Binary metal oxide (NiO/SnO2) composite with electrochemical bifunction: Detection of neuro transmitting drug and catalysis for hydrogen evolution reaction.

The synergetic effect between dual oxides in binary metal oxides (BMO) makes them promising electrode materials for the detection of toxic chemicals, and biological compounds. In addition, the interaction between the cations and anions of diverse metals in BMO tends to create more oxygen vacancies which are beneficial for energy storage devices. However, specifically targeted synthesis of BMO is still arduous. In this work, we prepared a nickel oxide/tin oxide composite (NiO/SnO2) through a simple solvothermal technique. The crystallinity, specific surface area, and morphology were fully characterized. The synthesized BMO is used as a bifunctional electrocatalyst for the electrochemical detection of dopamine (DPA) and for the hydrogen evolution reaction (HER). As expected, the active metals in the NiO/SnO2 composite afforded a higher redox current at a reduced redox potential with a nanomolar level detection limit (4 nm) and excellent selectivity. Moreover, a better recovery rate is achieved in the real-time detection of DPA in human urine and DPA injection solution. Compared to other metal oxides, NiO/SnO2 composite afforded lower overpotential (157 mV @10 mA cm-2), Tafel slope (155 mV dec-1), and long-term durability, with a minimum retention rate. These studies conclude that NiO/SnO2 composite can act as a suitable electrode modifier for electrochemical sensing and the HER.

Oxidative Addition of Silicon-Chloride Bonds to a Zerovalent Ruthenium Center and Direct Generation of an Ethylene Insertion Complex.

The oxidative addition of a silicon-chloride (Si-Cl) bond to a metal center can be a key reaction step in coordinative silicon chemistry, but this reaction is seldom observed. Herein, we report direct oxidative addition of the Si-Cl bonds of dimethyldichlorosilane (Me2SiCl2) and cyclotrimethylenedichlorosilane [(CH2)3SiCl2] to low-valent ruthenium complexes, yielding the 16e- chloro(organosilyl)ruthenium complexes [N3]Ru(Cl)(SiMe2Cl) (4a) and [N3]Ru(Cl)(SiCl(CH2)3) (4b) ([N3] = 2,6-(MesN═CMe)2C5H3N; Mes = 1,3,5-trimethylphenyl; Me = methyl). The reversible reaction of 4a with ethylene yields an 18e- ethylene adduct, in which an ethylene is subsequently inserted into a ruthenium-silicon (Ru-Si) bond to produce the 16e- complex [N3]Ru(Cl)(CH2CH2SiMe2Cl) (7). This study provides a good example of the direct generation of an ethylene insertion product, which is an important intermediate in the catalytic reduction of unsaturated molecules.

Controllable Nitric Oxide Storage and Release in Cu-BTC: Crystallographic Insights and Bioactivity.

Crystalline metal-organic frameworks (MOFs) are extensively used in areas such as gas storage and small-molecule drug delivery. Although Cu-BTC (1, MOF-199, BTC: benzene-1,3,5-tricarboxylate) has versatile applications, its NO storage and release characteristics are not amenable to therapeutic usage. In this work, micro-sized Cu-BTC was prepared solvothermally and then processed by ball-milling to prepare nano-sized Cu-BTC (2). The NO storage and release properties of the micro- and nano-sized Cu-BTC MOFs were morphology dependent. Control of the hydration degree and morphology of the NO delivery vehicle improved the NO release characteristics significantly. In particular, the nano-sized NO-loaded Cu-BTC (NO⊂nano-Cu-BTC, 4) released NO at 1.81 µmol·mg-1 in 1.2 h in PBS, which meets the requirements for clinical usage. The solid-state structural formula of NO⊂Cu-BTC was successfully determined to be [CuC6H2O5]·(NO)0.167 through single-crystal X-ray diffraction, suggesting no structural changes in Cu-BTC upon the intercalation of 0.167 equivalents of NO within the pores of Cu-BTC after NO loading. The structure of Cu-BTC was also stably maintained after NO release. NO⊂Cu-BTC exhibited significant antibacterial activity against six bacterial strains, including Gram-negative and positive bacteria. NO⊂Cu-BTC could be utilized as a hybrid NO donor to explore the synergistic effects of the known antibacterial properties of Cu-BTC.

