are 0.0225, 0.024, 0.0296, 0.0005, and 0.002 g/g, respectively. This suggests that UiO-66-NH2 is an excellent adsorbent for PA, TNR, and 2,4-DNP and is promising material for the removal of PA, TNR, and 2,4-DNP from wastewater. The excellent adsorption performance is attributed to the hydrogen-bond interactions between UiO-66-NH2 and these explosives.

The design and fabrication of a novel multimaterial Ge25Se10Te65/As2S3 chalcogenide glass fiber with ultra-high numerical aperture (NA) by using the rod-in-tube method was reported. The NA of fiber of approximately 2.2 is the maximum NA of step-index chalcogenide fibers obtained experimentally. The Ge25Se10Te65 glass was selected as the core material, and its mechanical and thermal properties were investigated. The optical properties and bending strength were measured to investigate fiber performance. The low bending loss of fiber was demonstrated through a simulation and an experiment. The fundamental dispersion characteristic, effective-mode-area, and nonlinear coefficient of fiber were simulated numerically.

In this work, we report the microfluidic preparation of monodisperse imidazolium-based poly(ionic liquid) (PIL) microgels with a controlled size and morphology, and show that the imidazolium units in the microgel network can be exploited as reactive sites to efficiently access desired functional materials by a simple counteranion-exchange or conversion reaction. Moreover, based on the counteranion-exchange reaction, spatio-temporal engineering of the surface of the PIL microgels could also be realized, and a new and simple strategy for the fabrication of diverse anisotropic microgels (patchy particles) with great flexibility was developed. In addition, by exploiting the convenient generation of carbene units from the imidazolium moieties, as well as the carbonizable feature of PIL, the prepared PIL microgels could be further converted into stable carbene spheres and monodisperse carbon particles. All the results show that these monodisperse PIL-based microgels can serve as a very useful platform for facilely accessing various functional materials.

Effective deposition of MOFs on "inert" solid surfaces is very challenging. In this work, we found that polydopamine, which can be facilely and tightly formed on any types as well as any forms of solid surfaces, could be used as an effective nucleation center for MOF deposition. Based on this finding, various MOFs were successfully deposited onto nanofibrous polymer membranes, especially the commercially available "inert" ones, affording hierarchically structured porous films.

Self-standing thiol-functionalized fibrous membrane with bimodal pore structure was successfully fabricated through the combination of electrospinning and surfactant-directing pore formation technique. We also found that the interference of electric field as well as the rapid solvent evaporation during the electrospinning process has a negative effect on the formation of ordered mesoporous structures. As high-performance adsorption-based filtration system, such hierarchically structured membrane is found to efficiently remove Cu (II) ions under high flux.

An effective online method for molecular ion yield enhancement in static secondary ion mass spectrometry (SIMS) is demonstrated using a custom-built soft landing (SL) instrument equipped with SIMS capabilities. Dramatic molecular ion yield enhancement has been observed for amino acids and peptides on silica substrates after soft landing a mixture of protonated water clusters [H(H2O)n]+ (n = 4 to > 100). Image current measurements and experiments on semiconducting and metal substrates confirmed that protonation of the analyte molecule and effective charge retention on the substrate is the reason for the observed phenomenon. Enhancement could also be observed-less conveniently-by offline treatment of the surface using electrospray deposition of 2% acetic acid in methanol/water solution. Copyright © 2010 John Wiley & Sons, Ltd.

This paper investigates the electrospinning process of liquid crystalline polysiloxane with cholesterol as side chain (LCPC) and the influence on the morphology of the formed fibers by mixing LCPC solution with small-molecule liquid crystal, triethylamine, and poly(ethylene oxide)(PEO). The mechanical properties of single fibers were characterized by a novel approach. The results indicate that, under appropriate conditions, fine liquid crystal fibers can be obtained and the preferable mechanical properties can be achieved, especially after annealing. WXRD was used to investigate the orientation of polymer molecules in the formed fibers, suggesting that strong interaction exists between LCPC and PEO molecule in the resulting composite fibers, and polymer molecular tends to arrange regularly during electrospinning processing. This research work provides a new and facile method of using electrospinning to prepare liquid crystal fibers, which would be useful for designing the related high-performance materials.

