Synthesis and characterization of nanoporous phospho-tungstate organic-inorganic hybrid materials

Nanoporous phospho-tungstate organic-inorganic hybrid materials have been synthesized from sodium tungstate and mono-n-dodecyl phosphate (MDP), which was used as both surfactant and phosphorus precursor. These hybrid materials were thoroughly characterized by N2 adsorption, elemental analysis, powder XRD, FTIR, Raman, TG, TEM and XPS and possess lamellar structures with interlayer spacings of 3.2 nm. A plausible method for formation of hybrid materials comprised of lacunary Keggin anions and micelles of surfactants is proposed. © The Royal Society of Chemistry 2008.

New hybrid system:poly (ethylene glycol) hydrogel with covalently bonded pegylated nanotubes

Hydrogels containing carbon nanotubes (CNTs) are expected to be promising conjugates because they might show a synergic combination of properties from both materials. Most of the hybrid materials containing CNTs only entrap them physically, and the covalent attachment has not been properly addressed yet. In this study, single-walled carbon nanotubes (SWNTs) were successfully incorporated into a poly(ethylene glycol) (PEG) hydrogel by covalent bonds to form a hybrid material. For this purpose, SWNTs were functionalized with poly(ethylene glycol) methacrylate (PEGMA) to obtain water-soluble pegylated SWNTs (SWNT–PEGMA). These functionalized SWNTs were covalently bonded through their PEG moieties to a PEG hydrogel. The hybrid network was obtained from the crosslinking reaction of poly(ethylene glycol) diacrylate prepolymer and the SWNT–PEGMA by dual photo-UV and thermal initiations. The mechanical and swelling properties of the new hybrid material were studied. In addition, the material and lixiviates were analyzed to elucidate any kind of SWNT release and to evaluate a possible in vitro cytotoxic effect. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.

Synthesis and characterisation of polyacrylonitrile and its derived carbon materials

Carbon is a versatile material which is composed of different allotropes, and also come in with different structures. Carbon nanofibres (CNFs) is one dimensional carbon nanomaterials, which have exhibited superior mechanical properties, great specific area, good electrical conductivity, good biocompatibility, and ease of modification. In addition to the lower cost associated to compare with carbon nanotubes (CNTs), CNFs have been attracted in numerous applications, such as reinforcement materials, filtrations, Li-ion battery, supercapacitor as well as tissue engineering, just to list a few. Therefore, it is a great deal to understand the relationship between the fabrication conditions and the characteristics of the resulted CNFs. In this project, electrospun PAN NFs were used as precursor material to fabricate carbon nanofibres. In order to produce CNFs with good morphology, the processing parameters of PAN nanofibres by electrospinning was optimized toward to the morphology at solution concentration of 12 wt%. The optimized processing parameters at given concentration were 16 kV, 14 cm and 1.5 mL/h, which led to the formation of PAN NFs with average fibre diameter of approximately 260 nm. Along with the effect of processing parameter study, the effect of concentration on the morphology was also carried out at optimized processing parameters. It was found that by increasing concentration of PAN solution from 2 to 16%, the resulted PAN transformed from beads only, to beaded fibres and finally to smooth fibres. With further increasing concentration the morphology of smooth fibres remain with increase in the fibre diameter. Electrospun PAN NFs with average fibre of 306 nm was selected to be converted into CNFs by using standard heating procedures, stabilisation in air at 280 °C and carbonization in N2. The effect of carbonization temperature ranging from 500 to 1000 °C was investigated, by using SEM, FTIR, Raman, and Impedance spectroscopy. With increasing carbonization temperature from 500 to 1000 °C, the diameter of NFs was decreased from 260 to 187, associated with loss of almost all functional groups of NFs. It was indicated by Raman results, that the graphitic crystallite size was increased from 2.62 to 5.24 nm, and the activation energy obtained for this growth was 7570 J/mol. Furthermore, impedance results (i.e. Cole-Cole plot) revealed that the electrical characteristic of CNFs transitioned from being insulating to electrically conducting in nature, suggested by the different electrical circuits extracted from Cole-Cole plots with carbonization temperature from 500 to 800 °C. The carbonization on PAN NFs with diameter of ~431nm was carried out by using novel route, microwave plasma enhance chemical vapour deposition (MPECVD) process. To compare with carbonized PAN NFs by using conventional route, MPECVD was not only able to facilitate carbonization process, but more interestingly can form carbon nanowalls (CNWs) grown on the surfaces of carbonized PAN NFs. Suggested by the unique morphology, the potential applications for the resulted carbon fibrous hybrid materials are supercapacitor electrode material, filtrations, and etc., The method developed in this project required one step less, compared with other literature. Therefore, using MPECVD on stabilised PAN NFs is proposed as economical, and straightforward approach towards mass production of carbon fibrous hybrid materials containing CNWs.

