Advanced Materials in Cultural Heritage Conservation

Cultural Heritage is a crucial socioeconomic resource; yet, recurring degradation processes endanger its preservation. Serendipitous approaches in restoration practice need to be replaced by systematically addressing conservation issues through the development of advanced materials for the preservation of the artifacts. In the last few decades, materials and colloid science have provided valid solutions to counteract degradation, and we report here the main highlights in the formulation and application of materials and methodologies for the cleaning, protection and consolidation of works of art. Several types of artifacts are addressed, from murals to canvas paintings, metal objects, and paper artworks, comprising both classic and modern/contemporary art. Systems, such as nanoparticles, gels, nanostructured cleaning fluids, composites, and other functional materials, are reviewed. Future perspectives are also commented, outlining open issues and trends in this challenging and exciting field.     

Liquid-Phase Synthesis of Iron Oxide Nanostructured Materials and Their Applications

Owing to their high natural abundance, low cost, easy availability, and excellent magnetic properties, considerable interest has been devoted to the synthesis and applications of iron oxide nanostructured materials. Liquid-phase synthesis methods are economical and environmentally friendly with low energy consumption and volatile emissions, and as such have received much attention for the preparation of iron oxide nanostructured materials. Herein, the liquid-phase synthesis methods of iron oxide nanostructured materials including the co-precipitation method, microemulsion method, conventional hydrothermal and solvothermal methods, microwave-assisted heating method, sonolysis method, and other methods are summarized and reviewed. Many iron oxide nanostructured materials, self-assembled nanostructures, and nanocomposites have been successfully prepared, which are of great significance to enhance their structure-dependent properties and applications. The specific roles of liquid-phase chemical reaction parameters in regulating the chemical composition, structure, crystallinity, morphology, particle size, and dispersive behavior of the as-prepared iron oxide nanostructured materials are emphasized. The biomedical, environmental, and electrochemical energy storage applications of iron oxide nanostructured materials are discussed. Finally, challenges and perspectives are proposed for future investigations on the liquid-phase synthesis and applications of iron oxide nanostructured materials.     

以胶体粒子为模板制备核壳纳米复合粒子

核壳纳米复合粒子具有许多不同于单组分胶体粒子的独特的光、电、磁、催化等物理与化学性质,是构筑新型功能复合材料的重要组元,在光子带隙材料、微波吸收材料、电磁流变液、催化剂和生物等领域有重要应用.本文从控制核壳复合粒子的微观结构及壳层均匀性与厚度的角度,详细评述了目前以胶体粒子为模板制备粒径从纳米到微米尺度的核壳复合粒子的方法.指出利用胶体粒子模板表面与壳层物质或其前驱物间的特殊相互作用(包括静电和化学相互作用),是完善现有制备方法和发展新方法来制备具有设定组成、结构和性能的核壳复合粒子的关键,同时也是将来的粒子表面纳米工程和获取有序的、先进纳米复合材料的主要方向。     

Nanostructured materials in potentiometry

Potentiometry is a very simple electrochemical technique with extraordinary analytical capabilities. It is also well known that nanostructured materials display properties which they do not show in the bulk phase. The combination of the two fields of potentiometry and nanomaterials is therefore a promising area of research and development. In this report, we explain the fundamentals of potentiometric devices that incorporate nanostructured materials and we highlight the advantages and drawbacks of combining nanomaterials and potentiometry. The paper provides an overview of the role of nanostructured materials in the two commonest potentiometric sensors: field-effect transistors and ion-selective electrodes. Additionally, we provide a few recent examples of new potentiometric sensors that are based on receptors immobilized directly onto the nanostructured material surface. Moreover, we summarize the use of potentiometry to analyze processes involving nanostructured materials and the prospects that the use of nanopores offer to potentiometry. Finally, we discuss several difficulties that currently hinder developments in the field and some future trends that will extend potentiometry into new analytical areas such as biology and medicine.     