Two types of N-substituted pyrroles with azide and terminal alkyne groups have been synthesized and electropolymerized. "Click" chemistry, specifically Huisgen 1,3-dipolar cycloaddition, was used as a general method for functionalization of the polypyrrole films. Several model compounds, including redox active (quinone), bioactive (cholic acid) and recognition elements (carbohydrate and thymidine) could easily be attached onto the electrode surfaces without loss of functionality or the electroactivity of the underlying conducting polymers. The results suggest that the polypyrrole films are clickable and provide a novel biocompatible and versatile platform for efficient modifications on electrode surfaces.

A novel cucurbit[8]uril–fullerene complex was synthesized via ultrasonic. The product was characterized by UV/vis, FTIR, elemental analysis, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results of elemental analysis demonstrate that the cucurbit[8]uril–fullerene complex was formed by the 1:2 intermolecular inclusion mode. TEM analysis shows that it exists some sphere structures with size in the range of 15–20 nm, which are joined together through approximately 6–8 units of the inclusion complex of cucurbit[8]uril with two fullerene molecules. Four-ball tests shows that the addition of a certain concentration of the fullerene complex to base stock (2 wt.% triethanolamine aqueous solution) can effectively increase both the load-carrying capacity (PB value), and resistance to wear. SEM observations confirm that the additive results in a reduced diameter of the wear scar and decreased wear.

A series of novel “jellyfish-like” graft copolymers with chitooligosaccharide (COS) as shorter backbone and poly(e-caprolactone) as longer branches were synthesized using ring-opening polymerization of e-caprolactone via a protection-polymerization-deprotection procedure with trimethylsilylchitooligosaccharide as intermediate and triethylaluminum as catalyst precursor. The obtained chitooligosaccharide-graft-poly(e-caprolactone) polymers possess amphiphilic structure with hydrophilic COS backbone and hydrophobic polycaprolactone branches. Because of this unique “jellyfish-like” structure, these graft copolymers could self-assemble to form various morphologies of aggregates in a mixture solution of water and tetrahydrofuran. The transmission electron microscopy studies revealed that the formed aggregates exhibited necklace-like, flower-like onion vesicle, and tubular morphologies. It is found that the hydrogen-bonding formed by the hydroxyl and amino groups remained on the COS backbone played an important role during the aggregation of these graft copolymers, and their morphologies were changed with the varying length of poly (e-caprolactone) branches, the concentration of the graft copolymer, and the self-assembly process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4889–4904, 2008

A series of imidazolium-based ionic liquid monomers bearing a terminal pyrrole moiety were synthesized and electrochemically polymerized. It is found that the polymerizability of the synthesized ionic liquids is strongly dependent on the type of the counteranions. Although bromide monomer is not polymerizable, well-defined polymeric films can be formed on various substrates in the cases of flour-containing anions (BF4−, PF6−). The performed characterizations show that all resulting polypyrrole films are electroactive, and the imidazolium-based ionic liquid moieties are correctly incorporated in polymer films during the electropolymerization process. This work not only provides a facile new method to immobilize ionic liquids on solid surface. Interestingly, without use of any template unique “knit” morphology and nanostructure, even hierarchical structures could also be produced by the electropolymerization of these new functionalized pyrrole monomers. We found that the properties of the pendant ionic liquid units on the surface of the formed polymer films preserved, and by simple anion exchange their surface energy and tension could be easily tuned without loss of the electrical, optical properties, and morphology of the polypyrrole films. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4151–4161, 2008