Photoluminescent materials based on PMMA and a highly-emissive octahedral molybdenum metal cluster complex

Materials that combine photoluminescence, optical transparency and facile processability are of high importance in many applications. This article reports on the development of photoluminescent poly(methyl methacrylate) materials based on novel highly emissive anionic molybdenum cluster complex [{Mo6I8}(OTs)6]2– (where OTs– is the p-toluenesulfonate ion). The materials were obtained by both solution and bulk copolymerisation of methyl methacrylate and (dMDAEMA)2[{Mo6I8}(OTs)6], where dMDAEMA+ is the polymerisable cation [2-(methacryloyloxy)ethyl]dimethyl-dodecylammonium. Evaluation of the resultant hybrid materials showed that one could combine the excellent photoluminescent properties of the cluster complex with the transparency and processability of PMMA.

Photoluminescent materials based on PMMA and a highly-emissive octahedral molybdenum metal cluster complex

Materials that combine photoluminescence, optical transparency and facile processability are of high importance in many applications. This article reports on the development of photoluminescent poly(methyl methacrylate) materials based on novel highly emissive anionic molybdenum cluster complex [{Mo6I8}(OTs)6]2- (where OTs- is the p-toluenesulfonate ion). The materials were obtained by both solution and bulk copolymerisation of methyl methacrylate and (dMDAEMA)2[{Mo6I8}(OTs)6], where dMDAEMA+ is the polymerisable cation [2-(methacryloyloxy)ethyl]dimethyl-dodecylammonium. Evaluation of the resultant hybrid materials showed that one could combine the excellent photoluminescent properties of the cluster complex with the transparency and processability of PMMA.

Effect of calcium source on structure and properties of sol-gel derived bioactive glasses

The aim was to determine the most effective calcium precursor for synthesis of sol-gel hybrids and for improving homogeneity of sol-gel bioactive glasses. Sol-gel derived bioactive calcium silicate glasses are one of the most promising materials for bone regeneration. Inorganic/organic hybrid materials, which are synthesized by incorporating a polymer into the sol-gel process, have also recently been produced to improve toughness. Calcium nitrate is conventionally used as the calcium source, but it has several disadvantages. Calcium nitrate causes inhomogeneity by forming calcium-rich regions, and it requires high temperature treatment (>400 C) for calcium to be incorporated into the silicate network. Nitrates are also toxic and need to be burnt off. Calcium nitrate therefore cannot be used in the synthesis of hybrids as the highest temperature used in the process is typically 40-60 C. Therefore, a different precursor is needed that can incorporate calcium into the silica network and enhance the homogeneity of the glasses at low (room) temperature. In this work, calcium methoxyethoxide (CME) was used to synthesize sol-gel bioactive glasses with a range of final processing temperatures from 60 to 800 C. Comparison is made between the use of CME and calcium chloride and calcium nitrate. Using advanced probe techniques, the temperature at which Ca is incorporated into the network was identified for 70S30C (70 mol % SiO, 30 mol % CaO) for each of the calcium precursors. When CaCl was used, the Ca did not seem to enter the network at any of the temperatures used. In contrast, Ca from CME entered the silica network at room temperature, as confirmed by X-ray diffraction, Si magic angle spinning nuclear magnetic resonance spectroscopy, and dissolution studies. CME should be used in preference to calcium salts for hybrid synthesis and may improve homogeneity of sol-gel glasses.

