Competing Roles of Two Kinds of Ligand during Nonclassical Crystallization of Pillared-Layer Metal-Organic Frameworks Elucidated Using Microfluidic Systems.

To diversify metal-organic frameworks (MOFs), multi-component MOFs constructed from more than two kinds of bridging ligand have been actively investigated due to the high degree of design freedom afforded by the combination of multiple ligands. Predicting the synthesis conditions for such MOFs requires an understanding of the crystallization mechanism, which has so far remained elusive. In this context, microflow systems are efficient tools for capturing non-equilibrium states as they facilitate precise and efficient mixing with reaction times that correspond to the distance from the mixing point, thus enabling reliable control of non-equilibrium crystallization processes. Herein, we prepared coordination polymers with pillared-layer structures and observed the intermediates in the syntheses with an in-situ measurement system that combines microflow reaction with UV/Vis and X-ray absorption fine-structure spectroscopies, thereby enabling their rapid nucleation to be monitored. Based on the results, a three-step nonclassical nucleation mechanism involving two kinds of intermediate is proposed.

Formation of Metal-Organic Frameworks on a Metal Ion-Doped Polymer Substrate: In-Depth Time-Course Analysis Using Scanning Electron Microscopy.

The growth of metal-organic frameworks (MOFs) on a metal ion-doped polymer as a precursor and support substrate was investigated based on mechanistic and kinetic analyses. The studies were performed by varying the reaction temperature and the concentrations of the organic ligand and nucleation-promoted additive. Using the NH2-MIL-53(Al) framework as a model system, a systematic study of the mechanism of formation of tetragonal- and rod-shaped NH2-MIL-53(Al) crystals on the substrate was performed. The nucleation rate in the early stage of the reaction is a major factor in determining the surface morphology of the resultant NH2-MIL-53(Al) crystal films, as confirmed by changing the concentration of organic ligands and by employing pyridine additives. These results provide a fundamental understanding of the influence of the nucleation rate on the ability to control the morphology and structure of MOF crystal films.

A Turn-On Detection of DNA Sequences by Means of Fluorescence of DNA-Templated Silver Nanoclusters via Unique Interactions of a Hydrated Ionic Liquid.

Nucleic acid stability and structure, which are crucial to the properties of fluorescent DNA-templated silver nanoclusters (DNA-Ag NCs), significantly change in ionic liquids. In this work, our purpose was to study DNA-Ag NCs in a buffer containing the hydrated ionic liquid of choline dihydrogen phosphate (choline dhp) to improve fluorescence for application in DNA detection. Due to the stabilisation of an i-motif structure by the choline cation, a unique fluorescence emission-that was not seen in an aqueous buffer-was observed in choline dhp and remained stable for more than 30 days. A DNA-Ag NCs probe was designed to have greater fluorescence intensity in choline dhp in the presence of a target DNA. A turn-on sensing platform in choline dhp was built for the detection of the BRCA1 gene, which is related to familial breast and ovarian cancers. This platform showed better sensitivity and selectivity in distinguishing a target sequence from a mutant sequence in choline dhp than in the aqueous buffer. Our study provides new evidence regarding the effects of structure on properties of fluorescent DNA-Ag NCs and expands the applications of fluorescent DNA-Ag NCs in an ionic liquid because of improved sensitivity and selectivity.

DNA G-Wire Formation Using an Artificial Peptide is Controlled by Protease Activity.

The development of a switching system for guanine nanowire (G-wire) formation by external signals is important for nanobiotechnological applications. Here, we demonstrate a DNA nanostructural switch (G-wire <--> particles) using a designed peptide and a protease. The peptide consists of a PNA sequence for inducing DNA to form DNA-PNA hybrid G-quadruplex structures, and a protease substrate sequence acting as a switching module that is dependent on the activity of a particular protease. Micro-scale analyses via TEM and AFM showed that G-rich DNA alone forms G-wires in the presence of Ca2+, and that the peptide disrupted this formation, resulting in the formation of particles. The addition of the protease and digestion of the peptide regenerated the G-wires. Macro-scale analyses by DLS, zeta potential, CD, and gel filtration were in agreement with the microscopic observations. These results imply that the secondary structure change (DNA G-quadruplex <--> DNA/PNA hybrid structure) induces a change in the well-formed nanostructure (G-wire <--> particles). Our findings demonstrate a control system for forming DNA G-wire structures dependent on protease activity using designed peptides. Such systems hold promise for regulating the formation of nanowire for various applications, including electronic circuits for use in nanobiotechnologies.

