Volume 80, Issue 11

Novelty and creativity make life more beautiful and enjoyable! As a result, the International Symposium on Novel Materials and their Synthesis (NMS) was initiated in 2005 [1]. This is the 3rd serial symposium (NMS-III) together with the 17th International Symposium on Fine Chemistry and Functional Polymers (FCFP-XVII), which was organized by Fudan University in Shanghai 17-21 October 2007. The National Natural Science Foundation of China, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Shanghai Society of Chemistry and Chemical Industry,and the National Basic Research Program of China (2007CB209700) provided valuable financial support.The symposium was carried out under the auspices of IUPAC. The main objectives of the symposium were to present state-of-the-art preparation of novel materials, and to discuss their performance and application potentials. The wide scope of the symposium provided a valuable multidisciplinary academic exchange on new ideas and the latest findings for the scientific community. At the same time, the forum gave young scientists the opportunity to meet with the international authorities in their specialized areas and to quickly increase their knowledge. The symposium also opened other doors for the participants to learn something more about Fudan University, Shanghai, and China. The symposium was joined by 212 overseas participants from 34 countries and areas and some local distinguished delegates. The scientific program comprised 206 lectures and 90 posters, including one plenary lecture and one public lecture delivered by Prof. J. M. Lehn from France, the 1987 Nobel laureate in chemistry. Detailed, active, and lively discussions were covered by the following five themes: - innovative catalytic and other synthetic methods, including chiral and asymmetrical synthesis - innovative polymer materials, including supramolecular (supermolecular, dynamers), conducting, semiconducting, optoelecronic, and biobased polymers, their properties, and characteristics - innovative energy materials, including fuel cells, solar cells, lithium batteries, Ni-MH batteries, and supercapacitors - innovative nanomaterials and their preparation, characteristics, and applications - other novel materials, including drugs, perfumes, agricultural chemicals, electrical materials, photosensitive materials, displaying materials, and fine ceramics and their preparation The program emphasized that novel materials and their preparation are dynamic research areas that are attracting growing interest from researchers, engineers, industries, and policy-makers. Furthermore, novel materials continue to find applications that serve the needs and interests of producers and consumers. Among these, energy and nanotechnologies are two urgent and important themes. A selection of 23 papers based on specially invited presentations to NMS-III/FCFP-XVII is published in this issue to demonstrate the quality and scope of the two themes of this symposium. During the symposium, the role and contributions of this academic platform to novel materialsand their synthesis are well realized by the participants and sponsors. Holding this symposium inOctober of every odd year in Shanghai is strongly recommended by the advisory board and adopted bythe organization committee. Yuping Wu Conference editor 1. Y. P. Wu. Pure Appl. Chem. 78 , iii (2006).

Organic thin-film field-effect transistors (OTFTs) are emerging as attractive candidates for low-price, large-area, and flexible circuit applications. A variety of organic compounds have been utilized as active semiconductor materials for OTFTs, among which phthalocyanine compounds have attracted considerable attention owing to their remarkable chemical and thermal stability as well as good field-effect performance. Here, we review recent results on the phthalocyanine-based OTFTs. The correlation between the crystal packing structure and the charge transport property is discussed, and we conclude with a description of the future prospects for phthalocyanine-based OTFTs.

Dye-sensitized solar cells (DSSCs) have aroused intense interest over the past decade owing to their low cost and simple preparation procedures. Much effort has been devoted to the study of electrolytes that enable light-to-electrical power conversion for DSSC applications. This review focuses on recent progress in the field of liquid, solid-state, and quasi-solid-state electrolytes for DSSCs. It is believed that quasi-solid-state electrolytes, especially those utilizing thermosetting gels, are particularly applicable for fabricating high photoelectric performance and long-term stability of DSSCs in practical applications.

Sheet-shaped carriers having both obverse and reverse surfaces (thus, a large contact area for targeting a site and adhesive properties without any chemical cross-linker onto tissue surface) have several advantages as surgical dressings. These advantages include active targeting over spherically shaped carriers, which thus have an extremely small contact area for targeting sites. Here, we propose a novel methodology for preparation of a free-standing, ultra-thin, and biocompatible polymer nanosheet having heterosurfaces, fabricated through macromolecular assembly. In the context of biomedical applications, the targeted properties include injectable sheet-shaped drug carriers having precisely controlled size by exploiting micropatterned substrate, and giant polymer nanosheets composed of biocompatible polysaccharides. A huge aspect ratio, in excess of 10 6 , is particularly applicable for novel surgical dressings. These biocompatible polymer nanosheets having heterosurfaces can thus be regarded as new biomaterials for minimally invasive treatment.