Polyurethane Foam Incorporated with Nanosized Copper-Based Metal-Organic Framework: Its Antibacterial Properties and Biocompatibility.

Polyurethane foams (PUFs) have attracted attention as biomaterials because of their low adhesion to the wound area and suitability as biodegradable or bioactive materials. The composition of the building blocks for PUFs can be controlled with additives, which provide excellent anti-drug resistance and biocompatibility. Herein, nanosized Cu-BTC (copper(II)-benzene-1,3,5-tricarboxylate) was incorporated into a PUF via the crosslinking reaction of castor oil and chitosan with toluene-2,4-diisocyanate, to enhance therapeutic efficiency through the modification of the surface of PUF. The physical and thermal properties of the nanosized Cu-BTC-incorporated PUF (PUF@Cu-BTC), e.g., swelling ratio, phase transition, thermal gravity loss, and cell morphology, were compared with those of the control PUF. The bactericidal activities of PUF@Cu-BTC and control PUF were evaluated against Pseudomonas aeruginosa, Klebsiella pneumoniae, and methicillin-resistant Staphylococcus aureus. PUF@Cu-BTC exhibited selective and significant antibacterial activity toward the tested bacteria and lower cytotoxicity for mouse embryonic fibroblasts compared with the control PUF at a dose of 2 mg mL-1. The Cu(II) ions release test showed that PUF@Cu-BTC was stable in phosphate buffered saline (PBS) for 24 h. The selective bactericidal activity and low cytotoxicity of PUF@Cu-BTC ensure it is a candidate for therapeutic applications for the drug delivery, treatment of skin disease, and wound healing.

Metal-Ion Tuning in Triple-Stranded Helicate-Based Metallosupramolecules.

Effective incorporation of multiple types of ligands in a given coordination structure provides structural complexity and functional diversity to the resultant coordination-driven assembly. One of the most widely used synthetic approaches is the utilization of the molecular symmetry principle to combine multiple ligands and specific metallic centers in a preferred manner. The variation of metal ions can be helpful to understand the importance of symmetry for the generation of structurally hierarchical supramolecular platforms. We describe the synthesis and characterization of isostructural supramolecular helicates, [M8 (PDA)6 (AIP)3 (DMF)6-x (H2 O)x ] (M=Ni (1), Co (2), and Mn (3); PDA=2,6-pyridinedicarboxylate; AIP=5-aminoisophthalate; x=0 for 1, and x=4 for 2 and 3). The effect of metal variation on the formation of supramolecular helicates and their solid-state crystal packing are discussed. Despite the disparity in the ionic radii and distinct coordination-geometry preferences of Co2+ , Ni2+ , and Mn2+ , all metal centers engaged in the assembly with the heteroleptic ligands in the same manner to form isostructural supramolecular helicates.

Nano Metal-Organic Framework-Derived Inorganic Hybrid Nanomaterials: Synthetic Strategies and Applications.

Nano- (or micro-scale) metal-organic frameworks (NMOFs), also known as coordination polymer particles (CPPs), have received much attention because of their structural diversities and tunable properties. Besides the direct use, NMOFs can be alternatively used as sacrificial templates/precursors for the preparation of a wide range of hybrid inorganic nanomaterials in straightforward and controllable manners. Distinct advantages of using NMOF templates are correlated to their structural and functional tailorability at molecular levels that is rarely acquired in any other conventional template/precursor. In addition, NMOF-derived inorganic nanomaterials with distinct chemical and physical properties are inferred to dramatically expand the scope of their utilization in many fields. In this review, we aim to provide readers with a comprehensive summary of recent progress in terms of synthetic approaches for the production of diverse inorganic hybrid nanostructures from as-synthesized NMOFs and their promising applications.

Synthesis of tridentate 2,6-bis(imino)pyridyl ruthenium(II) complexes with N-heterocyclic carbene ligands: activation of imidazolium salts.

