Luminescent iridium(III) porphyrin complexes as near-infrared-emissive biological probes.

We report herein the design, synthesis and characterisation of a series of luminescent iridium(III) porphyrin complexes [Ir(ttp)(CHCHOH)] (Http = 5,10,15,20-tetra-4-tolylporphyrin) (1), [Ir(tpp-Ph-NO)(CO)Cl] (Htpp-Ph-NO = 5-(4-((4-nitrophenoxy)carbonyloxymethyl)phenyl)-10,15,20-triphenylporphyrin) (2), [Ir(tpp-COOMe)(Py)](Cl) (Htpp-COOMe = 5-(4-methoxycarbonylphenyl)-10,15,20-triphenylporphyrin; Py = pyridine) (3) and [Ir(tpp-COOH)(Py)](Cl) (Htpp-COOH = 5-(4-carboxylphenyl)-10,15,20-triphenylporphyrin) (4). All the complexes displayed long-lived near-infrared (NIR) emission attributed to an excited state of mixed triplet intraligand (IL) (π → π*) (porphyrin) and triplet metal-to-ligand charge transfer (MLCT) (dπ(Ir) → π*(porphyrin)) character. The cytotoxicity of the complexes toward HeLa cells was examined by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide (MTT) assay.

Transcriptomic and proteomic studies of condylar ossification of the temporomandibular joint in porcine embryos.

Background: The ossification mechanism of the temporomandibular joint (TMJ) condyle remains unclear in human embryo. The size and structure of TMJ, shape of articular disc and the characteristics of omnivorous chewing in the pig are similar to those of humans. The pig is an ideal animal for studying the mechanism of ossification of the TMJ condyle during the embryonic period.

-Stereoselective C3-Spirocyclization and C2-Amination of 3-(2-Isocyanoethyl)indole Using ,-Cyclic Azomethine Imines.

By utilizing an underexplored reaction mode of ,-cyclic azomethine imines, a catalyst-free [1+2+3] cycloaddition/N-N bond cleavage sequential reaction for accessing spiroindolines with -stereoselectivity was developed. On the basis of experimental results and DFT calculations, peroxide and ethereal solvent were identified to trigger the hydrogen abstraction of the unstable [1+2+3] cycloaddition adducts, followed by homolytic cleavage of the N-N bond and hydrogen absorption.

Development of the temporomandibular joint in miniature pig embryos.

The temporomandibular joint (TMJ) is a synovial joint involved in sliding and hinge movements of lower jaw in mammals. Studies on TMJ development in embryos have been mainly performed using rodents. However, the TMJ structure in rodents differs in several aspects from that in humans.

Luminescent rhenium(I) perfluorobiphenyl complexes as site-specific labels for peptides to afford photofunctional bioconjugates.

We report herein new luminescent rhenium(I) perfluorobiphenyl complexes that reacted specifically with the cysteine residue of the π-clamp sequence (FCPF) to afford novel peptide-based imaging reagents, photosensitisers for singlet oxygen and enzyme sensors.

Divergent synthesis of α-functionalized amides through selective N-O/C-C or N-O/C-C/C-N cleavage of aza-cyclobutanone oxime esters.

Herein, a novel sequential ring opening reaction of aza-cyclobutanone oxime esters with isocyanides is described. The reaction proceeded smoothly under redox-neutral and mild conditions, leading to a divergent synthesis of α-cyanomethylaminoamides, α-acyloxyamides and α-acylaminoamides. In these transformations, a selective N-O/C-C or N-O/C-C/C-N cleavage was achieved only by changing the iron-catalyst system.

Direct 1,1-Bisphosphonation of Isocyanides: Atom- and Step-Economical Access to Bisphosphinoylaminomethanes.

An atom- and step-economical strategy for the synthesis of bisphosphinoylaminomethanes is reported. This metal-free bisphosphinylation reaction proceeded smoothly through a base-mediated direct 1,1-bisphosphonation of phosphine oxides and isocyanides under mild conditions. The present method offers a facile, efficient, and general approach to a broad range of bisphosphinoylaminomethane derivatives in moderate to good yields.

The rs6427384 and rs6692977 Single Nucleotide Polymorphisms of the Fc Receptor-Like 5 (FCRL5) Gene and the Risk of Ankylosing Spondylitis: A Case Control Study in a Single Center in China.

BACKGROUND The study aimed to explore the genetic association of Fc receptor-like 5 (FCRL5) gene variants (rs6427384 and rs6692977) with ankylosing spondylitis risk in Chinese Han population. MATERIAL AND METHODS Genotyping for FCRL5 gene variations rs6427384 and rs6692977 was implemented among 130 ankylosing spondylitis cases and 135 healthy persons, through polymerase chain reaction restriction fragment length polymorphism (PCR-RFLP) method. Frequency dissimilarity for 2 polymorphisms was compared between 2 groups using chi-square test.

Photofunctional Cyclometalated Iridium(III) Polypyridine Complexes Bearing a Perfluorobiphenyl Moiety for Bioconjugation, Bioimaging, and Phototherapeutic Applications.