Polymerisable octahedral rhenium cluster complexes as precursors for photo/electroluminescent polymers

New polymerisable photoluminescent octahedral rhenium cluster complexes trans-[{Re6Q8}(TBP)4(VB)2] (Q = S or Se; TBP-p-tert-butylpyridine; VB-vinyl benzoate) have been synthesised, characterised and used to construct rhenium cluster-organic polymer hybrid materials. These novel polymer systems are solution-processable and the rhenium clusters retain their photoluminescent properties within the polymer environment. Notably, when the rhenium cluster complexes are incorporated into the matrix of the electroluminescent polymer poly(N-vinylcarbazole), the resultant cluster polymer hybrid combined properties of both components and was used successfully in the construction of a polymer light emitting diode (PLED). These prototype devices are the first PLEDs to incorporate octahedral rhenium clusters and provide the first direct evidence of the electroluminescent properties of rhenium clusters and indeed, to the best of our knowledge, of any member of the family of 24-electron hexanuclear cluster complexes of molybdenum, tungsten or rhenium.

Zr-containing hybrid organic-inorganic mesoporous materials:hydrophobic acid catalysts for biodiesel production

Zirconium-containing periodic mesoporous organosilicas (Zr-PMOs) with varying framework organic content have been synthesized through a direct synthesis method. These materials display the excellent textural properties of the analogous inorganic solid acid Zr-SBA-15 material. However, the substitution of silica by organosilicon species provides a strong hydrophobic character. This substitution leads to meaningful differences in the environment surrounding the zirconium metal sites, leading the modification of the catalytic properties of these materials. Although lower metal incorporation is accomplished in the final materials, leading to a lower population of metal sites, hydrophobisation leads to an impressive beneficial effect on the intrinsic catalytic activity of the zirconium sites in biodiesel production by esterification/transesterification of free fatty acid -containing feedstock. Moreover, the catalytic activity of the highly hybridised materials is hardly affected in presence of large amounts of water, confirming their very good water-tolerance. This makes Zr-PMO materials interesting catalysts for biodiesel production from highly acidic water-containing feedstock. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterizing the hierarchical structures of bioactive sol-gel silicate glass and hybrid scaffolds for bone regeneration

Bone is the second most widely transplanted tissue after blood. Synthetic alternatives are needed that can reduce the need for transplants and regenerate bone by acting as active temporary templates for bone growth. Bioactive glasses are one of the most promising bone replacement/regeneration materials because they bond to existing bone, are degradable and stimulate new bone growth by the action of their dissolution products on cells. Sol-gel-derived bioactive glasses can be foamed to produce interconnected macropores suitable for tissue ingrowth, particularly cell migration and vascularization and cell penetration. The scaffolds fulfil many of the criteria of an ideal synthetic bone graft, but are not suitable for all bone defect sites because they are brittle. One strategy for improving toughness of the scaffolds without losing their other beneficial properties is to synthesize inorganic/organic hybrids. These hybrids have polymers introduced into the sol-gel process so that the organic and inorganic components interact at the molecular level, providing control over mechanical properties and degradation rates. However, a full understanding of how each feature or property of the glass and hybrid scaffolds affects cellular response is needed to optimize the materials and ensure long-term success and clinical products. This review focuses on the techniques that have been developed for characterizing the hierarchical structures of sol-gel glasses and hybrids, from atomicscale amorphous networks, through the covalent bonding between components in hybrids and nanoporosity, to quantifying open macroporous networks of the scaffolds. Methods for non-destructive in situ monitoring of degradation and bioactivity mechanisms of the materials are also included. © 2012 The Royal Society.