Low-valent Ru(0) complexes, [η(2)-N3]Ru(η(6)-Ar) (1) or {[N3]Ru}2(µ-N2) (2), where Ar = C6H6 or C6H5Me, and [N3] = 2,6-(2,4,6-(CH3)3C6H2N═CCH3)2C5H3N, activate C-H bonds in imidazolium salts to produce bis(imino)pyridyl ruthenium-(imidazolidin-2-ylidene) complexes, [N3]Ru(H)(X)(NHC) (4) (X = halides and tosylate). Formation of 4 is most likely to proceed via C-H oxidative addition, followed by anion coordination, which is expected to be a useful pathway in synthesizing new complexes with both N-heterocyclic carbene (NHC) and hydride ligands. A zwitterionic ruthenium complex with an ylidic ligand, bis(imino)pyridyl ruthenium-(2-methyleneimidazoline) complex, 7, was also successfully isolated and fully characterized. The (1)H NMR spectra and the solid-state structure confirm that complex 7 is an ylidic transition-metal complex with both NHC and hydride ligands, which was formed through the activation of imidazolium salts.

Nonionic surfactant-assisted, seed-mediated growth of gold nanotoroids.

Gold (Au) nanotoroids with ring-like structures and vacancies at their center are successfully synthesized through a seed-mediated method using nonionic Brij35 surfactant, which acted as a reducing, surface-stabilizing, and shape-directing agent. The relative amount of Au seed nanoparticles significantly affects the formation yield of Au nanotoroids and the morphologies of the resulting Au nanostructures. The possible formation mechanisms are discussed by analyzing time-resolved microscopy images and UV-Vis spectra.

Synthesis of highly emissive PIPES-stabilized gold nanoclusters and gold nanocluster-doped silica nanoparticles.

Stable and highly emissive gold nanoclusters were successfully synthesized by means of stabilization with PIPES (PIPES-Au NCs, where PIPES = 1,4-piperazinediethanesulfonic acid) using a thermal synthetic strategy. By varying the amount of PIPES, two Au NCs with different emission maxima were obtained. The synthesized Au NCs were successfully incorporated into a porous silica matrix to generate fluorescent PIPES-Au NC doped silica nanoparticles. Sequential doping of the PIPES-Au NCs with tetraethylorthosilicate (TEOS) and 3-(aminopropyl)triethoxysilane (APTS) furnished a silica matrix, which effectively protected the PIPES-Au NCs during repeated washing with polar solvent and the composite of which exhibited enhanced emission.

Recent strategies for constructing hierarchical multicomponent nanoparticles/metal-organic framework hybrids and their applications.

Hybrid nanoparticles with unique tailored morphologies and compositions can be utilized for numerous applications owing to their combination of inherent properties as well as the structural and supportive functions of each component. Controlled encapsulation of nanoparticles within nanospaces (NPNSs) of metal-organic frameworks (MOFs) (denoted as NPNS@MOF) can generate a large number of hybrid nanomaterials, facilitating superior activity in targeted applications. In this review, recent strategies for the fabrication of NPNS@MOFs with a hierarchical architecture, tailorability, unique intrinsic properties, and superior catalytic performance are summarized. In addition, the latest and most important examples in this sector are emphasized since they are more conducive to the practical applicability of NPNS@MOF nanohybrids.

Hierarchical packing of racemic metallosupramolecular cages with Ni(II)-based triple-stranded helicate building blocks.

Three novel hierarchical Ni-based metallosupramolecular cages were constructed from nickel ions, pyridine dicarboxylates and isophthalate derivative ligands (the substituents on C5 of isophthalate are methyl, tert-butyl and bromo groups). In every cage, two multinuclear nickel clusters, assembled from four nickel atoms and three pyridine dicarboxylate ligands, are interlinked by three isophthalate-derivative ligands to form a nickel-based triple-stranded helicate (TSH), which then becomes the supramolecular building block for the fabrication of a metallocage. Six homochiral TSH supramolecular building blocks, either left (M)-handed or right (P)-handed, are connected by four linking nickel atoms to generate M6 and P6 discrete racemic cage molecules (M6 - cage with six M-TSHs; P6 - cage with six P-TSHs). The crystal packing of the racemic cages was characterized by single-crystal X-ray diffraction. An additional cobalt-based molecular cage with 5-methylisophthalate bridging ligands was synthesized for host-guest interaction studies. The methyl groups in Co- and Ni-TSH can act as guest units to be accommodated in the cone-shaped metal clusters (host) of an adjacent cage.

