NUIG4: A biocompatible pcu metal-organic framework with an exceptional doxorubicin encapsulation capacity.

Metal-organic frameworks (MOFs) are promising multifunctional porous materials for biomedical and environmental applications. Here, we report synthesis and characterization of a new MOF based on the tetrahedral secondary building unit [Zn4O(CBAB)3]n (NUIG4), where CBABH2 = 4-((4-carboxybenzylidene)amino)benzoic acid. NUIG4 belongs to the family of MOFs with primitive cubic pcu topology, being a rare example with 4-fold interpenetration. The pore architecture enables unprecedentedly high doxorubicin (DOX) loading capacity (1955 mg DOX/g NUIG4) with pH-controlled release. Solid-state NMR and ab initio modeling confirmed formation of aromatic π-π stacking interactions between DOX and the framework. Preliminary cell-line experiments suggested a protective effect of NUIG4 on healthy HDF cells against DOX toxicity. NUIG4 also displays potential for adsorptive small-molecule gas separation, with a BET surface area of 1358 m2 g-1 and high selectivity of 2.75 for C2H2 over CO2.

Microbial electrosynthesis: Towards sustainable biorefineries for production of green chemicals from CO2 emissions.

Decarbonisation of the economy has become a priority at the global level, and the resulting legislative pressure is pushing the chemical and energy industries away from fossil fuels. Microbial electrosynthesis (MES) has emerged as a promising technology to promote this transition, which will further benefit from the decreasing cost of renewable energy. However, several technological challenges need to be addressed before the MES technology can reach its maturity. The aim of this review is to critically discuss the bottlenecks hampering the industrial adoption of MES, considering the whole production process (from the CO2 source to the marketable products), and indicate future directions. A flexible stack design, with flat or tubular MES modules and direct CO2 supply, is required for site-specific decentralised applications. The experience gained for scaling-up electrochemical cells (e.g. electrolysers) can serve as a guideline for realising pilot MES stacks to be technologically and economically evaluated in industrially relevant conditions. Maximising CO2 abatement rate by targeting high-rate production of acetate can promote adoption of MES technology in the short term. However, the development of a replicable and robust strategy for production and in-line extraction of higher-value products (e.g. caproic acid and hexanol) at the cathode, and meaningful exploitation of the currently overlooked anodic reactions, can further boost MES cost-effectiveness. Furthermore, the use of energy storage and smart electronics can alleviate the fluctuations of renewable energy supply. Despite the unresolved challenges, the flexible MES technology can be applied to decarbonise flue gas from different sources, to upgrade industrial and wastewater treatment plants, and to produce a wide array of green and sustainable chemicals. The combination of these benefits can support the industrial adoption of MES over competing technologies.

One-Step Controllable Synthesis of Mesoporous MgCo2 O4 Nanosheet Arrays with Ethanol on Nickel Foam as an Advanced Electrode Material for High-Performance Supercapacitors.

In recent years, ternary transition metal oxides (TTMOs), especially spinel type TTMOs have attracted widespread attention as promising candidates for electrode materials. Among all of the popular TTMOs, MgCo2 O4 is an outstanding one, owing to its superior theoretical capacitance. In this work, MgCo2 O4 nanosheet arrays (NSAs) grown directly on nickel foams were fabricated through a facile hydrothermal process at 120 °C for 4 h. With a series of structural and morphological characterization techniques, it was found that the ethanol played a key role in controlling the composition and morphology during the synthesis process. The MgCo2 O4 NSAs exhibited a superior specific capacitance of 853.06 C g-1 (at 1 mA cm-2 ) and enhanced cycling performance, with 94.65 % of initial capacitance retained after 3000 cycles when used as a binder-free integrated electrode for electrochemical supercapacitors; much higher than other reported data for MgCo2 O4 as well. The excellent electrochemical properties mainly came from the unique morphology of the MgCo2 O4 NSAs. This study will demonstrate the applications of MgCo2 O4 NSAs based large-scale supercapacitors grown on low-cost nickel foams.