Efficient recovery of rare earth elements from coal based resources: a bioleaching approach

Rare earth element (REE) resources in coal-related materials are vast. Assuming a coal production rate of 600 million short tons per year with an average REE content of 200 ppm, the potential REE resource is 120,000 tons per year, which is similar to the annual global production of REEs. Most of those resources that are associated with coal-related materials are found in association with the gangue or ash-based content from the coal ore. Under normal coal plant operation, the REEs often end up in refuse piles or tailings impoundments. In many cases, these REEs can be recovered at low cost using appropriate coal preparation, heap leaching, solvent extraction and/or selective precipitation, followed by subsequent separation and purification of individual REEs. In the present research, the processing approach uses a natural pyrite stream, which was removed during coal cleaning and used to enhance leaching. Bio-oxidation has been used commercially to accelerate leaching, and this approach has been applied to coal-based materials. The ferric ions generated from bio-oxidation oxidize sulfide minerals such as pyrite, which generates acid. Both acid and ferric ions are helpful for leaching REEs, as well as for removing residual sulfides, thereby preventing future acid mine drainage and related liabilities. It can be seen that, recovery of REEs from coal waste materials can enable coal producers to use untapped REEs resources to produce revenue and extend resource life while simultaneously reducing future environmental issues and costs.     

Functionalization of gold and carbon nanostructured materials using gamma-ray irradiation

Gold nanoparticles were successfully attached to the surface sites of carbon nanotubes (CNT). Both nanostructured materials were functionalized by λ-ray irradiation without chemical treatments for creating active sites. UV–visible absorption spectra of the un-irradiated and gamma ray-irradiated nanomaterials are also studied. The absorption spectrum of the irradiated CNT shows a new strong peak located at 700 nm, which might act as the active site on the surface of CNT, the result being an attachment of gold nanoparticles. This approach provides an efficient method to attach other nanostructures to carbon nanotubes for using them in different applications such as medicine and synthesis of catalytic materials.     

From diatoms to silica-based biohybrids

This critical review shows that diatoms can be a source of inspiration for the synthesis of advanced nanostructured biohybrids. These single cell microalgae are living inside a porous silica shell called 'frustule'. Mimicking this model, silica-based biohybrids have been produced via the so-called sol-gel process. Biomolecules such as proteins, enzymes or antibodies can be trapped within a silica matrix leading to hybrid biosensors and bioreactors. Whole cells remain viable and retain their metabolic activity leading to the formation of living biohybrids that offer new possibilities in the field of biotechnology and nanomedicine. Diatom frustules exhibit an incredible variety of sophisticated shapes; they can be used as 3D hierarchically structured materials for the realization of sensors, photonic devices or microfluidics. They can also be a model for the bio-templated synthesis of nanostructured materials. Diatom nanotechnology is becoming a new field of research where biologists and materials scientists are working together! (125 references).     

纳米发光材料研究的若干进展

本文综述纳米发光材料的研究进展情况,着重总结了（稀土）掺杂型纳米发光材料的制备方法和表征手段,同时介绍了这些纳米发光材料的性质和应用,并对其未来发展趋势进行了展望。     

Ionic liquids as amphiphile self-assembly media

In recent years, the number of non-aqueous solvents which mediate hydrocarbon-solvent interactions and promote the self-assembly of amphiphiles has been markedly increased by the reporting of over 30 ionic liquids which possess this previously unusual solvent characteristic. This new situation allows a different exploration of the molecular "solvophobic effect" and tests the current understanding of amphiphile self-assembly. Interestingly, both protic and aprotic ionic liquids support amphiphile self-assembly, indicating that it is not required for the solvents to be able to form a hydrogen bonded network. Here, the use of ionic liquids as amphiphile self-assembly media is reviewed, including micelle and liquid crystalline mesophase formation, their use as a solvent phase in microemulsions and emulsions, and the emerging field of nanostructured inorganic materials synthesis. Surfactants, lipids and block co-polymers are the focus amphiphile classes in this critical review (174 references).     

Nanoparticles,Proteins, and Nucleic Acids: Biotechnology Meets Materials Science

Based on fundamental chemistry, biotechnology and materials science have developed over the past three decades into today's powerful disciplines which allow the engineering of advanced technical devices and the industrial production of active substances for pharmaceutical and biomedical applications. This review is focused on current approaches emerging at the intersection of materials research, nanosciences, and molecular biotechnology. This novel and highly interdisciplinary field of chemistry is closely associated with both the physical and chemical properties of organic and inorganic nanoparticles, as well as to the various aspects of molecular cloning, recombinant DNA and protein technology, and immunology. Evolutionary optimized biomolecules such as nucleic acids, proteins, and supramolecular complexes of these components, are utilized in the production of nanostructured and mesoscopic architectures from organic and inorganic materials. The highly developed instruments and techniques of today's materials research are used for basic and applied studies of fundamental biological processes.     