Novel Genome-Wide Interactions Mediated via BOLL and EDNRA Polymorphisms in Intracranial Aneurysm.

OBJECTIVE: The association between boule (BOLL) and endothelin receptor type A (EDNRA) loci and intracranial aneurysm (IA) formation has been reported via genome-wide association studies. We sought to identify genome-wide interactions involving BOLL and EDNRA loci for IA in a Korean adult cohort. METHODS: Genome-wide pairwise interaction analyses of BOLL and EDNRA involving 250 patients with IA and 296 controls were performed using the additive effect model after adjusting for confounding factors. RESULTS: Among 512575 single-nucleotide polymorphisms (SNPs), 23 and 11 common SNPs suggested a genome-wide interaction threshold (p<1.25×10-8) involving rs700651 (BOLL) and rs6841581 (EDNRA). Rather than singe SNP effect of BOLL or EDNRA on IA development, they showed a synergistic effect on IA formation via multifactorial pair-wise interactions. The rs1105980 of PTCH1 gene showed the most significant interaction with rs700651 (natural log-transformed odds ratio [lnOR], 1.53; p=6.41×10-11). The rs74585958 of RYK gene interacted strongly with rs6841581 (lnOR, -19.91; p=1.64×10-9). Although, there was no direct interaction between BOLL and EDNRA variants, two EDNRA-interacting gene variants of TNIK (rs11925024 and rs1231) and FTO (rs9302654), and one BOLL-interacting METTL4 gene variant (rs549315) exhibited marginal interaction with BOLL gene. CONCLUSION: BOLL or EDNRA may have a synergistic effect on IA formation via multifactorial pair-wise interactions.

Elucidating the mechanism of the halide-induced ligand rearrangement reaction.

The formation of heteroligated Rh(I) complexes containing two different hemilabile phosphinoalkyl ligands, (κ(2)-Ph(2)PCH(2)CH(2)S-Aryl)(κ(1)-Ph(2)PCH(2)CH(2)O-C(6)H(5))RhCl, through a halide-induced ligand rearrangement (HILR) reaction has been studied mechanistically. The half-life of this rearrangement reaction depends heavily on the Rh(I) precursor used and the chelating ability of the phosphinoalkyl thioether (PS) ligand, while the chelating ability of the phosphinoalkyl ether (PO) ligand has less of an effect. An intermediate complex which contains two PO ligands, (nbd)(κ(1)-Ph(2)PCH(2)CH(2)O-C(6)H(5))(2)RhCl (nbd = norbornadiene), converts to (nbd)(κ(1)-Ph(2)PCH(2)CH(2)O-C(6)H(5))RhCl resulting in a free PO ligand. The free PO ligand can then react with a homoligated PS complex [(κ(2)-Ph(2)PCH(2)CH(2)S-Aryl)(2)Rh](+)Cl(-) producing the heteroligated product. The PS ligand generated during the reaction pathway can be trapped by the monoligated PO complex (nbd)(κ(1)-Ph(2)PCH(2)CH(2)O-C(6)H(5))RhCl, leading to the formation of the same heteroligated product. In this study, some of the key intermediates and reaction steps underlying the HILR reaction have been identified by variable temperature (31)P{(1)H} NMR spectroscopy and in two cases by single-crystal X-ray diffraction studies. Significantly, this work provides mechanistic insight into the HILR process, which is a key reaction used to prepare a large class of highly sophisticated three-dimensional metallosupramolecular architectures and allosteric catalysts.

Nonionic Brij surfactant-mediated synthesis of raspberry-like gold nanoparticles with high surface area.

We report a rapid, simple, single-step, and high-yielding solution-phase synthesis of raspberry-like gold nanoparticles (Au RLNPs) with rich edges and high surface areas. Au RLNPs were synthesized through the reduction of HAuCl4 simply mediated by nonionic Brij surfactant in basic conditions without any other reducing agents or organic molecules. The synthesized nanoparticles possessed high surface areas and were stable in basic or neutral conditions, which are potentially useful structural factors for the applications. The unique, highly red-shifted surface plasmon resonances (SPRs) of Au RLNPS originate from their rough, raspberry-like surfaces. The sizes of Au RLNPs were controllable by varying the amounts of NaOH and HAuCl4. However, there are very few reported facile syntheses of size-controlled multi-branched gold nanoparticles simply mediated by surfactant without any other reducing agents or organic molecules.