The evolution of size, shape, and surface morphology of gold nanorods.

We investigate the transformation of single crystal gold nanorod surface morphology over extended growth times. After initial rapid anisotropic growth and disappearance of {111} bridging facets, the aspect ratios converge across AgNO3 concentrations. The surface morphology transitions from faceted to curved. These observations imply the final aspect ratio has little dependence on the AgNO3 concentration, consistent with primary control of the AgNO3 over aspect ratio occurring at the symmetry breaking point.

A Mechanism for Symmetry Breaking and Shape Control in Single-Crystal Gold Nanorods.

The phenomenon of symmetry breaking-in which the order of symmetry of a system is reduced despite manifest higher-order symmetry in the underlying fundamental laws-is pervasive throughout science and nature, playing a critical role in fields ranging from particle physics and quantum theory to cosmology and general relativity. For the growth of crystals, symmetry breaking is the crucial step required to generate a macroscopic shape that has fewer symmetry elements than the unit cell and/or seed crystal from which it grew. Advances in colloid synthesis have enabled a wide variety of nanocrystal morphologies to be achieved, albeit empirically. Of the various nanoparticle morphologies synthesized, gold nanorods have perhaps been the most intensely studied, thanks largely to their unique morphology-dependent optical properties and exciting application potential. However, despite intense research efforts, an understanding of the mechanism by which a single crystal breaks symmetry and grows anisotropically has remained elusive, with many reports presenting seemingly conflicting data and theories. A fundamental understanding of the symmetry breaking process is needed to provide a rational framework upon which future synthetic approaches can be built. Inspired by recent experimental results and drawing upon the wider literature, we present a mechanism for gold nanorod growth from the moments prior to symmetry breaking to the final product. In particular, we describe the steps by which a cuboctahedral seed particle breaks symmetry and undergoes anisotropic growth to form a nanorod. With an emphasis on the evolving crystal structure, we highlight the key geometrical and chemical drivers behind the symmetry breaking process and factors that govern the formation and growth of nanorods, including control over the crystal width, length, and surface faceting. We propose that symmetry breaking is induced by an initial formation of a new surface structure that is stabilized by the deposition of silver, thus preserving this facet in the embryonic nanorod. These new surfaces initially form stochastically as truncations that remove high-energy edge atoms at the intersection of existing {111} facets and represent the beginnings of a {011}-type surface. Crucially, the finely tuned [HAuCl4]:[AgNO3] ratio and reduction potential of the system mean that silver deposition can occur on the more atomically open surface but not on the pre-existing lower-index facets. The stabilized surfaces develop into side facets of the nascent nanorod, while the largely unpassivated {111} facets are the predominant site of Au atom deposition. Growth in the width direction is tightly controlled by a self-sustaining cycle of galvanic replacement and silver deposition. It is the [HAuCl4]:[AgNO3] ratio that directly determines the particle size at which the more open atomic surfaces can be stabilized by silver and the rate of growth in the width direction following symmetry breaking, thus explaining the known aspect ratio control with Ag ion concentration. We describe the evolving surface faceting of the nanorod and the emergence of higher-index facets. Collectively, these observations allow us to identify facet-size and edge-atom effects as a simple fundamental driver of symmetry breaking and the subsequent development of new surfaces in the presence of adsorbates.

Symmetry breaking and silver in gold nanorod growth.

