Cyclopentadienyl-functionalised polyhedral silsesquioxanes as building blocks for new nanostructured materials

This work is to design new organosilicon precursors, which contain both siloxane and cyclopentadienyl functionalities and use these compounds as building blocks for new nanomaterials. Polyhedral silsesquioxanes, (RSiO_1.5)_n (n = 8 and 10) with cyclopentadienyl (R = -C₅H₅ or -(CH₂)₃-C₅H₅) functionalities have been prepared by hydrolytic condensation of the correspondent silicon organic precursors RSiCl₃ or RSi(OC₂H₅)₃. The products with cyclopentadienyl groups have been used to prepare new cross-linked 3D polymeric materials by Diels-Alder reaction. The compounds have been characterised by multinuclear (¹H and ²⁹Si) NMR, ESI MS and IR spectroscopy, UV/Vis spectrometry, gel permeation chromatography and scanning electron microscopy. The approach above seems to be very promising for the preparation of new nanostructured materials.     

Bottom-up strategy of materials fabrication: a new trend in nanotechnology of soft materials

Recent progresses in nanometer-scale molecular self-organization and mesoscopic pattern formation are reviewed from the view point of nanotechnology of bottom-up materials fabrication. Nanometer-scale layer-by-layer self-assemblies on nanoparticles will provide wide applications in many fields. The micro-contact printing technique is effectively used for up-sizing the nanostructured molecular assemblies as submicrometer- and micrometer-scale patterns. Dissipative structures formed in non-equilibrium systems as self-organized spatio-temporal structures are newly employed for the mesoscopic patterning of the nanostructured molecular assemblies.     

Utilising thermoporometry to obtain new insights into nanostructured materials

Thermoporometry is a relatively new method of characterising porous properties of nanostructured materials based on observation of solid–liquid phase transitions of materials confined in pores. It provides several advantages over the conventional characterisation methods, mercury porosimetry and gas sorption. The advantages include possibility of using short measurement times, non-toxic chemicals and wet samples. In addition, complicated sample preparation and specialised instruments are not required. Therefore, it has a great potential of becoming a widely utilised characterisation method, although its potential has not yet been widely realised. In recent years, there has been a significant increase in research activities regarding the method. In the first part of the review, we introduce thermoporometry and review related results of the confinement effects on materials and their solid–liquid phase transition.     

Utilising thermoporometry to obtain new insights into nanostructured materials

Thermoporometry is a relatively new method of characterising porous properties of nanostructured materials based on observation of solid–liquid phase transitions of materials confined in pores. It provides several advantages over the conventional characterisation methods, mercury porosimetry and gas sorption. The advantages include possibility of using short measurement times, non-toxic chemicals and wet samples. In addition, complicated sample preparation and specialised instruments are not required. Therefore, it has a great potential of becoming a widely utilised characterisation method, although its potential has not yet been widely realised. In recent years, there has been a significant increase in research activities regarding the method. In the second part of the review, results and conclusions of the recent studies about thermoporometry are surveyed and discussed focusing on the application of thermoporometry in extracting various structural information from the porous materials.     

Titanium oxo-clusters: precursors for a Lego-like construction of nanostructured hybrid materials

Titanium oxo-clusters, well-defined monodispersed nano-objects, are appropriate nano-building blocks for the preparation of organic-inorganic materials by a bottom up approach. This critical review proposes to present the different structures of titanium oxo-clusters referenced in the literature and the different strategies followed to build up hybrid materials with these versatile building units. In particular, this critical review cites and reports on the most important papers in the literature, concentrating on recent developments in the field of synthesis, characterization, and the use of titanium oxo-clusters for the construction of advanced hybrid materials (137 references).     

3-Fold-interpenetrated uranium-organic frameworks: new strategy for rationally constructing three-dimensional uranyl organic materials

The first series of 3-fold-interpenetrated uranium-organic frameworks, UOF-1 and UOF-2, have been synthesized by hydrothermal reactions of flexible semirigid carboxylic acids and uranyl nitrate. Structure analyses indicate that UOF-1 and UOF-2 possess flu and pts topologies, respectively.     

Heterogeneous nanostructured electrode materials for electrochemical energy storage

In order to fulfil the future requirements of electrochemical energy storage, such as high energy density at high power demands, heterogeneous nanostructured materials are currently studied as promising electrode materials due to their synergic properties, which arise from integrating multi-nanocomponents, each tailored to address a different demand (e.g., high energy density, high conductivity, and excellent mechanical stability). In this article, we discuss these heterogeneous nanomaterials based on their structural complexity: zero-dimensional (0-D) (e.g. core-shell nanoparticles), one-dimensional (1-D) (e.g. coaxial nanowires), two-dimensional (2-D) (e.g. graphene based composites), three-dimensional (3-D) (e.g. mesoporous carbon based composites) and the even more complex hierarchical 3-D nanostructured networks. This review tends to focus more on ordered arrays of 1-D heterogeneous nanomaterials due to their unique merits. Examples of different types of structures are listed and their advantages and disadvantages are compared. Finally a future 3-D heterogeneous nanostructure is proposed, which may set a goal toward developing ideal nano-architectured electrodes for future electrochemical energy storage devices.     