Morphology Control of Metal-Organic Frameworks Based on Paddle-Wheel Units on Ion-Doped Polymer Substrate Using an Interfacial Growth Approach.

A three-dimensional metal-organic framework (MOF) consisting of pillared square-grid nets based on paddle-wheel units was synthesized by interfacial self-assembly of the frameworks on a metal-ion-doped polymer substrate. Although this type of Cu-based MOF is typically synthesized by a two-step solvothermal method, the utilization of a metal-ion-doped polymer substrate as a metal source for the framework allowed for the one-pot growth of MOF crystals on the substrate. The morphology of the obtained MOF crystals could be controlled from tetragonal to elongated tetragonal with different aspect ratios by changing the concentrations of the dicarboxylate layer ligands and diamine pillar ligands. The present approach provides a new route for the design and synthesis of MOF crystals and thin films for future applications such as gas membranes, catalysts, and electronic devices.

Unusual Colorimetric Change for Alkane Solvents with a Porous Coordination Framework.

Alkane-selective colorimetric change from white to pink was observed with the simple system consisting of UiO-66 and 7-azaindole. The colorimetric change was strongly enhanced with increasing amounts of defects inside the UiO-66 framework, which indicates that interaction between the defects and 7-azaindole plays a pivotal role for this phenomenon.

Trapping of a spatial transient state during the framework transformation of a porous coordination polymer.

Structural transformability accompanied by molecular accommodation is a distinguished feature of porous coordination polymers (PCPs) among porous materials. Conventional X-ray crystallography allows for the determination of each structural phase emerged during transformation. However, the propagation mechanism of transformation through an entire crystal still remains in question. Here we elucidate the structural nature of the spatial transient state, in which two different but correlated framework structures, an original phase and a deformed phase, simultaneously exist in one crystal. The deformed phase is distinctively generated only at the crystal surface region by introducing large guest molecules, while the remaining part of crystal containing small molecules maintains the original phase. By means of grazing incidence diffraction techniques we determine that the framework is sheared with sharing one edge of the original primitive cubic structure, leading to the formation of crystal domains with four mirror image relationships.

Engineering of CdS-chain arrays assembled through S⋯S interactions in 1D semiconductive coordination polymers.

One-dimensional (1D) Cd(II) coordination polymers [Cd(x-SPhOMe)2]n (x = ortho, meta, and para; HSPhOMe = methoxybenzenethiol) containing inorganic 1D (-Cd-S-)n chains were synthesized. Among these, the KGF-31 polymer bearing para-SPhOMe featured a three-strand chain structure assembled via interchain S⋯S interactions and exhibited high photoconductivity and longevity.

Direct generation of polypyrrole-coated palladium nanoparticles inside a metal-organic framework for a semihydrogenation catalyst.

Herein, the direct synthesis of polypyrrole (PPy)-coated palladium nanoparticles (PdNPs) inside a metal-organic framework (MIL-101) was successfully demonstrated. Owing to the PPy coating of PdNPs, the resulting composites exhibited higher semihydrogenation capability (selectivity: up to 96%) than the analog composite without PPy coating.

Co-generation of palladium nanoparticles and phosphate supported on metal-organic frameworks as hydrogenation catalysts.

In this study, we demonstrated the direct synthesis of sodium dihydrogen phosphate (PA) containing palladium nanoparticles (PdNPs) supported on a metal-organic framework (MOF). The resulting composite containing PA molecules coexisting with PdNPs demonstrated improved hydrogenation catalytic performance compared to the composites without PA.

Cooperative catalysis in a metal-organic framework via post-synthetic immobilisation.

Herein, we generated a series of cooperative catalysts via post-synthetic immobilisation of a Co(salen) complex in a metal-organic framework (MOF). By tuning the amount of Co(salen) in the MOF, the cooperative catalytic activities can be successfully optimised.

Two-Dimensional Metal-Organic Framework-Based Cellular Scaffolds with High Protein Adsorption, Retention, and Replenishment Capabilities.

