Preparation, properties and applications of polysaccharide nanocrystals in advanced functional nanomaterials: a review

Intensive exploration and research in the past few decades on polysaccharide nanocrystals, the highly crystalline nanoscale materials derived from natural resources, mainly focused originally on their use as a reinforcing nanophase in nanocomposites. However, these investigations have led to the emergence of more diverse potential applications exploiting the functionality of these nanomaterials. Based on the construction strategies of functional nanomaterials, this article critically and comprehensively reviews the emerging polysaccharide nanocrystal-based functional nanomaterials with special applications, such as biomedical materials, biomimetic optical nanomaterials, bio-inspired mechanically adaptive nanomaterials, permselective nanostructured membranes, template for synthesizing inorganic nanoparticles, polymer electrolytes, emulsion nano-stabilizer and decontamination of organic pollutants. We focus on the preparation, unique properties and performances of the different polysaccharide nanocrystal materials. At the same time, the advantages, physicochemical properties and chemical modifications of polysaccharide nanocrystals are also comparatively discussed in view of materials development. Finally, the perspective and current challenges of polysaccharide nanocrystals in future functional nanomaterials are outlined.     

Surface‐engineered hydroxyapatite nanocrystal/ poly(ε‐caprolactone) hybrid scaffolds for bone tissue engineering

To achieve novel polymer/bioceramic composite scaffolds for use in materials for bone tissue engineering, we prepared organic/inorganic hybrid scaffolds composed of biodegradable poly(ε‐caprolactone) (PCL) and hydroxyapatite (HA), which has excellent biocompatibility with hard tissues and high osteoconductivity and bioactivity. To improve the interactions between the scaffolds and osteoblasts, we focused on surface‐engineered, porous HA/PCL scaffolds that had HA molecules on their surfaces and within them because of the biochemical affinity between the biotin and avidin molecules. The surface modification of HA nanocrystals was performed with two different methods. Using Fourier transform infrared, X‐ray diffraction, and thermogravimetric analysis measurements, we found that surface‐modified HA nanocrystals prepared with an ethylene glycol mediated coupling method showed a higher degree of coupling (%) than those prepared via a direct coupling method. HA/PCL hybrid scaffolds with a well‐controlled porous architecture were fabricated with a gas‐blowing/particle‐leaching process. All HA/PCL scaffold samples exhibited approximately 80–85% porosity. As the HA concentration within the HA/PCL scaffolds increased, the porosity of the HA/PCL scaffolds gradually decreased. The homogeneous immobilization of biotin‐conjugated HA nanocrystals on a three‐dimensional, porous scaffold was observed with confocal microscopy. According to an in vitro cytotoxicity study, all scaffold samples exhibited greater than 80% cell viability, regardless of the HA/PCL composition or preparation method. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Biomimetic multifunctional molecular coatings using engineered proteins

A molecular biomimetics approach is presented in developing polypeptide-based coatings for inorganic surfaces. In general, inorganic surface-binding polypeptides are genetically engineered using cell surface and phage display technologies. These peptides contain short amino acid sequences, known to bind specifically to selected inorganics. Based on the sequences of the polypeptides that were recently selected by this (e.g. Au, Pt and Pd) and other groups, one may find certain specificity, e.g. hydrophobic and hydroxyl amino acids, common among noble metal-binders. We show that an engineered gold-binding protein self-assembles onto gold surface forming monomolecular and highly structured crystallographic domains. The protein-based molecular films could provide robust templates for potential utility in practical nanotechnological and bionanotechnological applications.     

Virus-templated iridium oxide-gold hybrid nanowires for electrochromic application

A highly porous electrode comprised of biologically templated iridium oxide-gold (IrO(2)-Au) hybrid nanowires is introduced for electrochromic applications. A filamentous M13 virus is genetically engineered to display IrO(2)-binding peptides on the viral surface and used as a template for the self-assembly of IrO(2) nanoclusters into a nanowire. The open porous morphology of the prepared nanowire film facilitates ion transport. Subsequently, the redox kinetics of the IrO(2) nanowires seems to be limited by the electric resistance of the nanowire film. To increase the electron mobility in the nanowires, gold nanoparticles are chemically linked to the virus prior to the IrO(2) mineralization, forming a gold nanostring structure along the long axis of the virus. The resulting IrO(2)-Au hybrid nanowires exhibit a switching time of 35 ms for coloration and 25 ms for bleaching with a transmission change of about 30.5% at 425 nm. These values represent almost an order of magnitude faster switching responses than those of an IrO(2) nanowire film having the similar optical contrast. This work shows that genetically engineered viruses can serve as versatile templates to co-assemble multiple functional molecules, enabling control of the electrochemical properties of nanomaterials.     