The catalysts that can efficiently hydro-reform higher n-paraffin to lower isoparaffins for environmentally friendly gasoline were studied. The catalysts were examined by the conversion of n -hexadecane, n -C 16 H 34 to i -C 6 H 14 ~ i -C 12 H 26 . The tri-modally nanoporous (nanometer-size) catalysts composed of (Ni-Mo)/[γ-Al 2 O 3 ], nano-oxide, and nanocrystalline zeolite have some active and selective performances because of the cooperation between (Ni-Mo)/[γ-Al 2 O 3 ] and the composite of nano-oxide-nanozeolite. The (Ni-Mo)/[γ-Al 2 O 3 ] component holding the skeletal isomerization activity enhances the cracking activity on the composite of nanoporous (np)-Al 2 O 3 -USY (ultra-stable Y-type zeolite) to result in i -C 6 H 14 ~ i -C 12 H 26 as the isomerization of n -hexadecane followed the cracking reaction. The catalyst composed of nanocrystalline BEA (beta-type zeolite) or MFI (ZSM-5-type zeolite) zeolite can be more activated with the nano-SiO 2 than with the nano-Al 2 O 3 . The catalyst composed of the dealuminated zeolite, USY (SiO 2 /Al 2 O 3 = 12) cannot be activated with the nano-SiO 2 but with the nano-Al 2 O 3 . This activation depends on the SiO 2 /Al 2 O 3 ratio of the USY. It is considered that the catalytic property of the three components is partially due to the novel active sites formed concertedly at the interface of the nano-oxides and the nanozeolites. The novel sites have a major role for the isomerization and cracking as the moderate and strong acids and are generated when Si-OH in the nanopores of the USY resulted from the dealumination catches Al-OH in the nano-Al 2 O 3 to form Si-O-Al-O-Al-O-Si instead of Si-O-Al-O-Si-O-Si-O.

This paper focuses on the latest progress in the preparation of a series of nanostructured anode materials in our laboratory and their electrochemical properties for Li-ion batteries. These anode materials include core-shell structured Si nanocomposites, TiO 2 nanocomposites, novel MoO 2 anode material, and carbon nanotube (CNT)-coated SnO 2 nanowires (NWs). The substantial advantages of these nanostructured anodes provide greatly improved electrochemical performance including high capacity, better cycling behavior, and rate capability.

A novel class of single-chain magnets (SCMs), catena -[Fe II (ClO 4 ) 2 {Fe III (bpca) 2 }]ClO 4 and its derivative, were synthesized using the spin-carrier components possessing hard-axis anisotropy (or easy-plane anisotropy, D > 0). The easy-axis-type anisotropy of whole molecules of these compounds, which is essential for the formation of SCMs, arises from the twisted arrangement of easy-planes of Fe(II) along the chain axis. Alternating high-spin Fe(II) and low-spin Fe(III) chain complexes behave as an SCM with a typical frequency-dependent ac susceptibility which obeys Arrhenius law. Below 7 K, catena -[Fe II (ClO 4 ) 2 {Fe III (bpca) 2 }]ClO 4 showed a short-range spin-ordering even in zero external field in a time range of Mössbauer spectroscopy as well as the muon-spin-relaxation (μSR) spectroscopy. Since the easy-axis-type magnetic anisotropy originated from the structural motif of the twisting arrangement of Fe(II) ions, the overall magnetic property was very sensitive to the small structural changes arising from adsorption/desorption of the crystal solvents, and catena -[Fe II (ClO 4 ) 2 {Fe III (bpca) 2 }]ClO 4 showed a reversible change in magnetism that has been referred to as "a magnetic sponge". In its derivative, controls of the molecular structure, the arrangement of chains in the crystal, and magnetic properties both in dc and ac susceptibility have been achieved by the introduction of methyl group on a bpca - ligand, which bridges and mediates the magnetic interaction of the adjoining Fe(II)/Fe(III) ions.

