Clusters of anisotropic colloidal particles: From colloidal molecules to supracolloidal structures

Colloidal clusters have received considerable attention in recent years in the context of the fabrication of “colloidal molecules”, mimicking the symmetry of molecular structures, as well as for the self-assembly of finite supracolloidal structures, especially from anisotropic colloidal particles. Here we review recent studies on clusters of anisotropic colloidal particles, highlighting certain classes of supracolloidal structures that have emerged as recurrent themes in these studies. We emphasize the interplay of colloidal interactions, often arising from the presence of one or more anisotropy attributes, which drives the self-assembly into finite supracolloidal structures.     

Colloidal assembly: the road from particles to colloidal molecules and crystals

Colloidal particles may be considered as building blocks for materials, just like atoms are the bricks of molecules, macromolecules, and crystals. Periodic arrays of colloids (colloidal crystals) have attracted much interest over the last two decades, largely because of their unique photonic properties. The archetype opal structures are based on close-packed arrays of spheres of submicrometer diameter. Interest in structuring materials at this length scale, but with more complex features and ideally by self-assembly processes, has led to much progress in controlling features of both building blocks and assemblies. The necessary ingredients include colloids, colloidal clusters, and colloidal "molecules" which have special shapes and the ability to bind directionally, the control over short-range and long-range interactions, and the capability to place and orientate these bricks. This Review highlights recent experimental and theoretical progress in the assembly of colloids larger than 50 nm.     

An overview of lipid membrane supported by colloidal particles

In recent years, original hybrid assemblies composed of a particle core surrounded by a lipid shell emerged as promising entities for various biotechnological applications. Their broadened bio-potentialities, ranging from model membrane systems or biomolecule screening supports, to substance delivery reservoirs or therapeutic vectors, are furthered by their versatility of composition due to the possible wide variation in the particle nature and size, as well as in the lipid formulation. The synthesis, the characteristics, and the uses of these Lipid/Particle assemblies encountered in the literature so far are reviewed, and classified according to the spherical core size in order to highlight general trends. Moreover, several criteria are particularly discussed: i) the interactions involved between the particles and the lipids, and implicitly the assembly elaboration mechanism, ii) the most suited techniques for an accurate characterization of the entities from structural and physicochemical points of view, and iii) the remarkable properties of the solid-supported lipid membrane obtained.     

Furanoflavonoids: an overview

The review covers the phytochemistry and pharmacology of furanoflavonoids describing 291 compounds and containing 228 references.     

Photoprocesses of excited molecules in confined liquid environments: An overview

The photoprocesses like excited state proton transfer (ESPT), intramolecular charge transfer (ICT), fluorescence energy transfer (FET), occurring in the excited molecules find ample applications in the chemical and biochemical fields. These photoprocesses are markedly affected by the introduction of biomimicking liquid confining environments like micelles, reverse micelles, cyclodextrins, proteins, etc. The local polarity, viscosity and pH, induced by the confined environments have a significant role in modifying the photoprocesses. In this review we have presented a comprehensive report of the recent progress in the study of these photoprocesses in photoexcited molecules in different confined liquid environments. Mostly, recent works have been reviewed in this article to acquire information about progress in the photophysical and photochemical reactions in different confined environments.     

Synthetic glycopolymers: an overview

Glycopolymers, synthetic sugar-containing macromolecules, are attracting ever-increasing interest from the chemistry community due to their role as biomimetic analogues and their potential for commercial applications. Recent developments in polymerisation techniques have enabled the synthesis of glycopolymers featuring a wide range of controlled architectures and functionalities. This review covers the syntheses of pendant carbohydrate-carrying linear polymers and their subsequent properties.     

Natural withanolides: an overview

Withanolides are a group of naturally occurring C28 steroids built on an ergostane skeleton functionalized at carbons 1, 22 and 26, commonly known as the withanolide skeleton. Over the period of August 1996 to March 2010, 360 new naturally occurring withanolides were isolated and identified. This review provides a comprehensive summary of the structural classification and distribution of these new compounds. The diverse biological and pharmacological activities of natural withanolides are also discussed based on their structural features. A total of 211 references are cited in this review.     

