Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)3 (M=Sr,Ba)

We report the synthesis and spectroscopic identification of the trisbenzene complexes of strontium and barium M(Bz)₃ (M=Sr, Ba) in low‐temperature Ne matrix. Both complexes are characterized by a D₃ symmetric structure involving three equivalent η⁶‐bound benzene ligands and a closed‐shell singlet electronic ground state. The analysis of the electronic structure shows that the complexes exhibit metal–ligand bonds that are typical for transition metal compounds. The chemical bonds can be explained in terms of weak donation from the π MOs of benzene ligands into the vacant (n?1)d AOs of M and strong backdonation from the occupied (n?1)d AO of M into vacant π* MOs of benzene ligands. The metals in these 20‐electron complexes have 18 effective valence electrons, and, thus, fulfill the 18‐electron rule if only the metal–ligand bonding electrons are counted. The results suggest that the heavier alkaline earth atoms exhibit the full bonding scenario of transition metals.     

A convenient and practical heterogeneous palladium‐catalyzed carbonylative Suzuki coupling of aryl iodides with formic acid as carbon monoxide source

A practical heterogeneous palladium‐catalyzed carbonylative Suzuki coupling of aryl iodides with arylboronic acids under carbon monoxide gas‐free conditions has been developed using a bidentate phosphino‐functionalized magnetic nanoparticle‐immobilized palladium(II) complex as catalyst. Formic acid was utilized as the carbon monoxide source with dicyclohexylcarbodiimide as the activator, and a wide variety of biaryl ketones were generated in moderate to high yields. The new heterogeneous palladium catalyst can be prepared via a simple procedure and can easily be separated from a reaction mixture by simply applying an external magnet and recycled up to 10 times without any loss of activity.     

Fabrication and In vitro Bioactivity of Robust Hydroxyapatite Coating on Porous Titanium Implant

Compared witli the traditional dental implant, TixOs■ manufactured by direct laser metal forming(DLMF) technology exhibits improved capability for bone osteointegration due to its porous surface structure, and has achieved remarkable clinical effect. However, like the traditional titanium and other alloyed implants, the porous titanium implant TixOsR also has relatively weak bioactivity. To address this issue, a proper surface modification method may be needed. Hydroxyapatite(HA) has been widely used in implant surface coating for its similar chemical composition to bone tissue and its osteoconductive properties. Thus, combining TixOs■ implants with hydroxyapatite can be an efficient way to enhance their bioactivity. We herewith reported a competent pulsed laser deposition(PLD) method of coating nano-sized HA thin film onto the porous TixOs■ implant. The HA coatings were characterized by means of scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDS), X-ray photoelectron spectroscopy(XPS) and focused ion beam(FIB) method, and nanocrystal sized thin HA films were identified on the surface of TixOs■ implants. The low cytotoxicity and improved cell proliferation ability of HA coated implants were further tested and verified using MC 3T3 E1 cells with the consideration of the controlling group. Our results show that a stable and bioactive HA tliin film is able to form on the surtace of the porous titanium implant by PLD method.This may benefit the fiirther clinical application of TixOs■ implants.     

Enzyme-triggered model self-assembly in surfactant-cyclodextrin systems

We present here a host-guest approach to construct enzyme-triggered assembly systems on the basis of surfactant-cyclodextrin complexes and α-amylase. We realized enzyme-responsive model self-assembly systems including monolayers, micelles, and vesicles. The host-guest approach is expected to be extended to more complicated assembly systems with widespread applications.     

A novel high selectivity chemiluminescence sensor for fenvalerate based on double-sided hollow molecularly imprinted materials

Novel fenvalerate double-sided hollow molecularly imprinted microspheres (fenvalerate-DHMIMs) were fabricated by in situ polymerization with the help of mesoporous silica microspheres (MSMs) in this paper for the very first time. Scanning electron microscope was employed to characterize the surface morphology of the fenvalerate-DHMIMs. Taking advantage of the quenching effect of fenvalerate on the luminol-H(2)O(2)-NaOH chemiluminescence system, a new model was established to determine fenvalerate by a highly selective flow injection chemiluminescence method. The traditional flow-through cell was replaced by a novel Y-shaped column. The chemiluminescence intensity was linear with fenvalerate concentration over the range of 5.0 × 10(-8) to 2.0 × 10(-5) g mL(-1) and the detection limit was 2.2 × 10(-8) g mL(-1). The relative standard deviation (RSD) for the determination of 2.0 × 10(-6) g mL(-1) fenvalerate was 1.4% (n = 11). The proposed method was applied to the determination of fenvalerate in real samples with satisfactory results.     