Computational study of nanostructured materials

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Preparation of polymeric nanostructured materials

A procedure for forming nanostructured materials by impregnation filling of pores of poly(ethylene terephthalate) track membranes with polymeric compounds was examined. The relationships of formation of these materials were elucidated, and the structural and surface properties of these materials were studied.     

Modular domain structure: a biomimetic strategy for advanced polymeric materials

A long lasting challenge in polymer science is to design polymers that combine desired mechanical properties such as tensile strength, fracture toughness, and elasticity into one structure. A novel biomimetic modular polymer design is reported here to address this challenge. Following the molecular mechanism used in nature, modular polymers containing multiple loops were constructed by using precise and strong hydrogen bonding units. Single-molecule force-extension experiments revealed the sequential unfolding of loops as a chain is stretched. The excellent correlation between the single-molecule and the bulk properties successfully demonstrates our biomimetic concept of using modular domain structure to achieve advanced polymer properties.     

Iminoboronates: a new strategy for reversible protein modification

Protein modification has entered the limelight of chemical and biological sciences, since, by appending small molecules into proteins surfaces, fundamental biological and biophysical processes may be studied and even modulated in a physiological context. Herein we present a new strategy to modify the lysine's ε-amino group and the protein's N-terminal, based on the formation of stable iminoboronates in aqueous media. This functionality enables the stable and complete modification of these amine groups, which can be reversible upon the addition of fructose, dopamine, or glutathione. A detailed DFT study is also presented to rationalize the observed stability toward hydrolysis of the iminoboronate constructs.     

Discovering antimalarials: a new strategy

Recent discoveries have uncovered some key processes that occur in the food vacuole of the malarial parasite. Consequently, new families of potential antimalarials that inhibit HRP-2, a hitherto unexplored drug target, were identified using a novel screening method.     

Individual nanostructured materials: fabrication and surface-enhanced Raman scattering

The progress of surface-enhanced Raman scattering (SERS) microscopy and spectroscopy on individual nanostructured materials has been reviewed in this feature article. After a brief introduction on individual nanomaterial SERS, we provide a systematic overview on the fabrication and SERS studies of individual nanoparticulates, nano-junctions and hierarchical nano-aggregate. These SERS-active nanomaterials have great potential in designing novel highly sensitive SERS substrates for the development of SERS-based sensing devices with a broad range of applications.     

Functional block copolymers: nanostructured materials with emerging applications

Recent advances in polymer synthesis have significantly enhanced the ability to rationally design block copolymers with tailored functionality. The self-assembly of these macromolecules in the solid state or in solution allows the formation of nanostructured materials with a variety of properties and potential functions. This Review illustrates recent progress in the field of block copolymer materials by highlighting selected emerging applications.     

Folic acid-conjugated nanostructured materials designed for cancer cell targeting

Shell cross-linked nanoparticles (SCKs) constitute a unique class of materials with amphiphilic core-shell morphology; SCKs are characterised by their structural integrity and available functionality to attach receptor-recognising or receptor-specific ligands on the shell surface and, therefore, hold great potential in drug delivery applications; in an attempt to develop novel, cancer cell specific delivery vehicles, folate receptor targeted SCKs have been prepared.     

Polymeric ionic liquids: a strategy for preparation of novel polymeric materials

A novel polymeric ionic liquid (PIL), bearing high C-N and N-N content, potentially suitable for new safe energetic materials and catalyst supports was introduced. The PIL was prepared by way of radical co-polymerisation of 1-vinyl-3-p-nitrobenzylimidazolium bromide and 1-vinylimidazole at 80°C using azobisisobutyronitrile (AIBN) as an initiator. The PIL thus produced was successfully transformed into NO₃@PIL and N₃@PIL for potential application as safe energetic materials and/or catalyst supports. The polymers were obtained in quantitative yields and were characterised by NMR, FTIR, DSC and TGA data. This study reveals the adequate thermal stability of novel salt-based nitrogen-rich polymeric ionic liquids for application as safe energetic materials and/or supports in heterogeneous catalysis.     

High-resolution analytical TEM of nanostructured materials

This paper briefly reviews the potential applicability of analytical transmission electron microscopy (TEM) to elucidate both structural and chemical peculiarities of materials at high lateral resolution. Examples of analytical TEM investigations performed by energy-dispersive X-ray spectroscopy (EDXS), electron energy loss spectroscopy (EELS), and energy-filtered TEM (EFTEM) are presented for different materials systems including metals, ceramics, and compound semiconductors. In particular, results are given of imaging the element distribution in the interface region between gamma matrix and gamma' precipitate in the nickel-based superalloy SC16 by energy-filtered TEM. For core-shell structured BaTiO(3) particles the chemical composition and even the chemical bonding were revealed by EELS at a resolution of about 1 nm. A sub-nanometer resolution is demonstrated by energy-selective images of the Ga distribution in the surrounding of (In,Ga)As quantum dots. Moreover, the element distribution in (Al,Ga)As/AlAs multilayers with linear concentration gradients in a range of about 10 nm was investigated by EDXS line-profile analyses and EFTEM.