Nanoindentation of polymers: an overview

In this paper, the application of instrumented indentation devices to the measurement of the elastic modulus of polymeric materials is reviewed. This review includes a summary of traditional analyses of load‐penetration data and a discussion of associated uncertainties. Also, the use of scanning probe microscopes to measure the nanoscale mechanical response of polymers is discussed, particularly with regard to the associated limitations. The application of these methods to polymers often leads to measurements of elastic modulus that are somewhat high relative to bulk measurements with potentially artificial trends in modulus as a function of penetration depth. Also, power law fits to indentation unloading curves are often a poor representation of the actual data, and the power law exponents tend to fall outside the theoretical range. These problems are likely caused by viscoelasticity, the effects of which have only been studied recently. Advancement of nanoindentation testing toward quantitative characterization of polymer properties will require material‐independent calibration procedures, polymer reference materials, advances in instrumentation, and new testing and analysis procedures that account for viscoelastic and viscoplastic polymer behavior.     

Artifacts in chromatography: an overview

A brief overview of the field of analytical artifacts is provided, with examples of solvent impurities, stabilizers, polymer additives, and problems relating to Teflon, glassware, and laboratory contaminants.     

Lateral migration and focusing of colloidal particles and DNA molecules under viscoelastic flow

Much difficulty has been encountered in manipulating small-scale materials, such as submicron colloidal particles and macromolecules (e.g., DNA and proteins), in microfluidic devices since diffusion processes due to thermal (Brownian) motion become more pronounced with decreasing particle size. Here, we present a novel approach for the continuous focusing of such small-scale materials. First, we successfully focused fluorescent submicron polystyrene (PS) beads along equilibrium positions in microchannels through the addition of a small amount water-soluble polymer [500 ppm poly(ethylene oxide) (PEO)]. Lateral migration velocity significantly depends upon the viscoelastic effect (Weissenberg number: Wi) and the aspect ratio of particle size to channel height (a/h). Interestingly, focusing using viscoelastic flows was also observed for flexible DNA molecules (λ-DNA and T4-DNA), which have radii of gyration (R(g)) of approximately 0.69 μm and 1.5 μm, respectively. This small-scale material manipulation using medium viscoelasticity will contribute to the design of nanoparticle separation and genomic mapping devices.     

Aerogel-based thermal superinsulation: an overview

This review is focused on describing the intimate link which exists between aerogels and thermal superinsulation. For long, this applied field has been considered as the most promising potential market for these nanomaterials. Today, there are several indicators suggesting that this old vision is likely to become reality in the near future. Based on recent developments in the field, we are confident that aerogels still offer the greatest potential for non-evacuated superinsulation systems and consequently must be considered as an amazing opportunity for sustainable development. The practical realization of such products however is time-consuming and a significant amount of R&D activities are still necessary to yield improved aerogel-based insulation products for mass markets.     

Analytical applications of electrochemiluminescence: an overview

The chemical transformations of electrogenerated ion-radicals of a number of complex organic compounds may be accompanied by emission of photons. An electrochemiluminescence (ECL) quantum contains information both on the kinetics of the heterogeneous electrode processes and on the subsequent homogeneous chemical reactions in the solution. Application of ECL to solution analysis provides advantages in comparison to electrochemical methods. Using ECL for electrode surface analysis allows information to be obtained on the rate of an electrochemical process simultaneously at all points of the electrode under analysis in real time, and that is the main difference between this method and the point-by-point testing specific to electrochemical methods. The potential of ECL for analytical chemistry is examined concerning the homogeneous ECL-analysis of solutions and the heterogeneous ECL-analysis of electrode surfaces. Received: 6 April 2000 / Revised: 23 June 2000 / Accepted: 27 June 2000     

Vanadium-doped hafnia: elaboration and structural characterization

Powders of HfO₂ doped with various amounts of vanadium were prepared by pyrolysis of oxalic precursors at relatively low temperature (700 °C). This pyrolysis was carried out under different atmospheres in order to insert vanadium under different oxidation states into hafnia. The various amounts of inserted vanadium into HfO₂ were determined by energy dispersive spectroscopy. The powders were structurally characterized by X-ray diffraction, and electron diffraction. Nano particles of monoclinic HfO₂ were obtained when incorporating V⁵⁺. The solubility limit in that case was found to be less than 10 at %. The insertion of vanadium with a lower oxidation state than 5+ led to the stabilization of the cubic phase, with a solubility limit higher than 30 % at.     

Energy-filtered transmission electron microscopy: an overview

This paper aims to give an overview of the technique of energy-filtered transmission electron microscopy (EFTEM). It explains the basic principles of the technique and points to the relevant literature for more detailed issues. Experimental examples are given to show the power of EFTEM to study the chemical composition of nanoscale samples in materials science. Advanced EFTEM applications like imaging spectroscopy and EFTEM tomography are briefly discussed.     