Fabrication of hollow fibrous nanosilica with large pore channels.

The fabrication of hollow mesoporous nanosilica with well-defined structural features for optimizing the integration of functional components is a challenge. Herein, we report a facile preparation of hollow fibrous nanosilica (HFNS) with high specific surface area (666 m2 g-1), fiber-like mesoporous architectures in the inner and outer shells, and large pore channels (16.22 nm) via selective self-etching of dendritic fibrous nanosilica in an aqueous medium. The specific surface area and pore diameter increased significantly after the formation of a cavity in the center, resulting in HFNS. The HFNS can serve as a robust support for the controllable growth of gold nanoparticles with maximum catalytic performance for 4-nitrophenol reduction.

Gold nanodot assembly within a cobalt chalcogenide nanoshell: Promotion of electrocatalytic activity.

The assembly of functional nanoparticles within materials with unique architectures can improve the interfacial surfaces, defects, and active sites, which are key factors for the designing novel nanocatalysts. Nano metal-organic framework (NMOF) can be employed to fabricate nanodots-confined nanohybrids for use in electrocatalytic processes. Herein, we report a controlled synthesis of gold nanodot assembly within cobalt chalcogenide nanoshell (dots-in-shell Au/CoxSy nanohybrids). A cobalt-based NMOF (the cobalt-based zeolite imidazole framework, ZIF-67) is used as a versatile sacrificial template to yield dots-in-shell Au/CoxSy nanohybrids. Due to the synergistic effect of the well-dispersed Au nanodots and the thin CoxSy nanoshell, the obtained dots-in-shell Au/CoxSy nanohybrids exhibit enhanced performance for the oxygen evolution reaction (OER) with low overpotential values at a current density of 10 mA cm-2 and a small Tafel slope (343 mV and 62 mV dec-1, respectively).

Heteroleptic Triple-Stranded Metallosupramolecules with Hydrophobic Inner Voids.

The systematic combination of well-defined coordination spheres and multiple types of ligands (heteroleptic) can lead to the generation of hierarchical metallosupramolecules with a high level of complexity and functionality. In particular, a specific multilevel coordination-driven assembly through the initiate generation of multinuclear clusters can form unique heteroleptic multiple-stranded supramolecular complexes. Herein, we report novel triple-stranded nickel-based supramolecules constructed from two different ditopic ligands ([1,1':3',1''-terphenyl]-4,4''-dicarboxylate (TP) and 2,6-pyridinedicarboxylate (PDA)) and a nickel precursor. The solid-state structures of the as-synthesized supramolecules revealed that three PDA ligands are employed to fabricate a tetranuclear ({Ni4}) cluster, and two {Ni4} clusters are assembled to form the final triple-stranded metallosupramolecules by three TP ligands. The bridging TP ligands also provide large inner voids with highly hydrophobic environments. Structural investigation of the generated complexes provided a deeper understanding of the aspects driving the formation of heteroleptic supramolecules, which is crucial for the design of multiple-strands with desired morphologies and functionalities.

The Therapeutic Role of Nanoparticle Shape in Traumatic Brain Injury : An in vitro Comparative Study.

OBJECTIVE: To perform a comparative analysis of therapeutic effects associated with two different shapes of ceria nanoparticles, ceria nanorods (Ceria NRs) and ceria nanospheres (Ceria NSs), in an in vitro model of traumatic brain injury (TBI). METHODS: In vitro TBI was induced using six-well confluent plates by manually scratching with a sterile pipette tip in a 6×6-square grid. The cells were then incubated and classified into cells with scratch injury without nanoparticles and cells with scratch injury, which were treated separately with 1.16 mM of Ceria NSs and Ceria NRs. Antioxidant activities and anti-inflammatory effects were analyzed. RESULTS: Ceria NRs and Ceria NSs significantly reduced the level of reactive oxygen species compared with the control group of SH-SY5Y cells treated with Dulbecco's phosphate-buffered saline. The mRNA expression of superoxide dismutases was also reduced in nanoparticle-treated SH-SY5Y cells, but apparently the degree of mRNA expression decrease was not dependent on the nanoparticle shape. Exposure to ceria nanoparticles also decreased the cyclooxygenase-2 expression, especially prominent in Ceria NR-treated group than that in Ceria NS-treated group. CONCLUSION: Ceria nanoparticles exhibit antioxidant and anti-inflammatory effects in TBI models in vitro. Ceria NRs had better antiinflammatory effect than Ceria NSs, but showed similar antioxidant activity.