The objective of the present study is development of novel surface-active block, comb-like, and branched copolymers with peroxide-containing chains, as well as derived functional luminescent and magnetic nanoparticles. The main experimental approaches are based on tailored synthesis of the oligoperoxide surfactants of desired structures and derived coordinating complexes of transitional and rare earth elements. Oligoperoxide-based synthesis of luminescent, magnetic, and other functional nanocomposites with controlled size distribution, functionality, reactivity, and biocompatibility is described. Developed methods provide combining the formation of polymeric, metal, and metal-oxide nanoparticles with irreversible modification of their surface by functional fragments capable of radical and other reactions, including binding of physiologically active substances. Novel nanoparticles were studied by chemical, colloidal-chemical, and rheological methods, X-ray diffraction technique, luminescent spectroscopy, and transmission and scanning electronic microscopy. The availability of ditertiary peroxide fragments on the nanoparticle surface provides a possibility of radical grafting functional polymer chains. The developed functional nanoparticles have been used for phagocytosis measurement, as well as markers of pathological cells, antimicrobial remedies, and nanocarriers for targeted drug delivery.

Manganese oxides have been synthesized by a variety of techniques in different nanostructures and studied for their properties as electrode materials in two different storage applications, supercapacitors (SCs) and Li-ion batteries. The composites involving carbon nanotubes (CNTs) and manganese oxides were also prepared by a simple room-temperature method and evaluated as electrode materials in the above applications. The synthesis of nanostructured manganese oxides was carried out by simple soft chemical methods without any structure directing agents or surfactants. The prepared materials were well characterized using different analytical techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), surface area studies, etc. The electrochemical properties of the nanostructured manganese oxides and their composites were studied using cyclic voltammetry (CV), galvanostatic charge-discharge, and electrochemical impedance spectroscopic (EIS) studies. The influence of structural/surface properties on the electrochemical performance of the synthesized manganese oxides is reviewed.

Photosynthesis is a highly efficient solar energy transformation process. Exploiting this natural phenomenon is one way to overcome the shortage in the Earth’s fuel resources. This review summarizes the work carried out in the field of photobioreactor design via the immobilization of photosynthetically active matter within biologically inert matrices and the potential biotechnological applications of the obtained hybrid materials within the domain of solar energy to chemical energy transformation. The first part deals with the design of artificial photosynthetic reaction centers (RCs) by the encapsulation of pigments, proteins, and complexes. The action of thylakoids, chloroplasts, and whole plant cells, immobilized in biocompatible supports, in the conversion of CO 2 into chemical energy, is also addressed. Finally, the latest advances in the exploitation of the bioactivity of photosynthetically active micro-organisms are explored in terms of the production of secondary metabolites and hydrogen.

The key developments in polyaniline-carbon nanotube (PANI-CNT) composites are reviewed. Apart from in situ chemical polymerization and electrochemical deposition, a number of interesting approaches including the use of aniline functionalized CNTs and ultrasound/microwave/γ-radiation initiated polymerization have been used in the preparation of composites. The structure and properties of these composites have been investigated by a variety of techniques including absorption, infrared (IR), Raman, X-ray photoelectron spectroscopy methods, scanning electron and scanning probe microscopy techniques, cyclic voltammetry, and thermogravimetry. The experimental results indicate favorable interaction between PANI and CNTs. The CNT content in these composites controls their conductive, mechanical, and thermal properties. The most interesting characteristic is their easy dispersibility in aqueous solution. The performance evaluation studies of PANI-CNT composites in a number of applications including supercapacitors, fuel cells, sensors, and actuators are highlighted.

New unsupported Co catalysts were studied in the ethanol steam-reforming reaction by in situ diffuse reflectance infrared spectroscopy and on-line mass spectrometry (MS) techniques. The initial ethoxy surface species evolved to surface-acyl species and to acetaldehyde intermediate at temperatures ca. 473 K. The subsequent formation of surface-acetate species occurs at ca. 573 K. Further, the acetate species mainly evolve above 573 K to H 2 and CO 2 products. The route to ketone formation was inhibited on these materials. The presence of surface-hydroxyl groups, which are probably related to the formation of a CoO phase under the reforming conditions, was determined. Alkaline addition shows a beneficial effect on the ethanol steam-reforming over bulk Co catalysts.