A new series of pyrroles bearing bile acid moieties were synthesized and electrochemically polymerized in acetonitrile with tetrabutylammonium hexafluorophosphate (TBAFP 6 ) as the supporting electrolyte. It is found that these functionalized monomers could form polypyrrole films, but their electrochemical properties and the stability of the films are strongly dependent on the length of the alkyl spacer between pyrrole ring and the pendant bile acid moiety. Each of the resulting polymers with different bile acid groups shows a distinctive behaviour in terms of its microstructure of surface, as well as electrochemical and optical properties. Compared to other analogous polypyrroles, the optical property of the cholic acid functionalized polymer is sensitive to the polarity of the used solvents, exhibiting solvatochromic behaviour. This phenomenon is probably derived from its unique facial amphiphilic structure.

In this paper, monodispersed silica particles were synthesized using tetraethoxysiliane hydrolyzing in ethanol by a Stober-Fink-Bobn method and then self-assembled on cleaning glass slides to form silica colloidal crystals. After photopolymerization of methacrylic acid mixing with ethylene glycol dimethylacrylate and hydrofluoric acid etching, the pH-responsive polymers were obtained with highly 3D-ordered macroporous structures templated by silica colloidal crystals. These polymers films can swell or deswell in response to external stimuli, causing a change of Bragg diffraction to read pH or ionic strength of various solutions by optical signals or electrochemical signals. As an application, they can be used as chemical sensors to detect pH or ionic strength variation of environment.

The silica tubes were synthesized by template self-assembly from d,l-tartaric acid and hydrolysis of tetraethoxysilane (TEOS), and their surfaces were modified by a 3-aminopropyltriethoxysilane cou...

Two kinds of porphyrin-doped silica films with mesoporous structures were fabricated using evaporation-introduced self-assembly approach and examined for chemosensor applications to detect explosive compounds such as 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), and nitrobenzene (NB). All synthesized silica films showed high fluorescence quenching sensitivity toward the vapors of TNT, DNT, and NB but is strongly dependent on pore structure. The silica film with three dimensional pore structure exhibits the highest quenching efficiency close to the quenching efficiency reported for emissive conjugated polymers, indicating these kinds of mesostructured composites are potentially useful chemosensory materials for rapidly detecting trace explosives. The preparation conditions, the structures of the resulting films, their sensing performances, and the fluorescence quenching mechanism were discussed in this paper.

A novel fullerene-maleic anhydride derivative was synthesized via radical polymerization. It is soluble in polar solvents such as water, dimethyl sulfoxide, and tetrahydrofuran etc. The product was characterized by FTIR, UV-Vis, GPC, and Transmission electron microscope (TEM). TEM analysis shows that the average particle diameter is about 38 nm. The in vitro antitumor activity of the fullerene-maleic anhydride derivative has been tested and the result shows that the derivative exhibits better antitumor activity against HeLa cells and bone tumor cells. To prove water-soluble fullerene derivatives photodynamic effect on tumor cell, i.e., the photodynamic effect on mouse bone tumor in vivo we injected the fullerene -maleic anhydride derivatives into the mouse bone tumor body. We found that with I-W lamp (500 W) illumination the mouse bone tumor body was strongly damaged. The antitumor mechanism of water-soluble fullerene-maleic anhydride derivative was investigated for the first time. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

A series of tetraphenylethylene (TPE)-bile acid conjugates was described. It was found that the synergetic combination of the distinct properties of TPE and bile acid units could directly afford uniform fluorescent vesicles with amphiphilic binding pockets in the membrane. This structural features of such vesicles provides a unique opportunity for facile construction of functional chemical systems through host–guest chemistry.