Investigating polymer-peptide conjugates and electrospinning for the production of advanced materials

This thesis describes the production of advanced materials comprising a wide array of polymer-based building blocks. These materials include bio-hybrid polymer-peptide conjugates, based on phenylalanine and poly(ethylene oxide), and polymers with intrinsic microporosity (PIMs). Polymer-peptides conjugates were previously synthesised using click chemistry. Due to the inherent disadvantages of the reported synthesis, a new, simpler, inexpensive protocol was sought. Three synthetic methods based on amidation chemistry were investigated for both oligopeptide and polymerpeptide coupling. The resulting conjugates produced were then assessed by various analytical techniques, and the new synthesis was compared with the established protocol. An investigation was also carried out focussing on polymer-peptide coupling via ester chemistry, involving deprotection of the carboxyl terminus of the peptide. Polymer-peptide conjugates were also assessed for their propensity to self-assemble into thixotropic gels in an array of solvent mixtures. Determination of the rules governing this particular self-assembly (gelation) was required. Initial work suggested that at least four phenylalanine peptide units were necessary for self-assembly, due to favourable hydrogen bond interactions. Quantitative analysis was carried out using three analytical techniques (namely rheology, FTIR, and confocal microscopy) to probe the microstructure of the material and provided further information on the conditions for self-assembly. Several polymers were electrospun in order to produce nanofibres. These included novel materials such as PIMs and the aforementioned bio-hybrid conjugates. An investigation of the parameters governing successful fibre production was carried out for PIMs, polymer-peptide conjugates, and for nanoparticle cages coupled to a polymer scaffold. SEM analysis was carried out on all material produced during these electrospinning experiments.

Kerr nonlinear switching in a hybrid silicasilicon microspherical resonator

A hybrid silicon-core, silica-clad microspherical resonator has been fabricated from the semiconductor core fiber platform. Linear and nonlinear characterization of the resonator properties have shown it to exhibit advantageous properties associated with both materials, with the low loss cladding supporting high quality (Q) factor whispering gallery modes which can be tuned through the nonlinear response of the crystalline core. By exploiting the large wavelength shift associated with the Kerr nonlinearity, we have demonstrated all-optical modulation of a weak probe on the timescale of the femtosecond pump pulse. This novel geometry offers a route to ultra-low loss, high-Q silica-based resonators with enhanced functionality.

Optical modulators with 2D layered materials

Light modulation is an essential operation in photonics and optoelectronics. With existing and emerging technologies increasingly demanding compact, efficient, fast and broadband optical modulators, high-performance light modulation solutions are becoming indispensable. The recent realization that 2D layered materials could modulate light with superior performance has prompted intense research and significant advances, paving the way for realistic applications. In this Review, we cover the state of the art of optical modulators based on 2D materials, including graphene, transition metal dichalcogenides and black phosphorus. We discuss recent advances employing hybrid structures, such as 2D heterostructures, plasmonic structures, and silicon and fibre integrated structures. We also take a look at the future perspectives and discuss the potential of yet relatively unexplored mechanisms, such as magneto-optic and acousto-optic modulation.

g-C3N4/NaTaO3 organic–inorganic hybrid nanocomposite:high-performance and recyclable visible light driven photocatalyst

Novel g-C3N4/NaTaO3 hybrid nanocomposites have been prepared by a facile ultrasonic dispersion method. Our results clearly show the formation of interface between NaTaO3 and g-C3N4 and further loading of g-C3N4 did not affect the crystal structure and morphology of NaTaO3. The g-C3N4/NaTaO3 nanocomposites exhibited enhanced photocatalytic performance for the degradation of Rhodamine B under UV–visible and visible light irradiation compared to pure NaTaO3 and Degussa P25. Interestingly, the visible light photocatalytic activity is generated due to the loading of g-C3N4. A mechanism is proposed to discuss the enhanced photocatalytic activity based on trapping experiments of photoinduced radicals and holes. Under visible light irradiation, electron excited from the valance band (VB) to conduction band (CB) of g-C3N4 could directly inject into the CB of NaTaO3, making g-C3N4/NaTaO3 visible light driven photocatalyst. Since the as-prepared hybrid nanocomposites possess high reusability therefore it can be promising photocatalyst for environmental applications.