Azobenzene-containing bent-core liquid crystals: an overview

ABSTRACT

Azo-functionalised materials are of special interest due to their photochromic nature, i.e. reversible trans–cis isomerisation upon photoirradiation. The combination of photosensitivity and liquid crystalline properties in the same molecule allows the material to be exploited for optical and optoelectronic devices. Azobenzene-based bent-core liquid crystals (BCLCs) have attracted considerable attention in recent years due to their rich mesomorphism. In this review, the main research directions and different molecular structures of bent-core molecules incorporating azobenzene unit and its subtype the so-called hockey-stick molecules are summarised. Additionally, azobenzene-based U-shaped molecules, hydrogen-bonded bent-shaped liquid crystalline materials and some selected examples of two different types of photoswitchable mesogenic dimers are provided. The nature, number and position of the lateral substitutions able to modify the phase behaviour of such BCLCs, affording in turn interesting liquid crystalline phases are discussed. Finally, the isomerisation process of these photosensitive BCLCs in solutions or in mesophases under the effect of UV–visible irradiation is summarised.     

Bioconjugation via azide-Staudinger ligation: an overview

Bioconjugation techniques using organic azides are compared in this critical review. A particular focus is on chemical ligation reactions and their application to chemical biology (179 references).     

Synthetic routes for phenazines: an overview

Phenazines are known to exhibit a diverse range of biological properties, such as antimicrobial, antitumor, antioxidant, antimalarial, neuroprotectant, etc. Owing to their significant applications in both medicinal and industrial fields, the phenazine framework has emerged as a remarkable synthetic target. The most general approaches for synthesis of phenazines include the Wohl–Aue method, Beirut method, condensation of 1,2-diaminobenzenes with 2C-units, reductive cyclization of diphenylamines, oxidative cyclization of 1,2-diaminobenzene/diphenylamines, Pd-catalyzed N-arylation, multicomponent approaches, etc. Advances in the exploitation of synthetic routes for assembly of this scaffold are reported in this review.     

Compostability of bioplastic packaging materials: an overview

Packaging waste accounted for 78.81 million tons or 31.6% of the total municipal solid waste (MSW) in 2003 in the USA, 56.3 million tons or 25% of the MSW in 2005 in Europe, and 3.3 million tons or 10% of the MSW in 2004 in Australia. Currently, in the USA the dominant method of packaging waste disposal is landfill, followed by recycling, incineration, and composting. Since landfill occupies valuable space and results in the generation of greenhouse gases and contaminants, recovery methods such as reuse, recycling and/or composting are encouraged as a way of reducing packaging waste disposal. Most of the common materials used in packaging (i.e., steel, aluminum, glass, paper, paperboard, plastics, and wood) can be efficiently recovered by recycling; however, if packaging materials are soiled with foods or other biological substances, physical recycling of these materials may be impractical. Therefore, composting some of these packaging materials is a promising way to reduce MSW. As biopolymers are developed and increasingly used in applications such as food, pharmaceutical, and consumer goods packaging, composting could become one of the prevailing methods for disposal of packaging waste provided that industry, governments, and consumers encourage and embrace this alternative. The main objective of this article is to provide an overview of the current situation of packaging compostability, to describe the main mechanisms that make a biopolymer compostable, to delineate the main methods to compost these biomaterials, and to explain the main standards for assessing compostability, and the current status of biopolymer labeling. Biopolymers such as polylactide and poly(hydroxybutyrate) are increasingly becoming available for use in food, medical, and consumer goods packaging applications. The main claims of these new biomaterials are that they are obtained from renewable resources and that they can be biodegraded in biological environments such as soil and compost. Although recycling could be energetically more favorable than composting for these materials, it may not be practical because of excessive sorting and cleaning requirements. Therefore, the main focus is to dispose them by composting. So far, there is no formal agreement between companies, governments and consumers as to how this packaging composting will take place; therefore, the main drivers for their use have been green marketing and pseudo-environmental consciousness related to high fuel prices. Packaging compostability could be an alternative for the disposal of biobased materials as long as society as a whole is willing to formally address the challenge to clearly understand the cradle-to-grave life of a compostable package, and to include these new compostable polymers in food, manure, or yard waste composting facilities.