Three Silver(I) Coordination Polymers Based on Pyridyl Ligands and Auxiliary Carboxylic Ligands: Luminescence and Efficient Sensing Properties.

Easily producible sensors for harmful industrial waste compounds are of significant interest for both human health and the environment. Three novel coordination polymers, [Ag(µ-aca)(µ4-bztpy)1/2] (1), [Ag(µ-bza)(µ-bpa)] (2), and [Ag2(µ-aca)2(µ-bpa)2]·EtOH·2H2O (3), were assembled in this study by reactions using Ag+ as a node with the pyridyl ligand 1,2,4,5-tetrakis(4-pyridyl)benzene (bztpy) or 9,10-bis(4-pyridyl)anthracene (bpa) and an auxiliary chelating carboxylic ligand. Single-crystal X-ray structural analyses revealed that compound 1 has a 3D framework consisting of 1D [Ag(aca)]∞ chains and bztpy linkers, while 2 and 3 have 2D layered structures consisting of binuclear Ag-carboxylate units and bpa linkers, respectively. Topological studies revealed that 1 has a bbf topology, while 2 and 3 are 2D [4,4] rhombic grids. The compounds were further characterized by powder X-ray diffraction, IR, elemental analysis, thermogravimetric analysis, and a luminescence study. The solids of 1-3 exhibited intense photoluminescent emission with λemmax at ca. 493, 472, and 500 nm, respectively. Remarkably, due to their excellent framework stability, 1 and 2 can act as multiresponsive luminescent sensors for nitrobenzene, Fe3+, and Cr2O72- with a high selectivity and sensitivity ascribed to their quenching effect.

Analysis of Correlation Between Vertebral Endplate Change and Lumbar Disc Degeneration.

BACKGROUND To evaluate the correlation between vertebral endplate change and the level of lumbar disc degeneration via magnetic resonance imaging (MRI). MATERIAL AND METHODS A total of 345 patients who were recruited from our hospital from May 2012 to May 2016 were evaluated for the presence of intervertebral disc degeneration or herniation. The degree of degeneration was assessed according to Pfirrmann grade. Vertebral endplate change was evaluated based on the endplate concave angle (ECA), and Modic change on sagittal MRI. The correlation between ECA and lumbar disc degeneration or Modic change and lumbar disc degeneration was analyzed. RESULTS The results showed that there was no statistically significant difference in comparison of the ECAs in adjacent L3-5 vertebra between males and females. With the aggravation in degenerative changes of L3-5 discs, the ECAs of adjacent L3 superior endplate, L4 inferior and superior endplates and L5 inferior endplate were gradually enlarged, indicating the positive correlation between the lumbar disc degeneration and ECAs. The rate of Modic change in females was higher than that in males without a statistically significant difference. Area of Modic change was positively correlated with the degree of lumbar disc degeneration. Additionally, we also identified the positive correlation between the rate of Modic change and the degree of lumbar disc degeneration. CONCLUSIONS Endplate angle and lumbar disc degeneration are positively correlated. The endplates and endplate signal changes can reflect the degree of disc degeneration and Modic changes can reflect the rate of clinical lumbar disc degeneration degree.

Multifunctional coatings fabricated from Chinese hemp-derived superhydrophobic micro-nanocellulose.

Ecologically feasible strategies for constructing superhydrophobic surfaces offer versatile applications in waterproofing, self-cleaning, selective absorption, and corrosion protection. Herein, we prepared low-surface-energy branched-chain-enriched micronanorod (F@SiO2@MNC) by hydrolyzing silane coupling agent and modifying fluoropolymer using micro-nanocellulose extracted from waste straw (Chinese hemp). These rods were sprayed and adhered to various substrates precoated with a binder, resulting in superhydrophobic surfaces. F@SiO2@MNC addition allowed for the formation of stable spherical liquid droplets when in contact with different types of aqueous liquids. Furthermore, these surfaces demonstrated excellent self-cleaning, robustness, abrasion resistance, UV resistance, cycling stability, and other multifunctionalities. They significantly enhanced the mechanical properties of filter paper, effectively separated oil water mixtures, and improved the corrosion resistance of metals. Our proposed strategy represents a novel approach for developing multifunctional coatings assembled from micronanocellulose.