Synthesis of a novel and stable g-C3N4–Ag3PO4 hybrid nanocomposite photocatalyst and study of the photocatalytic activity under visible light irradiation

A facile and reproducible template free in situ precipitation method has been developed for the synthesis of Ag3PO4 nanoparticles on the surface of a g-C3N4 photocatalyst at room temperature. The g-C3N4–Ag3PO4 organic–inorganic hybrid nanocomposite photocatalysts were characterized by various techniques. TEM results show the in situ growth of finely distributed Ag3PO4 nanoparticles on the surface of the g-C3N4 sheet. The optimum photocatalytic activity of g-C3N4–Ag3PO4 at 25 wt% of g-C3N4 under visible light is almost 5 and 3.5 times higher than pure g-C3N4 and Ag3PO4 respectively. More attractively, the stability of Ag3PO4 was improved due to the in situ deposition of Ag3PO4 nanoparticles on the surface of the g-C3N4 sheet. The improved performance of the g-C3N4–Ag3PO4 hybrid nanocomposite photocatalysts under visible light irradiation was induced by a synergistic effect, including high charge separation efficiency of the photoinduced electron–hole pair, the smaller particle size, relatively high surface area and the energy band structure. Interestingly, the heterostructured g-C3N4–Ag3PO4 nanocomposite significantly reduces the use of the noble metal silver, thereby effectively reducing the cost of the Ag3PO4 based photocatalyst.

Book review: Laurel Kamada, Hybrid Identities and Adolescent Girls: Being Half in Japan. Bristol: Multilingual Matters, 2010