Amphiphilic chitooligosaccharide-graft-poly(e-caprolactone) (COS-g-PCL) copolymers were controllably synthesized using protection/deprotection technique of COS via trimethylsilyl groups and ring-opening polymerization of e-caprolactone. Their crystalline properties were investigated with differential scanning calorimetry. With the increase of PCL content in graft copolymer, the values of ΔH and Xc became enhanced, and Tm shifted to higher temperatures. Micellar properties of amphiphilic graft copolymers were studied. Spherical micelles from COS11-g-PCL132 were prepared. However, due to the higher PCL content, the spherical micelles from COS11-g-PCL520 easily confused together so that the complicated network morphology was formed. Interestingly, hierarchical structure was observed in the formed network morphology, as being driven by the crystallization of PCL segments in micelles. Using pyrene as a model compound, the micelles from COS11-g-PCL132 copolymers can be loaded by hydrophobic therapeutic agent, potentially offering an appropriate vehicle for drug delivery.

Two new thiophene-substituted porphyrins and their zinc complexes were synthesized and electropolymerized via thiophene units on different electrode surfaces. Electrochemical characterizations show that the resultant polythiophenemetalloporphyrin hybrid materials are highly electroactive and exhibit remarkable higher electrochemical stability. Interestingly, they exhibit a charge-trapping effect. A mechanism for the observed charge-trapping phenomenon was proposed and supported by using model compounds. The deposited polymer films on different electrode surfaces exhibit a homogeneous morphology and possess good processability (soluble in polar solvents such as DMSO or DMF). Besides electrochemical method, UV/vis, NMR, FTIR, TEM and SEM were employed to characterize the new hybrid material.

Two new thiophene derivatives bearing redox active p-nitrophenyl units were synthesized and electropolymerized to conducting polymers. It is found that not only the structure of monomer, but also the employed polymerization conditions have considerable effect on the electroactivity of the bonded redox groups of resulting polymer films. Depending on used conditions such as polymerization time, the polymerization of the same monomer could result in a polymer with well-defined redox transition of the nitrophenyl group or a polymer, in which the redox group is completely electrochemical inaccessible. Using designed experiments, we explained this phenomenon. These investigations provide further knowledge about the behaviors of redox group attached to electrode surface.

Different nanoparticles coated with a variety of carboxyl groups were prepared and a facile, competitive approach to engineering of colloid assembles was established. As shown by UV–vis, florescence spectroscopy and TEMtransmission electron microscopy, various aggregate structures of nanoparticles could be easily created by using hydrogen-bonding interaction of attached carboxyl groups. The related assembling process is effective, controllable and reversible by varying the pH.

Molecularly imprinted photonic polymers can serve as ideal sensing elements for efficiently creating cross-reactive sensor arrays. Based on this concept, a new method for sensitive and label-free detection of challenging PBDEs was developed, by which the direct detection and discrimination of trace levels of PBDEs against a high-background of interferents was achieved with 100% accuracy.

Three new thiophene derivatives containing different activated ester groups covalently attached to the thiophene ring via a linear undecyl spacer have been synthesized. Electropolymerization of these monomers in acetonitrile led to stable electroactive polymers, while activated functional groups withstand the polymerization conditions and were correctly incorporated in the resulting polymers. These polymers show the characteristic electrochemical behavior of poly(3-alkylthiophene)s with the reversible redox transition in the range of 0.7–0.9 V. UV/Vis spectra of them exhibit an absorption maximum at around 460 nm. Conductivity measurements on oxidized films of these polymers by means of the two-probe method gave values in the range of 10 −3 –10 −2 S cm −1 . The reactivity of the pendant activated ester groups was demonstrated by the reaction with butylamine, (4-amino-2-oxabutyl) ferrocene and 2-aminoanthraquinone. Spectroscopic studies and electrochemical characterization confirmed that the immobilized amino compounds are covalently bound to the polymer surfaces. These results suggest that the obtained new polymers can be used as electrically conducting carrier materials for the immobilization of biochemically interesting molecules.