High loading of uniformly dispersed Pt nanoparticles on polydopamine coated carbon nanotubes and its application in simultaneous determination of dopamine and uric acid.

Multiwalled carbon nanotubes (MWCNT) were homogeneously covered with a bio-functional polydopamine (PDOP) by a simple dip-coating approach in mild basic solution. Then, uniformly dispersed and highly loaded platinum nanoparticles (PtNPs) were deposited on MWCNT@PDOP by a mild reductant, and were characterized by transmission electron microscopy and x-ray photoelectron spectroscopy. Afterwards, this nanocomposite was modified on the glass carbon electrode and applied to simultaneously determine dopamine (DA) and uric acid (UA) by differential pulse voltammetry (DPV). Results showed that a linear electro-oxidation response was found for DA and UA in the range of 0.25-20 µM and 0.3-13 µM with the detection limit (S/N = 3) of 0.08 µM and 0.12 µM, respectively. In addition, the detection sensitivities for DA and UA by DPV were 1.03 µA µM(-1) and 2.09 µA µM(-1), respectively, which were much higher than those from a cyclic voltammogram. Finally, the reproducibility and stability of the nanocomposite were also evaluated, demonstrating that such MWCNT@PDOP@PtNPs can be a promising candidate for advanced electrode material in electrochemical sensing and other electrocatalytic applications.

SOX11 promotes osteoarthritis through induction of TNF-α.

OBJECTIVE: Osteoarthritis (OA) is a degenerative disease and the molecular mechanism of OA remains unclear. Transcription factor SOX11 has been proved to be involved in the development progress of OA. The present study aimed to evaluate the potential function of SOX11 during the development of OA. METHODS: SOX11 expression in patients with OA and health donator was determined with qRT-PCR. Subsequently, in vitro OA model was established by treating the chondrocyte cells CHON-001 with IL-1ß. Next, we validated the function of SOX11 in in vitro OA model by using siRNAs. Finally, the relationship between SOX11 and TNF-α was explored. RESULTS: SOX11 was upregulated in patients with OA and in IL-1ß treated cells. IL-1ß significantly increased both the mRNA and protein levels of MMP13 and cleaved caspase 3, while decreased collagen II and aggrecan in CHON-001 cells. In addition, knockdown of SOX11 could significantly decrease IL-1ß-induced apoptosis in CHON-001 cells. Meanwhile, IL-1ß induced OA like phenomenon was significantly reversed by siRNA interference. Moreover, inhibition of SOX11 decreased the level of TNF-α in patients with OA and in IL-1ß treated cell supernatant. CONCLUSION: Inhibition of SOX11 could improve IL-1ß-induced OA like phenomenon in CHON-001 cells, which suggesting SOX11 played an important role during the pathogenesis of OA. Thus, we hypothesized that SOX11 could be a potential target for the treatment of patients with OA.

Syntheses, crystal structures, weak interaction, magnetic and photoluminescent properties of two new organic-inorganic molecular solids with disubstituted benzyl triphenylphosphinium and tetra(isothiocyanate)cobalt(II) anion.