In recent years, tetrathiafulvalene (TTF) and its derivatives have been used as semiconducting materials for organic field-effect transistors (OFETs). In this review, we summarize the recent progress in the field of TTF-based OFETs. We introduce the structure and operation of OFETs, and focus on TTF derivatives used in OFETs. TTF derivatives used in OFETs can be divided into three parts by the semiconductor's morphology and the device fabrication technique: (1) TTF derivatives used for single-crystal OFETs, (2) TTF derivatives used for vacuum-deposited thin-film OFETs, and (3) TTF derivatives used for solution-processed thin-film OFETs. The single-crystal OFETs based on TTF derivatives were fabricated by drop-casting method and showed high performance, with the mobility up to 1.4 cm 2 /Vs. The vacuum-deposited thin-film OFETs based on TTF derivatives were well developed, some of which have shown high performance comparable to that of amorphous silicon, with good air-stability. Although the mobilities of most solution-processed OFETs based on TTF derivatives are limited at 10 -2 cm 2 /Vs, the study on solution-processable TTF derivatives and their devices are promising, because of their low-cost, large-area-coverage virtues. The use of organic charge-transfer (OCT) compounds containing TTF or its derivatives in OFETs is also included in this review.

Stabilization of metal nanoparticles (MNPs) in polymeric matrices of different types has proven to be one of the most promising strategies to prevent their aggregation and to retain their properties. Polymer-stabilized MNPs (PSMNPs) and those based on polymer-metal nanocomposite materials are starting to find wide application in various fields of science and technology. In this paper, we demonstrate that metal-polymer nanocomposite membranes (MPNCMs) containing MNPs can easily be prepared in an ion-exchange such as, for example, sulfonated polyetherether ketone (SPEEK) matrix by using the polymeric membranes as nanoreactors for synthesis and to characterize the composition and structure of the formed MNPs. Metal ions (or metal ion complexes) are first incorporated into the polymeric matrix where they undergo reduction, leading to formation of corresponding MPNCMs. Since this technique allows successive metal loading-reduction cycles to be carried out, it enables synthesis of both monometallic and bimetallic (e.g., core-shell) MNPs. The proposed approach is illustrated by synthesis and characterization of MPNCMs containing both monometallic and bimetallic core-shell MNPs, formed by combinations of Pd, Pt, Co, Ni, and Cu, along with their application in electrochemical sensor and biosensor constructions.

Using three synchronized, in situ, nonintrusive, real-time characterization techniques to conduct transient observations, we revealed mechanistic details of a polymer film growth. A thin methylene green (MG) polymer coating (of the order of 35 nm) was used as a model system in this electrochemical microgravimetric imaging ellipsometry (EmIE) investigation. The direct correlation of changes in mass (via quartz crystal microbalance, QCM), ellipsometric angles (via imaging ellipsometry) with electrochemical conditions (in cyclic voltammetry, CV) provides discrete temporal and spatial information to help us decipher the underlying steps, from which we were able to separate adsorption, reduction, oxidation, desorption, and polymerization regimes involved in the deposition process. The evidence revealed in this study could have broad impact on the general understanding regarding how a film is deposited onto a metal surface.