The synthesis and electropolymerization of 3-alkylthiophenes functionalized with a terminal amino group and its protected forms are reported. As expected, due to the strong electronic interference of the amino group, the electropolymerization of the unprotected monomer is fully inhibited. After protection of the amino group the polymerizability of the corresponding monomers is considerably improved; however, the successful polymerization process clearly depends on the nature of the used protective group. Only such monomers in which the nucleophilic character of the amino group is strongly suppressed by a suitable proctective group undergo electropolymerization to form the corresponding electroactive polymers. The obtained polymers are electrochemically stable and, besides the typical properties such as redox behavior and electrochromism, they exhibit a distinct solvatochromic behavior. Electrical conductivity measurements on their oxidized forms by means of the two-probe method give values in the range of 10 -3 to 10 -2 S . cm -1 . The feasibility of using the resulting polymers as conducting carrier materials was demonstrated by the removal of the protecting groups and the subsequent attachment of a redox active ferrocene compound. Electrochemical and spectroscopic experiments confirmed that after the polymer analogous reaction the used redox active ferrocene model compound is covalently immobilized onto the polymer surface and the electroactivity of the bonded redox groups as well as the carrier materials is retained.

Two new functionalized thiophene derivatives bearing epoxy and carbonate groups were synthesized. The electrooxidative polymerization of both monomers led to stable electroactive polymers, while the functional groups remained unchanged during the polymerization process. Electrochemical and spectroscopic data of the resulting homopolymers reveal that these polymers possess an extended conjugated π-electron system comparable to unfunctionalized poly(3-alkylthiophene)s. Both monomers can also easily copolymerize with 3-methylthiophene to form the corresponding conducting copolymers. SEM photographs show that the obtained homopolymers and copolymers exhibit a very compact homogeneous morphology, indicating that the new thiophene monomers have good formability of polymer films. The measurement of electrical conductivity of these polymers by means of two-probe method gave values in the range of 10 2 to 10 -1 S . cm -1 . Using butylamine and 2-aminoanthraquinone as model compounds, it was demonstrated that amino compounds easily react with pendant epoxy and cyclic carbonate groups and are convalently attached to the new electroactive polymer surfaces. Thus, a new type of conducting polymers with pendant reactive groups was developed.

Electrooxidative polymerization of three new p-nitrophenyl-functionalized thiophene derivatives leads to materials which show the electroactivities of both nitrobenzene and polythiophene. However, other than the reversible redox transition in solution, the nitro groups exhibit a complex nature of the cyclic voltammetric curve in the obtained solid polymeric films. It was found that the electrochemical behavior of the nitro groups has a dramatic effect on the conjugated π-electron systems of the substituted polythiophenes. Upon electrochemical addressing of the nitro groups the electroactivities of the corresponding polymers decrease rapidly compared to their analogous polymers without nitro groups. FTIR studies of these polymers revealed that after the reduction/oxidation process of the nitro groups still a large amount of electrolyte salt remains in the polymer films. As typical of functionalized polythiophenes. however, these new polymers can be switched under controlled conditions between their oxidized and neutral forms and exhibit the typical properties of electroactive polythiophenes, e.g., electrochromism.

With the synthesis of two new functionalized thiophene activated esters and their electrocopolymerization with 3-methylthiophene, two types of redox active polymers have been prepared. FTIR studies of the resultant polymers reveal that both types of activated ester groups withstand the applied electrooxidative conditions and are correctly integrated into the corresponding polymers. The electrocopolymerization experiments show that the composition of the obtained polymers strongly depends on the ratio of the components in the reaction medium. With the increase of the ratios of pentafluorophenyl thiophene-3-acetate/3-methylthiophene or succinimido thiophene-3-acetate/3-methylthiophene, a higher concentration of functionalized thiophene units is incorporated into the polymer chains. The measurement of the conductivity on these polymeric films gave a value in the range of 10 -3 to 10 -2 S.cm -1 , which is comparable to that of the unsubstituted polythiophene and consistent with the conjugation grade suggested by electrochemical and UV-vis spectroscopic data. As expected, the pendant reactive ester groups on the electrode surfaces react rapidly with different amino compounds without loss of the electroactivity of the polymers. Therefore, these novel polymeric materials can be used as electrode interfaces for further functionalizations, especially for the immobilization of amines, peptides, and enzymes.