Two new organic-inorganic molecular solids of tetra(isothiocyanate)cobalt(II) dianion and disubstituted benzyl triphenylphosphinium, [2Cl4FBzTPP]2[Co(NCS)4] (1) and [2Cl4ClBzTPP]2[Co(NCS)4] (2) ([2Cl4FBzTPP](+)=1-(2'-chloro-4'-fluorobenzyltriphenylphosphonium) and [2Cl4ClBzTPP](+)=1-(2',4'-dichlorobenzyltriphenylphosphonium), were synthesized and characterized by elemental analysis, FT-IR, UV-Vis spectra, ESI-MS and single crystal X-ray diffraction method. Compounds 1 and 2 crystallize in the monoclinic Pc and triclinic P-1, respectively. The Co(II) ion of the [Co(NCS)4](2-) anion shows a distorted tetrahedral coordination geometry. The [2Cl4FBzTPP](+) cations containing P(2) atoms in 1 form a column by the Cl⋯π interactions, while the [2Cl4ClBzTPP](+) cations in 2 form two columns by the C-H⋯π and π⋯π interactions. The anion and the cation are linked by C-H⋯S hydrogen bonds and Cl⋯S interactions. Magnetic susceptibility measurement in the temperature range 2-300K shows that both 1 and 2 exhibit a weak antiferromagnetic exchange interaction as the temperature falls, and ultraviolet fluorescence emission in the solid state at room temperature.

Syntheses, crystal structures, luminescent and magnetic properties of two molecular solids containing naphthylmethylene triphenylphosphinium cations and tetra(isothiocyanate)cobalt(II) dianion.

The reaction of CoCl2 with the naphthalene methylated triphenylphosphinium bromide [n-NAPMeTPP]Br (n=1, 2) and KSCN, in a methanolic medium at ambient temperature, leads to the self-assembly formation of hybrid 2:1 organic-inorganic molecular solids, [1-NAPMeTPP]2[Co(NCS)4](1) and [2-NAPMeTPP]2[Co(NCS)4](2) ([NAPMeTPP](+)=(naphthylmethylene)(triphenyl)phosphinium), which have been characterized by elemental analyses, IR spectroscopy, UV-Vis spectra, ESI-MS, molar conductivity and single-crystal X-ray diffraction structural analyses. Compound 1 crystallizes in the orthorhombic space group Pna21, while 2 does in the monoclinic space group C2/c. The cations form a dimer through the weak intermolecular C-H⋯π interactions in 1 and π⋯π interaction in 2, while the anion and cation are linked by the C-H⋯S hydrogen bond in 1. Two molecular solids show dual functionalities: (1) the broad fluorescence emission around 400nm in the solid state at room temperature; (2) the weak antiferromagnetic coupling behavior.

Self-assembly of a 1D heterotrimetallic Cu(II)-Sr(II)-Na(I) propeller-like chiral coordination polymer with ferromagnetic interactions.

Self-assembly of metalloligand [CuL](-)(H(3)L =N-5-bromosalicylaldehydeglycyl-l-tyrosine) with Sr(2+) and Na(+) results in a 1D micro(2)-carboxylate- and H(2)O-bridged heterotrimetallic chiral coordination polymer [[Na(CuL)(3)Sr(H(2)O)(3)].9H(2)O]](n), which exhibits weak ferromagnetic exchange interactions and optical activity.

[Synthesis and spectral properties of tailed sercine tetraphenylporphyrin cobalt complex].

A new tailed sercine tetraphenylporphinatozinc, 5-(p-butoxyphenyl-10,15,20-trichlorophenyl)porphine and cobalt complex (Co[Ser-TPP]) was synthesized and characterized by elementary analysis, UV, IR, 1HNMR and Raman spectra. The electronic absorption spectra of axial coordination reactions of Co[Ser-TPP] with pyridine, 4-methylpyridine, 4-aminopyridine, 4,4-bipyridine, imidazole, 1-methylimidazole and 2-methylimidazole were inverstigated. The results showed that the changes of electronic absorption spectra of Co[Ser-TPP] could be attributed to the axial coordination reactions of Co[Ser-TPP] with pyridine and imidazole series.

Poly(dopamine) coated gold nanocluster functionalized electrochemical immunosensor for brominated flame retardants using multienzyme-labeling carbon hollow nanochains as signal amplifiers.