Nanoparticles of several titanates and zirconates in the range of 20-60 nm have been obtained using the reverse micellar route. Important oxides like CeO 2 (mixture of nanorods; 7 nm diameter and 30 nm length and nanoparticles; 10 nm), ZrO 2 (3-4 nm) and SnO 2 (8 nm) have also been synthesized. Nanorods and nanoparticles of CaCO 3 in all three forms (aragonite, vaterite, and calcite) have been obtained using reverse micelles as nanoreactors. The specific reactions vary depending on the nature of the target nanomaterial. For synthesis of ternary oxides like BaTiO 3 , a modified and convenient route using microemulsions (avoiding Ba-alkoxide) has evolved. Monophasic tin dioxide (SnO 2 ) was obtained when liquid NH 3 was used as precipitating agent. Transmission electron microscopy (TEM) studies show that the SnO 2 nanoparticles are highly uniform and particle size was found to be 6-8 nm at 500 °C. The gas sensing characteristics of SnO 2 have also been investigated using n -butane, which shows high sensitivity and fast recovery time. Reverse micelles have been used, for the first time, to mimic the conditions suitable for the room-temperature synthesis of the high-temperature and -pressure orthorhombic phase of calcium carbonate (aragonite). Other forms of calcium carbonate (vaterite and calcite) could be obtained by varying the atmospheric conditions. At a lower temperature (5 °C), homogeneous and monodisperse spheres of vaterite are obtained. The spherical particles aggregate after longer aging (168 h) to form nanorods, and the self-assembly is clearly seen at various stages by electron microscopy images. The samples were well characterized using powder X-ray diffraction (PXRD), line-broadening studies, TEM, variation in the dielectric properties with frequency and temperature, were measured on disks sintered at high temperature.

Two UV-curable polymers, i.e., a star-shaped poly(ethylene glycol) (PEG) and a linear perfluorinated polyether (PFPE), are investigated as novel biomaterials in a systematic study of the cellular responses to surface chemistry, topography, and elasticity. Based on the wettability it was expected that the two novel biomaterials were too hydrophilic or -phobic, respectively, to support cell adhesion. Indeed, no cell adhesion was observed on the smooth, unstructured elastomers, whereas the materials showed no cytotoxicity. However, when the materials bear defined, topographic patterns (prepared by UV-based imprinting), cells do react strongly to the surfaces; they adhere, spread, and change their shape depending on the geometry of the features. Typically, cells were found to align along line patterns and "float" on pillar structures. It should be noted that the chemistry of the surface is not altered by the imprinting process, hence, there are no biofunctional molecules present at the surface to aid the cell adhesion. Finally, a remarkable effect of elasticity on the cellular behavior was discovered. Thus, the three parameters of chemistry, topography, and elasticity were investigated in- and interdependently, and it was found that the biomaterials may lose their resistance to protein adsorption and cell adhesion depending on the surface topography.

Electrochromic (EC) oxide films with nanocrystalline and nanoporous structure constitute the basis of a number of devices for modulating the throughput of radiant energy. One example is in architectural windows capable of providing energy efficiency and indoor comfort simultaneously. This paper introduces EC technology with particular attention to applications to the built environment. The nanostructural features of the EC films are emphasized, and it is pointed out that reactive magnetron sputtering can be used for large area manufacturing. Electrochromics is discussed from the viewpoints of materials, device technology, and applications.

Control of structural and morphological features of silk fibroin (SF), one of the most popular and stable structural proteins, prepared by near infrared (1064 nm) pulsed laser deposition (PLD) are discussed, based mainly on the recent experimental studies made in the authors' laboratory. The small deposition rate and mingling of much larger units, called chunks or debris, are the main problems. The structure and properties of irradiation targets are highlighted, in an attempt to make the protein PLD technique affordable for practical purposes. Firm adhesion among fibroin powder particles is a straightforward way to avoid pull-out of the particles from the powder-consolidated target, being one of the main sources of debris. This alone cannot, however, satisfactorily increase the homogeneity of the nanostructures and increase the deposition rate. Finer control of the properties of grain-boundary in the target was therefore devised by using binders, including an autogenous one. A unique feature of the ablation mechanisms of fibroin was also discussed by taking account of the optical properties of fibroin, being transparent to a 1064 nm laser beam.

This paper outlines the synthesis of nanocrystalline silicon (nc-Si) by nanosecond pulsed laser fragmentation of Si micrograins in liquid solutions, and characterization of the products. We compare micrograin fragmentations in deionized water, and in undoped and phosphorus-doped ethylpolysilicate (C 2 H 5 O[SiO(C 2 H 5 O) 2 ] n C 2 H 5 ) based polymers. We show that dissolution and subsequent laser fragmentation of micrograins is more efficient in both polymeric media than in water. In the case of water, micrograin surface wetting by ethanol prior to introduction into water is essential to achieve fragmentation. Prepared nc-Si/polymer nanocomposites display visible photoluminescence (PL) (~430 nm) at room temperature. The phosphorus polymer induces a blue shift of the PL peak. In addition, induced shock waves generated at sufficiently high laser irradiation intensities (>4.3 mJ/pulse) cause carbon nanotube (CNT) cavities to be filled by freshly prepared luminescent nc-Si/polymer nanocomposite.