By the protection of the carboxyl group of 3-thiopheneacetic acid with differently substituted benzyl groups a series of new thiophene derivatives were synthesized. While 3-thiopheneacetic acid is not electropolymerizable, the new obtained monomers can be easily electrooxidized to form stable electroactive polymers. The electrochemical characterizations show that the substitution of the benzyl groups exerts little effect on the electropolymerization process and that the obtained polymers exhibit the typical properties of polythiophene derivatives, e. g., redox behavior and electrochromism. SEM studies show that all synthesized monomers possess a very good film formability and the resulting polymers exhibit a rather compact and homogeneous morphology on the Pt electrodes also containing scattered particles. Using p-nitrobenzyl-protected polymer as an illustrative example, it was demonstrated that the used protecting group can be easily split off in the solid state and the desired reactive carboxyl group can be produced on the polymer surface. Therefore, through the protection of the carboxyl group, the electropolymerization and the following removal of the protecting group, a new type of polymer matrix material with reactive carboxyl groups was simply prepared by using commercially available 3-thiopheneacetic acid monomer.

Gas transport of carbon dioxide, oxygen, nitrogen and methane gases in a series of poly(phenylene thioether imide)s based on 2,2-bis(3,4-decarboxyphenyl) hexafluoropropane dianhydride and diamine-terminated oligo(phenylene thioether)s has been investigated. The effects of the oligo(phenylene thioether) length on the gas permeabilities and diffusivities were determined and correlated with chain packing of the polymers. The incorporation of a long oligo(phenylene thioether) segment in the polymer backbone decreases gas permeability and permselectivity simultaneously. The decreases in permeability coefficients can be related to decreases in both the diffusion coefficients and the solubility coefficients of all the gases. Finally, the physical and gas transport properties are simply compared between poly(phenylene thioether imide)s and poly(phenylene thioether).

Based on azide-containing clickable inverse opal, a strategy for efficiently fabricating functional photonic materials was developed. By using three types of ethynylated compounds as model molecules, it is found that different functional groups can be facilely introduced into the prepared inverse opal via click reaction to access various inverse opaline materials.

Using chitooligosaccharides (COS) as the backbones and polycaprolactones (PCL) as the branches, a novel type of amphiphilic graft copolymers with a large amount of free OH and NH2 groups remained on the COS backbones was synthesized. The obtained Chitooligosaccharide-graft-poly(e-caprolactone)(COS-g-PCL) was self-assembled into giant vesicles which served as templates for the preparation of hollow spheres of a series of metals(Au, Ag, Cu, Pt, and Pd). The method involved the initial mixing of COS-g-PCL and metal-containing groups or metal ions to generate corresponding complex, followed by adding the selective solvent of water to induce the self-assembly of the graft copolymers into giant vesicles; Metal ions were reduced and crosslinked by a subsequent calcination procedure to form metal hollow spheres. In addition, hybrid hollow spheres with fluorescent quantum dots and silica hollow spheres were also prepared by slightly modified procedures. A preliminary study on the trinitrotoluene sensor of CdS/vesicle hybrid hollow spheres revealed a considerable sensitivity, which exemplifies the distinct properties imparted by the hybrid hollow structure. All of the results demonstrate that the giant vesicles self-assembled from COS-g-PCL could be utilized as effective templates for the synthesis of various hollow spheres. Using Chitooligosaccharide-graft-poly(e-caprolactone) vesicles as general templates, the hollow spheres of a series of metals such as Au, Ag, Cu, and Pt were produced. The method involved the initial absorption of metal ions from solution into the functional surface layer of the graft copolymer giant vesicles. Metal ions were reduced and crosslinked by a subsequent calcination procedure to form metal hollow spheres. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Based on stepwise deposition of MOF films on a colloid crystal substrate, a strategy for fabricating photonic MOF films was developed. We found that the integration of a photonic structure endows MOF materials with unique optical properties, which can be used as a general and effective transduction scheme for a convenient study of the host–guest chemistry of MOFs.