Imaging latent fingerprints by electrochemiluminescence

By exposing an electrode surface with a latent fingerprint to electrochemiluminescence (ECL)-generating luminophore, ECL is produced from the surface not covered by the fingerprint, generating a negative image. The fingerprint can also be pre-stained by luminophores, which generates ECL and yields a positive image (right). ITO=indium tin oxide.     

Determination of the concentration and the average number of gold atoms in a gold nanoparticle by osmotic pressure

For an ideal solution, an analytical expression for the macromolecule concentration, electrolyte concentration, and solution osmotic pressure is obtained on the basis of the van't Hoff equation and the Donnan equilibrium. The expression was further applied to a colloid solution of about 3 nm glutathione-stabilized gold nanoparticles. The concentration of the colloid solution and the average net ion charge number for each gold nanoparticle were determined with the measured osmotic pressure data. Meanwhile, the gold contents of the solutions were analyzed by means of atomic absorption spectrophotometry, and the results were combined with the determined concentration of gold nanoparticle colloids to determine that the average number of gold atoms per 3 nm gold nanoparticle is 479, which is 1/1.7 times the number of atoms in bulk metallic gold of the same size. The same proportion also occurred in the 2 nm 4-mercaptobenzoic acid monolayer-protected gold nanoparticles prepared by Ackerson et al., who utilized the quantitative high-angle annular dark-field scanning transmission electron microscope to determine the average number of gold atoms per nanoparticle (Ackerson, C. J.; Jadzinsky, P. D.; Sexton J. Z.; Bushnell, D. A.; Kornberg, R. D. Synthesis and Bioconjugation of 2 and 3 nm-Diameter Gold Nanoparticles. Bioconjugate Chem. 2010, 21, 214-218).     

Multi-walled carbon nanotube-based ternary rare earth (Eu3+, Tb3+) hybrid materials with organically modified silica-oxygen bridge

A series of ternary rare earth (Eu(3+), Tb(3+)) complexes are covalently coated to the 3-aminopropyltriethoxysilane functionalized multi-walled carbon nanotube (MWCNT) by a simple in situ sol-gel method by the bifunctional silylated monomer TTA-Si and TAA-Si (TTA-Si and TAA-Si are 3-(triethoxysilyl)propylisocyanate (TEPIC) modified thenoyltrifluoroacetone (TTA) and trifluoroacetylacetone (TAA), respectively). The resulting materials are characterized by Fourier transform infrared spectra, scanning electronic microscope, transmission electron microscope, thermogravimetric analysis, ultraviolet visible diffused reflection measure, photoluminescence spectra, and X-ray diffraction. The photoluminesce measurements indicated that these hybrids exhibit characteristic red and green luminescence originating from the corresponding ternary rare earth ion (Eu(3+), Tb(3+)). The luminescence quenching effect of MWCNT networks have been successfully restrained by coating a relatively thicker silica-oxygen-based organic-inorganic complex. Furthermore, the fluorescence lifetimes and emission quantum efficiencies of Eu(3+) hybrid materials are also determined.     

A self-catenated network containing unprecedented 0D + 2D → 2D polycatenation array

Herein, we report a new acylamide ligand and its application in the construction of a metal-organic framework. The resultant acylamide metal-organic framework, namely [Zn(2)(L)(OH)(btc)](n) (1, L = N(1),N(4)-bis(pyridin-3-ylmethyl) naphthalene-1,4-dicarboxamide, H(3)btc = benzene-1,3,5-tricarboxylic acid), was obtained by hydrothermal synthesis. The outstanding structural feature of it is the 0D + 2D → 2D polycatenation array containing a self-catenated feature which has never previously been observed. To the best of our knowledge, the coexistence of self-catenation and polycatenation phenomena is highly exceptional.