Surface modification of electrodes by carbon nanotubes and gold and silver nanoparticles in monoaminoxidase biosensors for the determination of some antidepressants

Surface modification of screen-printed graphite electrodes with nanostructured materials (multiwall carbon nanotubes, gold and silver nanoparticles) allow their application as supports of amperometric monoaminoxidase biosensors for the determination of antidepressant drugs (moclobemide, tianeptine, and amitriptyline). This approach improves analytical characteristics of the corresponding biosensors because of the inhibitory effect of antidepressants (two-parameter concerted inhibition) on the catalytic activity of an immobilized enzyme. The analytical capabilities of the developed biosensor types were compared. The range of working concentrations was from 5 × 10^–9 to 1 × 10^–4 M and the lower limit of the analytical range was of about 8 × 10^–10 M. Biosensors based on electrodes modified with nanostructured materials were tested in the control of the concentration of drugs in body fluids (urine) and dosage forms.     

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.     

Quantifying protein adsorption and function at nanostructured materials: enzymatic activity of glucose oxidase at GLAD structured electrodes

Nanostructured materials strongly modulate the behavior of adsorbed proteins; however, the characterization of such interactions is challenging. Here we present a novel method combining protein adsorption studies at nanostructured quartz crystal microbalance sensor surfaces (QCM-D) with optical (surface plasmon resonance SPR) and electrochemical methods (cyclic voltammetry CV) allowing quantification of both bound protein amount and activity. The redox enzyme glucose oxidase is studied as a model system to explore alterations in protein functional behavior caused by adsorption onto flat and nanostructured surfaces. This enzyme and such materials interactions are relevant for biosensor applications. Novel nanostructured gold electrode surfaces with controlled curvature were fabricated using colloidal lithography and glancing angle deposition (GLAD). The adsorption of enzyme to nanostructured interfaces was found to be significantly larger compared to flat interfaces even after normalization for the increased surface area, and no substantial desorption was observed within 24 h. A decreased enzymatic activity was observed over the same period of time, which indicates a slow conformational change of the adsorbed enzyme induced by the materials interface. Additionally, we make use of inherent localized surface plasmon resonances in these nanostructured materials to directly quantify the protein binding. We hereby demonstrate a QCM-D-based methodology to quantify protein binding at complex nanostructured materials. Our approach allows label free quantification of protein binding at nanostructured interfaces.     

Nanostructured alkyl carboxylic acid-based restricted access solvents: Application to the combined microextraction and cleanup of polycyclic aromatic hydrocarbons in mosses

Alkyl carboxylic acid-based nanostructured solvents, synthesized in mixtures of tetrahydrofuran (THF) and water through self-assembly and coacervation, were proved to behave as restricted access liquids. Both physical and chemical mechanisms were found responsible for exclusion of macromolecules such as proteins and polysaccharides. The potential of these solvents for extracting small molecules from complex solid samples, without interference from large biomolecules, was here evaluated. For this purpose, they were applied to the extraction of 14 priority polycyclic aromatic hydrocarbons (PAHs) from mosses prior to their separation by liquid chromatography and fluorescence detection (LC-FLD). Sample treatment involved the vortex shaking of 200 mg of moss with 200 μL of decanoic acid-based solvent for 5 min, subsequent centrifugation for 8 min and analysis of the extract by LC-FLD using external calibration. Proteins precipitated during extraction because of both the decrease of the dielectric constant of the solution caused by THF and the formation of macromolecular complexes with decanoic acid. Polysaccharides were not solubilized in the aqueous cavities of the solvent because of their size exclusion. In-house method validation was performed according to the recommendations of the European Commission Decision 202/657/EC. Method detection and quantification limits for the different PAHs were in the ranges 0.04–0.24 and 0.14–0.80 μg kg⁻¹, respectively. The method was applied to the determination of different moss species collected in both polluted and unpolluted sites in the South of Spain. Recoveries were within the range 71–110%. The results obtained show that solvents with restricted access properties have the potential to expand the scope of application of restricted access materials to areas other than biological fluids because of their suitability to combine analyte isolation and sample cleanup of solid samples in a single step.     