The integration of 3D-ordered macropores with poly(ionic liquid)s can significantly extend the functions of poly(ionic liquid)s, and afford a new type of material, which can serve as not only tunable photonic crystals and anion-directed molecular gating system, but also as a surface with enhanced tunable wettability and unique stable electro-optic switching.

A rapid and facile method was found to access one-molecule-thick free-standing organic nanosheets in a high yield with controllable size and shape by self-assembly of cucurbit[8]uril and small organic molecules.

A simple approach is described for the preparation of chitooligosaccharide-based giant vesicles with variable size by simply tuning the water content in the water-dioxane mixture, by which reactive vesicles with diameters in the range of 0.5-400 microm were easily prepared.

A new route to form multiple morphologies was outlined using amphiphilic graft copolymers with interesting biological and pharmacological properties by proper adjustment of backbone and graft chain length.

In this work, maleimide-containing polymer inverse opals have been successfully prepared by utilization of an acrylate monomer bearing a masked (protected) maleimide unit. As an ideal clickable functional group, maleimide can promote the Michael addition of thiol-containing molecules and the thermoreversible Diels–Alder reaction of furan derivatives, providing tremendous opportunities to produce various functional materials from one maleimide-containing polymer. As a demonstration, four chemical systems were facilely evolved from the prepared maleimide-containing inverse opal. By exploiting the nucleophilic thiol–ene reaction of maleimide, the zwitterionic pH-responsive inverse opal and electroactive inverse opal were first fabricated by reacting with cysteine and thiol-containing ferrocene derivatives, respectively. Based on the same reaction, it was also found that the maleimide-containing inverse opal could serve as a self-reporting sensing platform to sensitively detect the reduction of oxidized glutathione by specific enzymes. On the other hand, the thermoreversible nature of the Diels–Alder reaction of the maleimide groups made it possible to construct a dynamic molecule gating system by reacting with alkyl-chain-substituted furan derivatives from the prepared interconnected macroporous film. In fact, due to the unlimited variety provided by the two kinds of reactions mentioned above, the described photonic material exhibits a significant extendibility and could be easily post-modified for special purposes with maintenance of the opaline structure. Thus, this novel clickable maleimide-containing polymer inverse opal could serve as a reactive platform for producing a variety of functional photonic materials.

Active photonic crystals (PC) or photonic crystal heterostructures have many applications such as chemical and biological sensors, active colour displays, structural colour printing and fluorescence enhancement. However, photonic crystal structures with the different functions mentioned above require different preparation methods, and some of them require sophisticated instruments for specific production processes. Thus, development of a simple way or a useful platform for conveniently fabricating specific photonic crystal structures with different functions is highly desirable and significant. Herein, by exploiting the self-polymerization of dopamine, we successfully introduced polydopamine (PDA) into silica opaline templates and produced PDA photonic crystal structures. Based on the utilization of the unique properties of PDA such as reactivity, reductive ability, powerful adhesive capability as well as carbonizable feature, PDA-based photonic crystal structures provide a very useful platform for further convenient fabrication of multifunctional photonic crystal structures with a variety of potential applications. Due to the virtually unlimited variety provided by the active secondary reactions of PDA, the post-modification of PDA-based photonic crystals can readily afford photonic crystal based chemical or biological sensors. The reductive as well as adhesive ability of PDA provides another tremendous opportunity to produce photonic crystal heterostructures with various metals, metal oxides, polymer or semiconductor nanoparticles. As a demonstration, PDA/Ag/PDA and PDA/Pt/PDA opaline structures were prepared by PDA-assisted metallization or adsorption, respectively, which could find promising application in fluorescence enhancement of organic dyes or chemical solvent sensors. More importantly, the carbonizable feature of PDA allows for efficiently producing carbon inverse opaline films as well as metal particle doped carbon inverse opaline films by carbonizing the corresponding PDA, PDA/Ag/PDA or PDA/Pt/PDA photonic structures, which may show various potential applications in catalysis and energy conversion.