An electrochemical, signal amplified immunosensor was developed to detect 3-bromobiphenyl (BBP) by using a bio-inspired polydopamine (PDOP)/gold nanocluster (AuNc) as the sensor platform and multienzyme-labeled carbon hollow nanochains as the signal amplifier. The self-polymerized dopamine membrane on the AuNc-modified indium tin oxide (ITO) electrode were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle and electrochemical measurements. Such PDOP/AuNc platform featured the mild cross-linking reaction with the dense immobilization of BBP-antigens (BBP-Ag). Moreover, by using multiple horseradish peroxidase (HRP) and secondary antibodies (Ab2) modified one-dimensional carbon hollow nanochains (CHNc) as the signal enhancer, it held promise for improving the sensitivity and detection limit of the immunoassay. Based on the competitive immunoassay protocol, this immunosensor showed a linear range from 1 pM to 2 nM for BBP with a detection limit of 0.5 pM. Also, it exhibited high sensitivity, wide linear range, acceptable stability and reproducibility on a promising immobilization platform using a novel signal amplifier, which may extend its application in other environmental monitoring.

Electrochemical immunoassay of benzo[a]pyrene based on dual amplification strategy of electron-accelerated Fe3O4/polyaniline platform and multi-enzyme-functionalized carbon sphere label.

An electrochemical immunosensor, basing on a dual amplification strategy by employing a biocompatible Fe(3)O(4)/polyaniline/Nafion (Fe(3)O(4)/PANI/Nafion) layer as sensor platform and multi-enzyme-antibody functionalized highly-carbonized spheres (multi-HRP-HCS-Ab(2)) as label, was constructed for sensitive detection of benzo[a]pyrene (BaP). The stable film, Fe(3)O(4)/PANI/Nafion, can not only immobilize biomolecules, but also catalyze the reduction of hydrogen peroxide, indicating an accelerated electron transfer pathway of the platform. The experimental conditions, including the concentration of Nafion, concentration of Fe(3)O(4)/polyaniline (Fe(3)O(4)/PANI), pH of the detection solution and concentrations of biomolecules, were studied in detail. Basing on a competitive immunoassay, the current change was proportional to the logarithm of BaP concentration in the range of 8 pM and 2 nM with the detection limit of 4 pM. The proposed immunosensor exhibited acceptable reproducibility and stability. This new type of dual amplification strategy may provide potential applications for the detection of environmental pollutants.

Theoretical studies on the magnetic switching controlled by stacking patterns of bis(maleonitriledithiolato) nickelate(III) dimers.

Magnetic switchable maleonitriledithiolate (mnt) complexes were studied by density functional theory. The calculations were performed for anion dimers of [RBzPyR'][Ni(mnt)(2)] (RBzPyR' = derivatives of benzylpyridinium) to elucidate magnetostructural correlations and the nature of the weak intermolecular chemical bonding. The calculated results showed that the spin delocalization, favored by the eclipsed stacking and the shorter interlayer distance, was responsible for the diamagnetic character of [1-benzyl-4-aminopyridinium][Ni(mnt)(2)] at low temperature. The weak antiferromagnetic and ferromagnetic interactions were also reproduced for [1-benzyl-4-aminopyridinium][Ni(mnt)(2)] and [1-(4'-fluorobenzyl)pyridinium][Ni(mnt)(2)] at high temperature, respectively. The natural bond orbital analysis suggested that the cooperative effect of the weak intermolecular bondings may be the intrinsic driving force resulting in the switchable property, which is essentially similar to those in organic radicals exhibiting magnetic bistability. Further investigations with varying interlayer distance d, the extent of slippage (slipping distance r and deviation angle alpha), and rotational angle theta suggested that the extent of slippage played an important role in magnetic interactions. Therefore, the abrupt modulation of the extent of slippage in the [Ni(mnt)(2)](-) complexes by external perturbations provided new possibilities for the design of molecular magnetic switching devices.