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Journal: Chemical Society reviews


This tutorial review will introduce and explore the fundamental aspects of nanopore (bio)sensing, fabrication, modification, and the emerging technologies and applications that both intrigue and inspire those working in and around the field. Although nanopores can be classified into two categories, solid-state and biological, they are essentially two sides of the same coin. For instance, both garner popularity due to their ability to confine analytes of interest to a nanoscale volume. Due to the vast diversity of nanopore platforms and applications, no single review can cover the entire landscape of published work in the field. Therefore, in this article focus will be placed on recent advancements and developments taking place in the field of solid-state nanopores. It should be stated that the intention of this tutorial review is not to cite all articles relating to solid-state nanopores, but rather to highlight recent, select developments that will hopefully benefit the new and seasoned scientist alike. Initially we begin with the fundamentals of solid-state nanopore sensing. Then the spotlight is shone on the sophisticated fabrication methods that have their origins in the semiconductor industry. One inherent advantage of solid-state nanopores is in the ease of functionalizing the surface with a range of molecules carrying functional groups. Therefore, an entire section is devoted to highlighting various chemical and bio-molecular modifications and explores how these permit the development of novel sensors with specific targets and functions. The review is completed with a discussion on novel detection strategies using nanopores. Although the most popular mode of nanopore sensing is based upon what has come to be known as ionic-current blockade sensing, there is a vast, growing literature based around exploring alternative detection techniques to further expand on the versatility of the sensors. Such techniques include optical, electronic, and force based methods. It is perhaps fair to say that these new frontiers have caused further excitement within the sensing community.

Concepts: Molecule, Chemistry, Semiconductor, Mod, Nanopore, Nanopore sequencing, The Spotlight


The increasing human need for clean and renewable energy has stimulated research in artificial photosynthesis, and in particular water photoelectrolysis as a pathway to hydrogen fuel. Nanostructured devices are widely regarded as an opportunity to improve efficiency and lower costs, but as a detailed analysis shows, they also have considerably disadvantages. This article reviews the current state of research on nanoscale-enhanced photoelectrodes and photocatalysts for the water splitting reaction. The focus is on transition metal oxides with special emphasis of Fe(2)O(3), but nitrides and chalcogenides, and main group element compounds, including carbon nitride and silicon, are also covered. The effects of nanostructuring on carrier generation and collection, multiple exciton generation, and quantum confinement are also discussed, as well as implications of particle size on surface recombination, on the size of space charge layers and on the possibility of controlling nanostructure energetics via potential determining ions. After a summary of electrocatalytic and plasmonic nanostructures, the review concludes with an outlook on the challenges in solar fuel generation with nanoscale inorganic materials.

Concepts: Oxygen, Energy, Hydrogen, Atom, Photoelectrochemical cell, Transition metal, Photocatalytic water splitting, Artificial photosynthesis


This tutorial review discusses the structural and electronic consequences of the Jahn-Teller effect in transition metal complexes, focussing on copper(ii) compounds which tend to be the most studied. The nature of a Jahn-Teller distortion in molecular complexes and extended lattices can be manipulated by application of pressure or temperature, by doping a molecule into a host lattice, or simply by molecular design. Many of these results have been achieved using compounds with a trans-[CuX(4)Y(2)] coordination sphere, which seems to afford copper centres that are particularly sensitive to their environment. Jahn-Teller distortions lead to some unusual phenomena in molecular magnetism, and are important to the functionality of important classes of conducting and superconducting ceramics.

Concepts: Electron, Oxygen, Chemical bonding, Zinc, Coordination chemistry, Inorganic chemistry, Silver, Jahn–Teller effect


C-S bond activation, cleavage and transformations by means of transition metal compounds have recently become more and more important in the petroleum industry and synthetic chemistry. Homogeneous transition metal compounds have been investigated in order to provide the fundamental insight into the C-S bond cleavage in problematic organosulfur compounds such as thiophene, benzo- and dibenzothiophene derivatives. Rendering transition-metal mediated reactions with organosulfur compounds catalytic may provide promising routes to deep hydrodesulfurization of petroleum feedstocks, and offer potentially useful synthetic protocols for cross-couplings and biomimetic organic synthesis. During the last few decades increasing work was documented on C-S bond activation and transformations by means of transition metal compounds. This review summarizes the recent advances in C-S bond cleavage via the insertion of transition metals into the inert C-S bonds of these problematic organosulfur compounds, and transition-metal mediated C-S bond transformations via C-S activation through cross-couplings of thioesters, ketene dithioacetals, sulfonyl chlorides, and other diverse organosulfur compounds.