Metal-organic frameworks (MOFs) are porous materials with adsorption, storage, and separation capabilities due to their high specific surface areas and large pore volumes. MOFs are thus used in biomedical applications, and MOF nanoparticles have been widely studied as nanocarriers for drug delivery systems. Several research groups recently reported that specific MOF nanoparticles can adsorb and retain proteins, suggesting to us that MOF nanoparticles may have advantages as novel cell culture scaffolds. However, MOF nanoparticles cannot be used as two-dimensional scaffolds for cells. We therefore established a bottom-up technique to construct two-dimensional MOFs [MIL-53 (Al)] on polymer films. The developed two-dimensional MIL-53 (Al) film [fMIL-53 (Al)] exhibited high serum protein adsorption, retention, and replenishment capabilities as compared to conventional cell culture scaffolds. ß-Galactosidase, used as a model protein, adsorbed on fMIL-53 (Al) exhibited original enzymatic activity, indicating that proteins are not denatured during the adsorption process. The viability of mouse myoblast cells (C2C12) cultured on fMIL-53 (Al) was 100%, indicating the cell compatibility of fMIL-53 (Al). Importantly, C2C12 cells cultured on serum protein-preadsorbed fMIL-53 (Al) exhibited excellent long-term adhesion, morphology, and proliferation even in a medium lacking serum proteins, demonstrating an important advantage of fMIL-53 (Al) as a cell culture scaffold, given that conventional cell culture scaffolds typically require a serum-containing medium to support stable cell adhesion and proliferation. To our knowledge, this is the first report regarding the application of MOFs as cell culture scaffolds and will serve as a starting point for studying two- and three-dimensional MOF-based cellular scaffolds for cell culture systems and for in vitro and in vivo tissue engineering.

Rational and site-selective formation of coordination polymers consisting of d10 coinage metal ions with thiolate ligands using a metal ion-doped polymer substrate.

Here, we report an interfacial approach for fabricating coordination polymers (CPs) consisting of d10 coinage metal ions with thiolate ligands on a polymer substrate. It was found that CPs were selectively formed on the polymer substrate, resulting in the formation of CP-based thin films. In addition, utilizing a mixed metal ion-doped polymer substrate leads to the formation of mixed-metal CP-based films.

Morphology design of porous coordination polymer crystals by coordination modulation.

The design of crystal morphology, or exposed crystal facets, has enabled the development (e.g., catalytic activities, material attributes, and oriented film formation) of porous coordination polymers (PCPs) without changing material compositions. However, because crystal growth mechanisms are not fully understood, control of crystal morphology still remains challenging. Herein, we report the morphology design of [Cu(3)(btc)(2)](n) (btc = benzene-1,3,5-tricarboxylate) by the coordination modulation method (modulator = n-dodecanoic acid or lauric acid). A morphological transition (octahedron-cuboctahedron-cube) in the [Cu(3)(btc)(2)](n) crystal was observed with an increase in concentration of the modulator. By suitably defining a coarse-grained standard unit of [Cu(3)(btc)(2)](n) as its cuboctahedron main pore and determining its attachment energy on crystal surfaces, Monte Carlo coarse-grain modeling revealed the population and orientation of carboxylates and elucidated an important role of the modulator in determining the <100>- and <111>-growth throughout the crystal growth process. This comprehension, in fact, successfully led to designed crystal morphologies with oriented growth on bare substrates. Because selective crystal orientations on the bare substrates were governed by crystal morphology, this contribution also casts a new light on the unexplored issue of the significance of morphology design of PCPs.

Fabrication of silver patterns on polyimide films based on solid-phase electrochemical constructive lithography using ion-exchangeable precursor layers.

We report a fully additive-based electrochemical approach to the site-selective deposition of silver on a polyimide substrate. Using a cathode coated with ion-doped precursor polyimide layers, patterns of metal masks used as anodes were successfully reproduced at the cathode-precursor interface through electrochemical and ion-exchange reactions, which resulted in the generation of silver patterns on the polyimide films after subsequent annealing and removal from the substrate. Excellent interfacial adhesion was achieved through metal nanostructures consisting of interconnecting silver nanoparticles at the metal-polymer interface, which are electrochemically grown "in" the precursor layer. This approach is a resist- and etch-free process and thus provides an effective methodology toward lower-cost and high-throughput microfabrication.

Intracellular mineralization of gold nanoparticles using gold ion-binding peptides with cell-penetrating ability.

We developed a system to directly produce gold nanoparticles in cells by intracellular mineralization in lower concentration than conventional methods using a peptide consisting of a cell-penetrating sequence and a gold ion-binding sequence. Furthermore, we could control the uniquely shaped gold nanostructures that were produced by changing peptide structures.