Arguably, the catalyst for the best research studies using social analysis of discourse is personal ‘lived’ experience. This is certainly the case for Kamada, who, as a white American woman with a Japanese spouse, had to deal first hand with the racialization of her son. Like many other mixed-ethnic parents, she experienced the shock and disap-pointment of finding her child being racialized as ‘Chinese’ in America through peer group taunts, and constituted as gaijin (a foreigner) in his own homeland of Japan. As a member of an e-list of the (Japan) Bilingualism Special Interest Group (BSIG), Kamada learnt that other parents from the English-speaking foreign community in Japan had similar disturbing stories to tell of their mixed-ethnic children who, upon entering the Japanese school system, were mocked, bullied and marginalized by their peers. She men-tions a pervasive Japanese proverb which warns of diversity or difference getting squashed: ‘The nail that sticks up gets hammered down’. This imperative to conform to Japanese behavioural and discursive norms prompted Kamada’s quest to investigate the impact of ‘otherization’ on the identities of children of mixed parentage. In this fascinat-ing book, she shows that this pressure to conform is balanced by a corresponding cele-bration of ‘hybrid’ or mixed identities. The children in her study are also able to negotiate their identities positively as they come to terms with contradictory discursive notions of ‘Japaneseness’, ‘whiteness’ and ‘halfness/doubleness’.The discursive construction of identity has become a central concern amongst researchers across a wide range of academic disciplines within the humanities and the social sciences, and most existing work either concentrates on a specific identity cate-gory, such as gender, sexuality or national identity, or else offers a broader discussion of how identity is theorized. Kamada’s book is refreshing because it crosses the usual boundaries and offers divergent insights on identity in a number of ways. First, using the term ‘ethno-gendering’, she examines the ways in which six mixed-ethnic girls living in Japan accomplish and manage the relationship between their gender and ethnic ‘differ-ences’ from age 12 to 15. She analyses in close detail how their actions or displays within certain situated interactions might come into conflict with how they are seen or constituted by others. Second, Kamada’s study builds on contemporary writing on the benefits of hybridity where identities are fluid, flexible and indeterminate, and which contest the usual monolithic distinctions of gender, ethnicity, class, etc. Here, Kamada carves out an original space for her findings. While scholars have often investigated changing identities and language practices of young people who have been geographi-cally displaced and are newcomers to the local language, Kamada’s participants were all born and brought up in Japan, were fluent in Japanese and were relatively proficient in English. Third, the author refuses to conceptualize or theorize identity from a single given viewpoint in preference to others, but in postmodernist spirit draws upon multiple perspectives and frameworks of discourse analysis in order to create different forms of knowledge and understandings of her subject. Drawing on this ‘multi-perspectival’ approach, Kamada examines grammatical, lexical, rhetorical and interactional features from six extensive conversations, to show how her participants position their diverse identities in relation to their friends, to the researcher and to the outside world. Kamada’s study is driven by three clear aims. The first is to find out ‘whether there are any tensions and dilemmas in the ways adolescent girls of Japanese and “white” mixed parentage in Japan identify themselves in terms of ethnicity’. In Chapter 4, she shows how the girls indeed felt that they stood out as different and consequently experienced isolation, marginalization and bullying at school – although they were able to make better sense of this as they grew older, repositioning the bullies as pitiable. The second aim is to ask how, if at all, her participants celebrate their ethnicity, and furthermore, what kind of symbolic, linguistic and social capital they were able to claim for themselves on the basis of their hybrid identities. In Chapter 5, Kamada shows how the girls over time were able to constitute themselves as insiders while constituting ‘the Japanese’ as outsiders, and their network of mixed-ethnic friends was a key means to achieve this. In Chapter 6, the author develops this potential celebration of the girls’ mixed ethnicity by investigating the privileges they perceived it afforded them – for example, having the advantage of pos-sessing English proficiency and intercultural ‘savvy’ in a globalized world. Kamada’s third aim is to ask how her participants positioned themselves and performed their hybrid identities on the basis of their constituted appearance: that is, how the girls saw them-selves based on how they looked to others. In Chapter 7, the author shows that, while there are competing discourses at work, the girls are able to take up empowering positions within a discourse of ‘foreigner attractiveness’ or ‘a white-Western female beauty’ discourse, which provides them with a certain cachet among their Japanese peers. Throughout the book, Kamada adopts a highly self-reflexive perspective of her own position as author. For example, she interrogates the fact that she may have changed the lived reality of her six participants during the course of her research study. As the six girls, who were ‘best friends’, lived in different parts of the Morita region of Japan, she had to be proactive in organizing six separate ‘get-togethers’ through the course of her three-year study. She acknowledges that she did not collect ‘naturally occurring data’ but rather co-constructed opportunities for the girls to meet and talk on a regular basis. At these meetings, she encouraged the girls to discuss matters of identity, prompted by open-ended interview questions, by stimulus materials such as photos, articles and pic-tures, and by individual tasks such as drawing self-portraits. By giving her participants a platform in this way, Kamada not only elicited some very rich spoken data but also ‘helped in some way to shape the attitudes and self-images of the girls positively, in ways that might not have developed had these get-togethers not occurred’ (p. 221). While the data she gathers are indeed rich, it may well be asked whether there is a mismatch between the girls’ frank and engaging accounts of personal experience, and the social constructionist academic register in which these are later re-articulated. When Kamada writes, ‘Rina related how within the more narrow range of discourses that she had to draw on in her past, she was disempowered and marginalized’ (p. 118), we know that Rina’s actual words were very different. Would she really recognize, understand and agree with the reported speech of the researcher? This small omission of self-reflexivity apart – an omission which is true of most lin-guistic ethnography conducted today – Kamada has written a unique, engaging and thought-provoking book which offers a model to future discourse analysts investigating hybrid identities. The idea that speakers can draw upon competing discourses or reper-toires to constitute their identities in contrasting, creative and positive ways provides linguistic researchers with a clear orientation by which to analyse the contradictions of identity construction as they occur across time in different discursive contexts