Formation of anisotropic nanocrystals from isotropic single-crystal precursors requires an essential symmetry breaking event. Single-crystal gold nanorods have become the model system for investigating the synthesis of anisotropic nanoparticles, and their growth mechanism continues to be the subject of intense investigation. Despite this, very little is known about the symmetry breaking event that precedes shape anisotropy. In particular, there remains limited understanding of how an isotropic seed particle becomes asymmetric and of the growth parameters that trigger and drive this process. Here, we present direct atomic-scale observations of the nanocrystal structure at the embryonic stages of gold nanorod growth. The onset of asymmetry of the nascent crystals is observed to occur only for single-crystal particles that have reached diameters of 4-6 nm and only in the presence of silver ions. In this size range, small, asymmetric truncating surfaces with an open atomic structure become apparent. Furthermore, {111} twin planes are observed in some immature nanorods within 1-3 monolayers of the surface. These results provide direct observation of the structural changes that break the symmetry of isotropic nascent nanocrystals and ultimately enable the growth of asymmetric nanocrystals.

Cation non-stoichiometry in multi-component oxide nanoparticles by solution chemistry: a case study on CaWO4 for tailored structural properties.

Chemical composition directly determines the structure and properties of almost all bulk inorganic solids, which are however popularly dismissed in the literature as a cause of property changes when studying multi-component oxide nanostructures by solution chemistries. The current work focuses on this subject through a systematic case study on CaWO(4) nanocrystals. CaWO(4) nanocrystals were prepared using room-temperature solution chemistry, in which a capping agent of citric acid was employed for kinetic grain size control. Sample characterizations by a set of techniques indicated that 5-7 nm CaWO(4) was obtained at room temperature, showing a pure-phase of tetrahedral scheelite structure. The molar ratio of Ca(2+) to W(6+) was found to be 1.2:1, apparently deviating from the unity expected for the stoichiometric CaWO(4). Such nonstoichiometry was further modulated via iso-valent incorporation of smaller Zn(2+) to the Ca(2+)-sites in CaWO(4). It is found that with increasing the Zn(2+) content, there appeared transformation from high to low nonstoichiometry, though a pure scheelite-typed structure was retained. Such a nonstoichiometry was primarily represented by excessive cations like Zn(2+) and/or Ca(2+) within the surface disorder layers, which in turn showed a great impact on the structure and properties as demonstrated by a lattice contraction, band-gap narrowing, luminescence quenching, as well as improved conductivity. The property changes were rationalized in terms of surface structural disorder, electro-negativity discrepancy, and effective activation on the mobile protons. Consequently, systematic control over the non-stoichiometry for single-phase multi-component oxide nanostructures by solution chemistry is proven fundamentally important, which may help to achieve quantitatively the structure-property relationship for materials design and performance optimization.

Metastable monoclinic ZnMoO4: hydrothermal synthesis, optical properties and photocatalytic performance.

Metastable monoclinic ZnMoO4 was successfully synthesized via a hydrothermal route with variation of reaction temperatures and time at pH value of 5.7. Systematic sample characterizations were carried out, including X-ray powder diffraction, scanning electron microscopy, Fourier transformed infrared spectra, UV-visible diffuse reflectance spectra, and photoluminescence spectra. The results show that all as-prepared ZnMoO4 samples were demonstrated to crystallize in a pure-phase of monoclinic wolframite structure. All samples were formed in plate-like morphology. Six IR active vibrational bands were observed in the wave number range of 400-900 cm(-1). The band gap of as-prepared ZnMoO4 was estimated to be 2.86 eV by Tauc equation. Photoluminescence measurement indicates that as-prepared ZnMoO4 exhibits a broad blue-green emission under excitation wavelength of 280 nm at room temperature. Photocatalytic activity of as-prepared ZnMoO4 was examined by monitoring the degradation of methyl orange dye in an aqueous solution under UV radiation of 365 nm. The as-prepared ZnMoO4 obtained at 180 degrees C for 40 h showed the best photocatalytic activity with completing degradation of MO in irradiation time of 120 min. Consequently, monoclinic ZnMoO4 proved to be an efficient near visible light photocatalyst.

Water-titanate intercalated nanotubes: fabrication, polarization, and giant dielectric property.