State-of-the-art technology: Recent investigations on laser-mediated synthesis of nanocomposites for environmental remediation

In both developing and industrialized/developed countries, various hazardous/toxic environmental pollutants are entering water bodies from organic and inorganic compounds (heavy metals and specifically dyes). The global population is growing whereas the accessibility of clean, potable and safe drinking water is decreasing, leading to world deterioration in human health and limitation of agricultural and/or economic development. Treatment of water/wastewater (mainly industrial water) via catalytic reduction/degradation of environmental pollutants is extremely critical and is a major concern/issue for public health. Light and/or laser ablation induced photocatalytic processes have attracted much attention during recent years for water treatment due to their good (photo)catalytic efficiencies in the reduction/degradation of organic/inorganic pollutants. Pulsed laser ablation (PLA) is a rather novel catalyst fabrication approach for the generation of nanostructures with special morphologies (nanoparticles (NPs), nanocrystals, nanocomposites, nanowires, etc.) and different compositions (metals, alloys, oxides, core-shell, etc.). Laser ablation in liquid (LAL) is generally considered a quickly growing approach for the synthesis and modification of nanomaterials for practical applications in diverse fields. LAL-synthesized nanomaterials have been identified as attractive nanocatalysts or valuable photocatalysts in (photo)catalytic reduction/degradation reactions. In this review, the laser ablation/irradiation strategies based on LAL are systematically described and the applications of LAL synthesized metal/metal oxide nanocatalysts with highly controlled nanostructures in the degradation/reduction of organic/inorganic water pollutants are highlighted along with their degradation/reduction mechanisms.     

Highly monodisperse Cu- and Ag-based bimetallic nanocrystals for the efficient utilization of noble metals in catalysis

Highly monodisperse Cu- and Ag-based bimetallic noble metal nanocrystals (BNMNs) with diameter 2-7 nm have been synthesized. The synthesis employs a successive reduction process by using inorganic metal salts as precursors at a low temperature (～110 °C). HRTEM, XPS and XRD analytical techniques were applied for the structural analysis of BNMNs. Catalytic activity investigation (CO oxidation) over different supports (silicate nanotubes and CeO2 nanoparticles) shows that BNMNs have identical and even enhanced performance over pure noble metal nanocrystals with similar size and size distribution, which proves that these BNMNs can significantly reduce the amount and thus make full use of noble metals in catalysis.     

Exposure assessment of engineered nanomaterials in the workplace

Nanotechnology is a rapidly growing field and numerous products containing engineered nanomaterials are already in the market. With the increasing use of engineered nanomaterials, it is expected to increase the exposures to nanomaterials in the workplace. However, the researches on the exposure assessment of nanomaterials to humans and the environment are just a beginning step, as the nanotechnology industries are expanding. Questionnaire surveys conducted by various organizations reveal that many nanotechnology companies are searching for information on exposure measurement for the protection of workers who handle nanomaterials. We analyze the trends of researches on the occupational exposure measurement of engineered nanomaterials and investigate the methodologies of exposure assessment recommended by the related working groups. This work is expected to fill the gaps in knowledge on the exposure assessment of nanomaterials.     

Ionic liquid-stabilized non-spherical gold nanofluids synthesized using a one-step method

Ionic liquid (IL)-stabilized non-spherical gold nanofluids have been synthesized by a one-step method in aqueous solution. The whole reaction proceeded in room temperature. In the presence of amino-functionalized ionic liquids, gold nanofluids with long-wave surface plasmon resonance (SPR) absorption (>600 nm) could be obtained by adopting tannic acid as the reductant. The specific SPR absorption was related to the non-spherical gold nanoparticles including gold triangle, decahedra, and icosahedra nanocrystals. All the nanocrystals were observed by transmission electron microscopy. It was deduced that the formation of non-spherical gold nanofluids was related to the hydroxyls in tannic acid while IL acted as the synthesis template.     

DNA-assisted rational design of BaF2 linear and erythrocyte-shaped nanocrystals

The synthesis of inorganic materials with special morphologies with the assistance of biological molecules is a potential development in the field of controllable growth and assembly of nanomaterials. In this paper, BaF2 nanocrystals in patterns of well-defined linear and erythrocyte-shaped structure were synthesized with the assistance of Escherichia coli DNA.Morphology and the arrangement of BaF2 particles on DNA were controllable by altering the reaction condition. Square nanoparticles arranged in linear chains were gained with the assistance of normal DNA; while, erythrocyte-shaped BaF2 nanospheres were synthesized with the assistance of denatured DNA. Besides, the influences of solvent, reaction temperature, concentration of reactants and the heating time on the morphology of the BaF2 particles were studied.     