Nanostructured Electrodes for High‐Performance Pseudocapacitors

The depletion of traditional energy resources as well as the desire to reduce high CO₂ emissions associated with energy production means that energy storage is now becoming more important than ever. New functional electrode materials are urgently needed for next‐generation energy storage systems, such as supercapacitors or batteries, to meet the ever increasing demand for higher energy and power densities. Advances in nanotechnology are essential to meet those future challenges. It is critical to develop ways of synthesizing new nanomaterials with enhanced properties or combinations of properties to meet future challenges. In this Minireview we discuss several important recent studies in developing nanostructured pseudocapacitor electrodes, and summarize three major parameters that are the most important in determining the performance of electrode materials. A technique to optimize these parameters simultaneously and to achieve both high energy and power densities is also introduced.     

Mechanistic study of silver nanoparticle formation on conducting polymer surfaces

Conducting polymer (polyaniline) sheets are shown to be active substrates to promote the growth of nanostructured silver thin films with highly tunable morphologies. Using the spontaneous electroless deposition of silver, we show that a range of nanostructured metallic features can be controllably and reproducibly formed over large surface areas. The structural morphology of the resulting metal-polymer nanocomposite is demonstrated to be sensitive to experimental parameters such as ion concentration, temperature, and polymer processing and can range from densely packed oblate nanosheets to bulk crystalline metals. The deposition mechanisms are explained using a diffusion-limited aggregation (DLA) model to describe the semi-fractal-like growth of the metal nanostructures. We find these composite films to exhibit strong surface-enhanced Raman (SERS) activity, and the nanostructured features are optimized with respect to SERS activity using a self-assembled monolayer of mercapto-benzoic acid as a model Raman reporter. SERS enhancements are estimated to be on the order of 10(7). Through micro-Raman SERS mapping, these materials are shown to exhibit uniform SERS responses over macroscopic areas. These metal-polymer nanocomposites benefit from the underlying polymer's processability to yield SERS-active materials of almost limitless shape and size and show significant promise for future SERS-based sensing and detection schemes.     

Effect of vegetable oils on obtaining lipid nanocarriers for sea buckthorn extract encapsulation

The principal aim of the present study was to develop new safe and highly antioxidant nanostructured lipid carriers loaded with sea buckthorn extract. Three vegetable oils — grape seed oil, sea buckthorn oil and St. John's wort oil (Hypericum perforatum oil) — were used as matrix components and the modified high shear homogenization technique has been employed for the synthesis of nanostructured materials. The effect of these oils on the antioxidant and antimicrobial activities of loaded sea buckthorn extract — nanostructured lipid carriers — has also been studied. For this purpose, a combination of two solid lipids: cetyl palmitate with glyceryl stearate and lecithin/block copolymer has been used. The obtained nanostructured lipid carriers have been characterized for the particle size and zeta potential by means of dynamic light scattering measurements. The nano-dimension morphology of loaded nanostructured lipid carriers was confirmed by transmission electron microscopy. Their crystallinity measured by differential scanning calorimetry has revealed a high disordered lipid matrix. The properties of sea-buckthorn-extract-loaded nanoparticles have been evaluated by an appropriate in vitro analysis (chemiluminescence method). The presence of the three vegetable oils influences extensively the antioxidant properties of the developed nano-formulations, as has been demonstrated using the chemiluminescence technique. The antimicrobial activity of the studied nanostructured lipid carriers, analyzed by the diffusion disc method, shows in most of the samples a high efficiency against Escherichia coli bacteria.     

Polymerization of and within self-organized media

Self-organized surfactant solutions, such as microemulsions, vesicular solutions or dispersions, or lyotropic mesophases can serve as templates for the structure directed synthesis of organic polymers. Recent developments of templating within these equilibrium nanostructured fluids are reviewed. Depending on the template structure and the reaction conditions, the outcomes may be polyampholytes, amphiphiles, nanoparticles, hollow spheres, or mesoporous polymers. For each structure and morphology, the final product materials reflect a delicate balance between phase behavior and the reaction and mass transfer parameters that set structure. Experimental and theoretical aspects of reaction kinetics and thermodynamics such as monomer partitioning, swelling behavior and polymerization-induced phase separation are discussed.     

Electrorheological fluids

Advances in one of the most promising fields of the chemistry of smart materials, specifically, electrorheological fluids are considered. The electrorheological effect and the structure and properties of electrorheological fluids are described. Modern views on the nature of the electrorheological effect are considered. The review focuses on the application of nanomaterials as the disperse phases in electrorheological fluids. Recent avances in the sol-gel synthesis of nanostructured colloid systems and the electrorheological characteristics of their based liquid systems are considered. Certain aspects of practical application of electrorheological fluids are presented.