5,15-Bis[acetylene-4-(ethylenedioxy)thiophene]-10,20-bis(4-carboxyphenyl)porphyrin was synthesized by a Sonogashira coupling and polymerized to fibres; TEM and AFM images show uniform porphyrin wires with a length of several micrometers and a thickness of less than 4 nm.

Molecularly imprinted photonic polymer (photonic MIP) film can be prepared based on the combination of colloidal-crystal templating and molecular imprinting techniques. This kind of film is an ideal sensing material due to its distinct advantages such as high selectivity, rapid response and signal self-reporting. However, for the successful formation of this kind of sensing material, with high selectivity towards the imprinted molecules, a highly ordered and interconnected 3D macroporous structure, and a visually perceptible color change like pH-paper, each fabrication is strongly dependent on the determination of the main factors and an arduous process of preparation. In this work, the rational design of molecularly imprinted photonic film was realized by using response surface methodology (RSM) based on central composite design (CCD). Design of experiments following CCD allows selected factors to be changed systematically and simultaneously, thus reducing the number of experiments necessary. 20 photonic MIPs with different ratios of monomer : crosslinker : solvent were synthesized and their sensing properties were checked. Data were analyzed using analysis of variance (ANOVA). A second-order polynomial model was used for predicting the response. This model revealed that the crosslinker was dominant in the performance of photonic MIPs, and also allowed the optimum polymer composition to be predicted. Creatinine was used as the model analyte. Under the predicted optimum conditions, a sensor for the convenient detection of creatinine was fabricated with high sensitivity, quick response, and good stability. This also testifies to the fact that the RSM approach is appropriate to investigate the interactive effect of the selected factors and optimize polymerization recipes with a limited number of experiments. It is anticipated that this method opens a way to the efficient fabrication of photonic MIPs.

In this work, polydopamine-coated electrospun polystyrene (PS) nanofibrous mats were successfully prepared by simply immersing the PS mats into dopamine alkaline Tris buffer solution for 24 h. The successful growth of polydopamine (Pdop) was confirmed with X-ray photoelectron spectroscopy (XPS). The thickness of the Pdop layer was about 20 nm observed by transmission electron microscope (TEM). The wetting behavior was changed tremendously into superhydrophilicity. Combining the unique characteristics of Pdop as active secondary reaction sites and electrospun mat as a flexible porous support, this hierarchically structured nanofibrous mat can serve as a useful platform for developing porous functional membranes. As demonstrated, oil/water separation and molecule gating membranes were fabricated by using the Michael reaction of Pdop coating with undecanethiol (UT) or 11-mercaptoundecanoic acid (MUA), respectively. As an oil/water separation membrane, the long alkyl chains of UT anchored on the membrane surface increased the contact angle (CA) of water distinctly, and water was blockaded completely while oil smoothly passed through the membrane. Similarly, a molecule gating membrane was constructed based on the pH-induced deprotonation of the carboxyl group of MUA, and its permeation selectivity was confirmed by cyclic voltammetry (CV) with an electrochemical probe. Moreover, the reductive property of the Pdop coating was also utilized to facilely introduce various metal nanoparticles into membrane systems for potential applications, for example, a silver nanoparticle-decorated membrane can be used as an effective antibacterial film as confirmed by the modified Kirby-Bauer method. All performed experiments demonstrate that polydopamine-coated nanofibrous mats can serve as a versatile platform for producing porous functional membranes.