Shape effect of cerium oxide nanoparticles on mild traumatic brain injury.

The catalytic performance and therapeutic effect of nanoparticles varies with shape. Here, we investigated and compared the therapeutic outcomes of ceria nanospheres (Ceria NSs) and ceria nanorods (Ceria NRs) in an in vivo study of mild traumatic brain injury (mTBI). In vivo TBI was induced in a mouse model of open head injury using a stereotaxic impactor. Outcomes including cytoprotective effects, cognitive function, and cerebral edema were investigated after retro-orbital injection of 11.6 mM of ceria nanoparticles. Ceria nanoparticles significantly reduced fluoro-jade B (FJB)-positive cells and terminal deoxynucleotidyl transferase dUTP nick-end labeling (TUNEL)-positive cells, and restored mRNA levels of superoxide dismutase 1 (SOD1) and SOD2. They also decreased the cyclooxygenase-2 (COX-2) expression compared with the untreated control group. Comparing the two nanomaterials, Ceria NRs showed less stable and high-energy (100) and (110) planes, which increased the number of active sites. The Ce3+/Ce4+ molar ratio of Ceria NRs (0.40) was greater than that of Ceria NSs (0.27). Ceria NRs (0.059 ± 0.021) appeared to exhibit better anti-inflammatory effect than Ceria NSs (0.133 ± 0.024), but the effect was statistically insignificant (p = 0.190). Ceria nanoparticles also improved cognitive impairment following mTBI compared with the control group, but the effect did not differ significantly according to the nanoshape. However, Ceria NRs (70.1 ± 0.5%) significantly decreased brain water content compared with Ceria NSs (73.7 ± 0.4%; p = 0.0015), indicating a more effective reduction in brain edema (p = 0.0015). Compared with Ceria NSs, the Ceria NRs are more effective in alleviating cerebral edema following in vivo mTBI.

Solvent and temperature induced switching between structural isomers of Rh(I) phosphinoalkyl thioether (PS) complexes.

To develop functional systems based on the weak-link approach (WLA), it is important to understand how solvent and ligand binding strength alter the coordination geometry of complexes formed from this method. A series of phosphinoalkyl thioether (PS) hemilabile ligands with varying electron donating abilities were synthesized and incorporated into homoligated Rh(I)(PS)2Cl complexes to help understand the effects of solvent and ligand binding strength on the preferred coordination modes. The switching between closed and semiopen structural isomers of these Rh(I)(PS)2Cl complexes was studied by variable temperature 31P NMR spectroscopy in different solvent mixtures of CH2Cl2 and tetrahydrofuran (THF) to obtain thermodynamic parameters (DeltaG(o), DeltaH(o), TDeltaS(o), and K(eq)). The isomers differ in the position of the chloride counterion. In the closed isomer, the Cl- anion occupies the outer coordination sphere, while in the semiopen isomer, the Cl- has moved inner sphere and displaced one of the Rh-S bonds. The closed isomer is favored in CH2Cl2 and the semiopen isomer is favored in THF. The preference for either isomer at equilibrium depends on the solvent polarity, based upon the E(T)(N) solvent polarity scale, as was determined from 15 different solvents, with more polar solvents favoring the closed isomer. The isomer preference also depends on the electron donating ability of the group attached to the sulfur of the PS ligand, with electron donating groups favoring the closed isomers and electron withdrawing groups favoring the semiopen isomers. The formation of the semiopen isomer from the closed isomer is entropically favored but enthalpically disfavored under all conditions studied. Elucidation of the principles and environments that determine the equilibrium between the two isomers will aid in the design of functional complexes prepared by the WLA.