What's the difference when water molecules are confined in a rather limited space? This work addresses this question by decorating water molecules within the scrolled titanate nanotubes. Both scrolled nanotubes Na(0.96)H(1.04)Ti(3)O(7)·nH(2)O and Na(0.036)H(1.964)Ti(3)O(7)·nH(2)O were first prepared to show large specific areas around 200 m(2) g(-1), within which quantities of water molecules were confined to form H(2)O tubes that are alternatively arranged with the titanate nanotubes. This unique double-tube structure exhibited remarkable polarization and dielectric performance, yielding a huge dielectric constant around ε = 14,000, comparable to some known giant-dielectric-constant ceramics. Depending on the measurement frequency and temperature, the dielectric relaxation peaks were monitored by the content of the water molecules confined within the nanotubes. A two-layer dielectric model that involves the distinct anisotropy and confinement effect of the double-tube structure was proposed to explain this dielectric behavior. The findings reported in this work may pave the way for optimizing many subtle hydrated nanostructures in nature that could create an abundance of confined water molecules for a broad class of applications.

Insights into the roles of organic coating in tuning the defect chemistry of monodisperse TiO(2) nanocrystals for tailored properties.

This work initiated a systematic study on the chemical nature of organic coating for monodispersed nanoparticles and its impact on the defect chemistry and the relevant properties. Monodispersed TiO(2) nanoparticles were prepared by a nonhydrolytic sol-gel reaction, which showed features of uniform diameter distribution around 5.2 nm, high crystallinity, and single anatase structure. These nanoparticles were terminated by oleate-related molecules, which stabilized the surface oxygen vacancies and further generated intense photoluminescence and co-existence of ferromagnetism and diamagnetism. After removal of organic coating, the nanoparticles became highly aggregated with no apparent changes in particle size, while the oxygen vacancy concentration was significantly reduced, as followed by energy position shift towards the deeper-levels which promoted the separation of photogenerated electrons and holes for improved photocatalytic activity. The results reported here are fundamentally important, which may be extended to comprehend the size-dependent defects and structure-property correlations of monodispersed nanoparticles for applications.

Supersaturated spontaneous nucleation to TiO2 microspheres: synthesis and giant dielectric performance.

A facile supersaturated spontaneous nucleation method was initiated to fabricate novel hierarchical microspheres assembled from roughly parallel rutile TiO2 nanowires, which showed a dielectric constant of 104 level, about one order of magnitude larger than those for all other polymorphic TiO2.

Preparation of cereal-like YVO(4):Ln(3+) (Ln = Sm, Eu, Tb, Dy) for high quantum efficiency photoluminescence.

In this work, preparation of cereal-like architectures Y V O(4) and Y V O(4):Ln(3 + ) (Ln = Eu, Sm, Dy, Tb) was initiated using a hydrothermal method. During the formation reaction, Na(3)C(6)H(5)O(7).2H(2)O was used to effectively adjust the concentration of Y(3 + ) species necessary for cereal-like architectures. Phase structure, surface chemistry, morphology, and photoluminescence were characterized by x-ray powder diffraction, Fourier transformed infrared spectra, scanning electron microscopy, transmission electron microscopy, and photoluminescence spectra. All samples crystallize in a tetragonal zircon structure, stably showing a homogeneous cereal-like morphology. This special morphology was constructed by self-assembly of tiny primary particles with a dimension of 31-32 nm. With increasing atomic number of Ln(3 + ), the lattice dimension of the cereal architectures became monotonously enlarged. This cereal-like architecture is proved unique in significantly improving the quantum efficiencies: the internal quantum efficiencies of (5)D(0) for Ln = Eu and (4)F(9/2) for Ln = Dy were 14.6% and 11.4%, respectively, which are all superior over those of the counterparts of nanoparticles reported in the literature. The average lifetime of the (5)D(0) level for Ln = Eu was calculated to be 98 micros, which is longer than that of 50 micros of the (4)F(9/2) level for Ln = Dy. The strong photoluminescence might be the consequence of the effective energy transfer due to the greatly reduced defect centers from this special self-assembly structure.