Concepts: Organosulfur compounds, Thioester


Bioluminescent imaging (BLI) has been widely applicable in the imaging of process envisioned in life sciences. As the most conventional technique for BLI, the firefly luciferin-luciferase system is exceptionally functional in vitro and in vivo. The state-of-the-art strategy in such a system is to cage the luciferin, in which free luciferin is conjugated with distinctive functional groups, thus accommodating an impressive toolkit for exploring various biological processes, such as monitoring enzymes activity, detecting bioactive small molecules, evaluating the properties of molecular transporters, etc. This review article summarizes the rational design of caged luciferins towards diverse biotargets, as well as their applications in bioluminescent imaging. It should be emphasized that these caged luciferins can stretch out the applications of bioluminescence imaging and shed light upon understanding the pathogenesis of various diseases.

Concepts: Fungus, In vivo, In vitro, Firefly, Bioluminescence, Luciferase, Luciferin, Bioluminescence imaging


This tutorial review could serve as an introduction of cardanol into the world of soft nanomaterials; it is a biobased lipid-mixture obtained from the plant Anacardium occidentale L. Cardanol is a renewable raw material derived from a byproduct of cashew nut processing industry: Cashew Nut Shell Liquid (CNSL). Cardanol is a rich mixture of non-isoprenoic phenolic compounds that is a valuable raw material for generating a variety of soft nanomaterials such as nanotubes, nanofibers, gels and surfactants. These nanostructures may then serve as templates for the synthesis of additional nanomaterials. The wealth and diversity of cardanol-derived functional nanomaterials has urged us to present an article that will give readers a taste of a new class of cardanol-derived functional amphiphiles, along with their ability to generate hierarchical functional nanomaterials through non-covalent soft-chemical routes. In this concise review, we discuss selected examples of novel biobased surfactants, glycolipids, and polymers derived from cardanol, and their subsequent self-assembly into functional soft materials.

Concepts: Nut, Cashew, Cashew nutshell liquid, Anacardic acid


Quantum dot nanoscale semiconductor heterostructures (QDHs) are a class of materials potentially useful for integration into solar energy conversion devices. However, realizing the potential of these heterostructured systems requires the ability to identify and synthesize heterostructures with suitably designed materials, controlled size and morphology of each component, and structural control over their shared interface. In this review, we will present the case for the utility and advantages of chemically synthesized QDHs for solar energy conversion, beginning with an overview of various methods of heterostructured material synthesis and a survey of heretofore reported materials systems. The fundamental charge transfer properties of the resulting materials combinations and their basic design principles will be outlined. Finally, we will discuss representative solar photovoltaic and photoelectrochemical devices employing QDHs (including quantum dot sensitized solar cells, or QDSSCs) and examine how QDH synthesis and design impacts their performance.

Concepts: Energy, Sun, Solar cell, Photovoltaics, Solar energy, Solar power, Photovoltaic array, Solar thermal energy


Some recent studies mainly addressing the preparation and the modification of nanostructured thin films based on WO(3) and their application to photoelectrolysis of aqueous electrolytes are reviewed with the aim of rationalizing the main factors at the basis of an efficient photoanodic response. WO(3) represents one of the few materials which can achieve efficient water photo-oxidation under visible illumination, stably operating under strongly oxidizing conditions; thus the discussion of the structure-related photoelectrochemical properties of WO(3) thin films and their optimization for achieving almost quantitative photon to electron conversion constitutes the core of this contribution.

Concepts: Light, Atom, Photoelectrochemical cell, The Core, Application software


BODIPY dyes tend to be highly fluorescent, but their emissions can be attenuated by adding substituents with appropriate oxidation potentials. Substituents like these have electrons to feed into photoexcited BODIPYs, quenching their fluorescence, thereby generating relatively long-lived triplet states. Singlet oxygen is formed when these triplet states interact with (3)O(2). In tissues, this causes cell damage in regions that are illuminated, and this is the basis of photodynamic therapy (PDT). The PDT agents that are currently approved for clinical use do not feature BODIPYs, but there are many reasons to believe that this situation will change. This review summarizes the attributes of BODIPY dyes for PDT, and in some related areas.

Concepts: Fluorescence, Electron, Spectroscopy, Oxygen, Ultraviolet, Singlet oxygen, Photodynamic therapy, Triplet oxygen


Nanocomposites, composed of organic and inorganic building blocks, can combine the properties from the parent constituents and generate new properties to meet current and future demands in functional materials. Recent developments in nanoparticle synthesis provide a plethora of inorganic building blocks, building the foundation for constructing hybrid nanocomposites with unlimited possibilities. The properties of nanocomposite materials depend not only on those of individual building blocks but also on their spatial organization at different length scales. Block copolymers, which microphase separate into various nanostructures, have shown their potential for organizing inorganic nanoparticles in bulk/thin films. Block copolymer-based supramolecules further provide more versatile routes to control spatial arrangement of the nanoparticles over multiple length scales. This review provides an overview of recent efforts to control the hierarchical assemblies in block copolymer-based hybrid nanocomposites.

Concepts: Nanoparticle, Polymer, Copolymer, Polymer chemistry, Organic compound, Nanomaterials, Nanocomposite