A Present Understanding of Colloidal Quantum Dot Blinking

Luminescence intermittency, also termed ‘blinking’, refers to spontaneous changes in the brightness of a luminescent fluorophore under continuous optical excitation. Blinking was first observed in colloidal semiconductor nanocrystals over fifteen years ago, shortly after synthetic protocols became advanced enough to produce brightly luminescent nanocrystals. The underlying physical mechanism was initially associated with long-lived photo-induced charging of the nanocrystals. In recent years, however, significant evidence has accumulated to point at a more complex physical picture of the process, which involves several distinct mechanisms and is mediated by surface charge trapping. In parallel, efforts to synthesize highly luminescent semiconductor nanocrystals that do not exhibit blinking have recently borne fruit. We review the recent progress in understanding of blinking and potential applications in bioimaging using inorganic fluorescent tags.     

On the nature and importance of the transition between molecules and nanocrystals: towards a chemistry of "nanoscale perfection"

This paper discusses the importance of the transition between molecular compounds and nanocrystals. The boundary between molecular and nanocrystals/nanoclusters can be defined by the emergence of the bulk phase; atoms in the core of the nanoclusters that are not bound to ligands. This transition in dimensions and structural organization is important because it overlaps with the boundary between atomically defined moieties (molecules can be isolated with increasing purity) and mixtures (nanocrystals have a distribution of sizes, shapes, and defects; they cannot be easily separated into batches of structurally identical species). Passing through this boundary, as the size of a structure increases beyond a few nanometres, the information about the position of each atom gradually disappears. This loss of structural information about a chemical structure fundamentally compromises our ability to use it as a part of a complex chemical system. If we are to engineer complex functions encoded in a chemical language, we will need pure batches of atomically defined (truly monodisperse) nanoscale compounds, and we will need to understand how to make them and preserve them over a broad range of length scales, compositions, and timeframes. In this review we survey most classes of monodisperse nanomaterials (mostly nanoclusters) and highlight the recent breakthroughs in this area which might be spearheading the development of a chemistry of "nanoscale perfection".     

A general procedure to synthesize highly crystalline metal oxide and mixed oxide nanocrystals in aqueous medium and photocatalytic activity of metal/oxide nanohybrids

A conventional and general route has been exploited to the high yield synthesis of many kinds of highly crystalline metal oxide and mixed oxide nanocrystals with different morphologies including belt, rod, truncated-octahedron, cubic, sphere, sheet via the hydrothermal reaction of inorganic precursors in aqueous solution in the presence of bifunctional 6-aminohexanoic acid (AHA) molecules as a capping agent. This method is a simple, reproducible and general route for the preparation of a variety of high-crystalline inorganic nanocrystals in scale-up. The shape of inorganic nanocrystals such as CoWO(4), La(2)(MoO(4))(3) can be controlled by simply adjusting the synthesis conditions including pH solution and reaction temperature. Further, by tuning precursor monomer concentration, the mesocrystal hierarchical aggregated microspheres (e.g., MnWO(4), La(2)(MoO(4))(3)) can be achieved, due to the spontaneous assembly of individual AHA-capped nanoparticles. These obtained AHA-capped nanocrystals are excellent supports for the synthesis of a variety of hybrid metal/oxide nanocrystals in which noble metal particles are uniformly deposited on the surface of each individual nanosupport. The photocatalytic activity of Ag/TiO(2) nanobelts as a typical hybrid photocatalyst sample for Methylene Blue degradation was also studied.     

A facile synthesis of Te nanoparticles with binary size distribution by green chemistry

Our work reports a facile route to colloidal Te nanocrystals with binary uniform size distributions at room temperature. The binary-sized Te nanocrystals were well separated into two size regimes and assembled into films by electrophoretic deposition. The research provides a new platform for nanomaterials to be efficiently synthesized and manipulated.     

Inorganic Enzyme Mimics

Enzyme mimics (or artificial enzymes) have emerged as valuable alternatives to natural enzymes since the pioneering work of Ronald Breslow. They have numerous advantages over natural enzymes, such as high stability, low cost, and tailorable activity. Among varieties of materials explored to mimic enzymes, the inorganic ones, including inorganic complexes and nanomaterials, have attracted increasing interest over the last decade and have the potential to address the current challenges in energy, environment, health, etc.     

Iron-oxide nanoparticles supported on sepiolite as a novel humidity sensor

In the present work, a new humidity sensor based on nanostructured hematite deposited by a wet chemical route on a low-cost natural inorganic phylosilicate (sepiolite) powder was obtained. The nanometric character of these particles has been evaluated by X-ray diffraction, thermal gravimetric analysis (TGA) and differential thermal analysis (DTA) and transmission electron microscopy. This material compacted as a pellet by uniaxial pressure with the corresponding interdigitated gold electrodes, was found to be very appropriate to operate as humidity sensor over a wide relative humidity (RH) range (5–98%).     