An inverse spinel LiCoVO 4 cathode material was synthesized by a citric acid-urea polymeric method, calcined at 773 K for 5 h. The synthesized LiCoVO 4 sample was surface-modified with La 2 O 3 and/or malonic acid. The composite materials were comprehensively characterized with the aid of various spectroscopic and analytical techniques. X-ray diffraction (XRD) patterns revealed that single-phase crystallinity occurred when they were heated at 773 K for 5 h in air. For the La 2 O 3 -coated samples, there was no evident signal corresponding to secondary-phase peaks. Fourier transform infrared (FTIR) spectra showed the complete elimination of organic residues, nitrates, and the formation of pure LiCoVO 4 at 773 K. The two strong peaks due to sp 2 and sp 3 carbon bonding in the Raman spectra clearly confirm the presence of carbon coating at the surface of LiCoVO 4 particles. Transmission electron microscopy (TEM) images showed that the 0.5 wt % La 2 O 3 -coated LiCoVO 4 material calcined with 60 wt % malonic acid was compact with an average thickness of about 15 nm. This composite cathode material also demonstrated the best cell performance with an initial capacity of 71 mAhg -1 and better thermal stability with lower heat evolution of 35 Jg -1 , and a higher onset temperature of thermal decomposition at 475 K, vs. 176 Jg -1 and 452 K for the bare LiCoVO 4 sample.

Ni 1/3 Co 1/3 Mn 1/3 (OH) 2 , a precursor of LiNi 1/3 Co 1/3 Mn 1/3 O 2 in new-generation Li-ion batteries, was prepared by a hydroxide coprecipitation method. Scanning electronic microscopy (SEM) micrographs reveal that the precursor particles thus obtained, show regular shape with uniform size under optimized conditions. X-ray diffraction (XRD) indicates that well-ordered layer-structured LiNi 1/3 Co 1/3 Mn 1/3 O 2 was prepared after calcination at high temperature. The final product exhibited a spherical morphology with uniform size distribution (10 μm in diameter). At the terminal charging voltage of 4.3 and 4.5 V (vs. Li/Li + ), the testing cells of LiNi 1/3 Co 1/3 Mn 1/3 O 2 delivered a specific capacity of 161.2 and 184.1 mAh g -1 , respectively. The high capacity retention of 98.0 and 96.1 % after charging to 4.3 and 4.5 V for 50 cycles, respectively, indicates that this material displays excellent cycling stability even at high cut-off voltage.

For electrochemical systems such as solid oxide fuel cells (SOFCs) or solid oxide electrolyzer cells (SOECs), perovskites are widely used as cathode material for the reduction of molecular oxygen. At present, strontium-substituted lanthanum manganite, La 1- x Sr x MnO 3-δ (LSM), is used as standard SOFC cathode material for operation at high temperatures, whereas strontium-substituted lanthanum ferrite (LSF) is alternatively explored for medium-temperature SOFCs. Moreover, LSF is considered to be a potential candidate for oxygen separation membranes as the material reported interesting electrical properties. The design of new perovskite-type La transition-metal oxides is of significant technological importance in order to reduce the operating temperature to 600-800 °C and thus to reduce the SOFC system cost. For investigations on a new material class, (La 1- x Sr x ) y Fe 1- z (Ni,Cu) z O 3-δ was synthesized by a spray-pyrolysis process and modified on the A-site in both stoichiometric and non-stoichiometric configurations and on the B-site by substituting Fe with Ni and Cu.

The preparation, physical, and electrochemical properties of Li-ion conducting membranes, poly(vinylidene fluoride-co-hexafluoropropylene) [P(VDF-HFP)]-based gel polymer electrolytes, are briefly reviewed in this paper. Phase separation or inversion method is mostly used to prepare microporous membranes because of the flexibility of its operation and controllable pore structure. The crystallinity of the polymer matrix and the pore structure of the membrane are the key issues to prepare P(VDF-HFP)-based gel polymer electrolytes with high Li + conductivity and good mechanical strength. As to their further directions, they are also discussed.