Elemental composition control of gold-titania nanocomposites by site-specific mineralization using artificial peptides and DNA.

Biomineralization, the precipitation of various inorganic compounds in biological systems, can be regulated in terms of the size, morphology, and crystal structure of these compounds by biomolecules such as proteins and peptides. However, it is difficult to construct complex inorganic nanostructures because they precipitate randomly in solution. Here, we report that the elemental composition of inorganic nanocomposites can be controlled by site-specific mineralization by changing the number of two inorganic-precipitating peptides bound to DNA. With a focus on gold and titania, we constructed a gold-titania photocatalyst that responds to visible light excitation. Both microscale and macroscale observations revealed that the elemental composition of this gold-titania nanocomposite can be controlled in several ten nm by changing the DNA length and the number of peptide binding sites on the DNA. Furthermore, photocatalytic activity and cell death induction effect under visible light (>450 nm) irradiation of the manufactured gold-titania nanocomposite was higher than that of commercial gold-titania and titania. Thus, we have succeeded in forming titania precipitates on a DNA terminus and gold precipitates site-specifically on double-stranded DNA as intended. Such nanometer-scale control of biomineralization represent a powerful and efficient tool for use in nanotechnology, electronics, ecology, medical science, and biotechnology.

Controlling Interfacial Ion-Transport Kinetics Using Polyelectrolyte Membranes for Additive- and Effluent-free, High-Performance Electrodeposition.

The development of high-performance, environmentally friendly electrodeposition processes is critical for emerging coating technologies because current technologies use highly complex baths containing metal salts, supporting electrolytes, and various kinds of organic additives, which are problematic from both environmental and cost perspectives. Here, we show that a 200 µm-thin polyelectrolyte membrane sandwiched between electrodes effectively concentrates metal ions through interfacial penetration, which increases the conductance between the electrodes to 0.30 S and realizes solid-state electrodeposition that produces no mist, sludge, or even waste effluent. Both, experimental results and theoretical calculations, reveal that electrodeposition is controlled by ion penetration at the solution/polyelectrolyte interface, providing an intrinsically different ion-transport mechanism to that of conventional diffusion-controlled electrodeposition. The setup, which includes 0.50 mol L-1 copper sulfate and no additives, delivers a maximum current density of 300 mA cm-2, which is nearly fivefold higher than that of a current commercial plating bath containing organic additives.

Fabrication of copper damascene patterns on polyimide using direct metallization on trench templates generated by imprint lithography.

Facile imprint and wet chemical processes were used to fabricate copper damascene patterns on polyimide substrate. Poly(amic acid) substrate with trench structures as template has been successfully prepared by imprint lithography using a poly(dimethylsiloxane) mold. The doped Ni(2+) ions into a template through ion-exchange reaction were reduced by an aqueous NaBH(4) solution, resulting in the formation of a nickel thin layer along the surface structure of the template. The resulting nickel films can act as catalyst for subsequent electrodeposition of copper. After electrodeposition, a polishing process was carried out for removing excess deposited copper films, followed by imidization of the substrate. The resulting damascene structured copper films exhibited fine and good adhesion with the polyimide substrate, and they could be utilized for good application in the fields of minute copper circuit patterns on insulating substrates.

Synthesis of pH-responsive nanocomposite microgels with size-controlled gold nanoparticles from ion-doped, lightly cross-linked poly(vinylpyridine).

The synthesis of composite microgels consisting of pH-responsive latexes with gold nanoparticles was investigated along with the optical properties of the products. The gold nanoparticles were deposited by wet chemical reduction from gold ions adsorbed in cross-linked poly(2-vinylpyridine) latexes, by which the mean particle size of the gold nanoparticles could be systematically controlled over a range of 10-30 nm simply by varying the reduction rate. Microscopic analysis showed that the gold nanoparticles were formed only on the surface of the microgels, resulting from diffusion of the gold ions from the interior to the surface of the microgels during reduction treatment. The resulting nanocomposites preserved the pH-responsive properties of the pure latexes. The degree of plasmon coupling, originating from dipole interactions among the gold nanoparticles, was dependent on the size of the nanoparticles and could be reversibly controlled by varying the pH of the aqueous solution. The process allowed independent control of the size and interparticle distance among gold nanoparticles, an ability that is important in increasing the fundamental understanding of the structure-dependent properties of gold nanoparticles and also for biological applications using functionalized composite latexes/microgels.