Review: is interplay between nanomaterial and membrane technology the way forward for desalination?

Nanomaterials, which have been the greatest impetus to technological and industrial development in the twenty‐first century, have spurred significant innovations and knowledge enhancement in the environmental applications particularly to revolutionize century‐old conventional water treatment processes. The established protocols to prepare such hybrid nanocomposites have triggered blossoming interest and to realize most of these applications practically. Similarly, engineered nanomaterials unfold avenues and offer myriad opportunities to explore their impact in various fields and have certainly a great impact on the future of desalination practice. After the review and examination of published materials describing the development of nano‐enabled membranes that have been undertaken in recent years, this short review aims at stimulating new ideas and thoughts in the membrane desalination field where we are strongly convinced that it will represent one of the key areas for the realization of a sustainable generation of materials that can benefit mankind. More particularly, this review draws attention to the incorporation of inorganic nanomaterials into conventional polymeric membranes and deals with the practical challenges to implementation of technology for desalination applications. © 2014 Society of Chemical Industry     

Pathways Related to NLRP3 Inflammasome Activation Induced by Gold Nanorods

The widespread and increasing use of engineered nanomaterials (ENM) increases the risk of human exposure, generating concern that ENM may provoke adverse health effects. In this respect, their physicochemical characteristics are critical. The immune system may respond to ENM through inflammatory reactions. The NLRP3 inflammasome responds to a wide range of ENM, and its activation is associated with various inflammatory diseases. Recently, anisotropic ENM have become of increasing interest, but knowledge of their effects on the immune system is still limited. The objective of the study was to compare the effects of gold ENM of different shapes on NLRP3 inflammasome activation and related signalling pathways. Differentiated THP-1 cells (wildtype, ASC- or NLRP3-deficient), were exposed to PEGylated gold nanorods, nanostars, and nanospheres, and, thus, also different surface chemistries, to assess NLRP3 inflammasome activation. Next, the exposed cells were subjected to gene expression analysis. Nanorods, but not nanostars or nanospheres, showed NLRP3 inflammasome activation. ASC- or NLRP3-deficient cells did not show this effect. Gene Set Enrichment Analysis revealed that gold nanorod-induced NLRP3 inflammasome activation was accompanied by downregulated sterol/cholesterol biosynthesis, oxidative phosphorylation, and purinergic receptor signalling. At the level of individual genes, downregulation of Paraoxonase-2, a protein that controls oxidative stress, was most notable. In conclusion, the shape and surface chemistry of gold nanoparticles determine NLRP3 inflammasome activation. Future studies should include particle uptake and intracellular localization.     

Extraction and characterization of cellulose nanocrystals from cotton fiber by enzymatic hydrolysis-assisted high-pressure homogenization

Cellulose nanocrystals (CNCs) have attracted increasing attention in the field of nanomaterials because of its high aspect ratio, good structure, and high thermal stability. In this study, enzymatic hydrolysis-assisted high-pressure homogenization was applied as an environmentally friendly technique to extract CNCs from cotton-derived microcrystalline cellulose (MCC). The overall optimization of enzymatic pretreatment was conducted by response surface methodology, and the maximum CNCs yield was 40.09% under the optimized experimental conditions. The extracted CNCs under the optimal conditions showed needle-like shape with a length of 100–250 nm and a width of 5–10 nm and exhibited an overall particle size range of 3–80 nm. The basic chemical structure of cellulose was not changed after enzymatic hydrolysis and high-pressure homogenization. The CNCs exhibited slightly lower crystallinity and higher thermal stability than MCC. High aspect ratio CNCs extracted in this present study have great potential as a reinforcing agent in biodegradable packaging materials.     

Effect of multiwall carbon nanotube and au nanoparticle on the structure–property relationship of poly(N‐isopropyl acrylamide)

Temperature‐sensitive poly(N‐isopropyl acrylamide) (PNIPAAm) was synthesized both in the presence and absence of nanomaterials like allyl mercaptan decorated gold nanoparticle and allyalcohol‐conjugated multiwall carbon nanotube. The influence of the nanomaterials on the structure–property relationship of PNIPAAm was analyzed and critically compared to the pristine PNIPAAm. During the in situ polymerization, the nanosphere shape of Au nanoparticle was converted into Au nanorod shape, which was confirmed through UV–vis spectroscopy. The glass transition temperature (T_g) of polymer/nanocomposites was greater than that of the pristine polymer. Thermogravimetric analysis declared that the polymer/nanocomposites exhibited higher thermal stability than the homopolymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012