In this article, we report the design, synthesis, and characterization of a series of cyclometalated iridium(III) polypyridine complexes containing a perfluorobiphenyl (PFBP) moiety [Ir(N^C)(bpy-PFBP)](PF) (bpy-PFBP = 4-(-(perfluoro-(1,1'-biphenyl)-4-yl)--mercaptoethylaminocarbonyloxymethyl)-4'-methyl-2,2'-bipyridine; HN^C = 2-phenylpyridine (Hppy) (), 2-(4-hydroxymethylphenyl)pyridine (Hppy-CHOH) (), 2-((1,1'-biphenyl)-4-yl)pyridine (Hpppy) (), 2-((4'-hydroxymethyl-1,1'-biphenyl)-4-yl)pyridine (Hpppy-CHOH) (), 2-phenylquinoline (Hpq) (), 2-(4-hydroxymethylphenyl)quinoline (Hpq-CHOH) ()). Their PFBP-free counterparts [Ir(N^C)(bpy-C4)](PF) (bpy-C4 = 4-(--butylaminocarbonyloxymethyl)-4'-methyl-2,2'-bipyridine; HN^C = Hppy (), Hppy-CHOH (), Hpppy (), Hpppy-CHOH (), Hpq (), Hpq-CHOH ()) were also prepared for comparison studies. Upon irradiation, all the complexes displayed intense and long-lived greenish-yellow to orange luminescence in solutions under ambient conditions and in low-temperature alcohol glass.

Efficient Cs-Sr Separation over a Microporous Silver Selenidostannate Synthesized in Deep Eutectic Solvent.

Efficient Cs-Sr separation, highly desirable for radionuclide recovery in medical and industrial applications, was achieved by the ion exchange technique over a novel microporous silver selenidostannate, [NHCH][NH(CH)]AgSnSe (). This material was synthesized in deep eutectic solvent (DES), where the alkylammonium cations play significant structure-directing roles in the construction of micropores that allow for selective ion exchange toward Cs against Sr. The much greater (1.

Identification, characterization and microRNA expression profiling of side population cells in human oral squamous cell carcinoma Tca8113 cell lines.

The present study aimed to evaluate the stem cell markers, characteristics and biological functions of cancer stem‑like side population (SP) cells in human oral cancer. SP cells were isolated from the human oral squamous cell carcinoma Tca8113 cell line by Hoechst 33342 fluorescence dye and flow cytometry. The colony forming and proliferative capability of SP and non‑SP cells were detected using a live‑cell analysis system in vitro.

Di-lacunary [InS] cluster: the building block of a highly negatively charged framework for superior Sr adsorption capacities.

In this study, the construction of a highly negatively charged layered material [CH3CH2NH3]6In6S12 (InS-1) by introducing a lacunary cluster as the building block is reported. The pronounced framework negative charge density (5.59 × 10-3) and the soft Lewis basic S component endow InS-1 with an effective ion exchange performance toward heavier Sr2+, with a top-level adsorption capacity qm of 105.

Base-Promoted Multicomponent Reactions: A Synthesis of 2-Amino-1,3-selenazole Derivatives.

New practical synthesis of 2-amino-1,3-selenazole with transition metal-free multicomponent reaction is reported here. A series of 2-amino-1,3-selenazole derivatives were afforded by the nucleophilic addition of amines to isoselenocyanate formed , followed by Michael addition reaction and aromatization. The products were isolated from moderate to excellent yields.

Deep eutectic solvothermal synthesis of an open framework copper selenidogermanate with pH-resistant Cs ion exchange properties.

Presented here is the deep eutectic solvothermal synthesis of an open framework copper selenidogermanate, namely [NH3CH3]0.75Cu1.25GeSe3 (CuGeSe-1), which exhibits a rapid and effective Cs+ ion exchange performance (qm = 225.

Stepwise Conversion from GeO to [MGeS] (M = Cu, Ag) Polymer via Isolatable [GeS] and [GeS] Anions by Virtue of Templating Technique.

Rational synthesis of inorganic matter remains a great challenge encountered with modern synthetic chemistry. Here we reported the stepwise solvothermal conversion from GeO to [MGeS] (M = Cu, Ag) polymer via isolatable [GeS] and [GeS] anions by virtue of templating technique. The facile sulfuration of GeO resulted in the methylammonium-templated dimeric thiogermanate [CHNH]GeS ().

Influence of the distribution of bone cement along the fracture line on the curative effect of vertebral augmentation.

Objective: The present study was performed to evaluate the effect of different bone cement distributions along the fracture line on clinical and imaging outcomes of vertebral augmentation.

Methods: In total, 84 patients who underwent vertebral augmentation for a single osteoporotic vertebral compression fracture from January 2016 to August 2018 were retrospectively reviewed. These patients were divided into two groups according to the relationship between the bone cement distribution and the fracture line: the unilateral group (n = 23) and the bilateral group (n = 61).

Luminescent Rhenium(I)-Polypyridine Complexes Appended with a Perylene Diimide or Benzoperylene Monoimide Moiety: Photophysics, Intracellular Sensing, and Photocytotoxic Activity.

This communication reports novel luminescent rhenium(I)-polypyridine complexes appended with a perylene diimide (PDI) or benzoperylene monoimide (BPMI) moiety through a non-conjugated linker. The photophysical and photochemical properties originating from the interactions of the metal polypyridine and perylene units were exploited to afford new cellular reagents with thiol-sensing capability and excellent photocytotoxic activity.

Selenidostannates and a Silver Selenidostannate Synthesized in Deep Eutectic Solvents: Crystal Structures and Thermochromic Study.

Deep eutectic solvents (DESs) have been adopted as reaction media for solvothermal synthesis of crystal materials. In the present work, we extended the scope of DESs in chalcogenidometalate preparation by including dimethylamine, ethylamine, and trimethylamine hydrochlorides and synthesized a series of novel Sn-Se and Ag-Sn-Se compounds: i.e.

Combined antibacterial and osteogenic in situ effects of a bifunctional titanium alloy with nanoscale hydroxyapatite coating.

To resolve the problems of bacterial infections and the low efficiency of osteogenesis of implanted titanium alloys in clinical dental and bone therapy, we developed a bifunctional titanium alloy (Ti) with a nano-hydroxyapatite (HA) coating (HBD + BMP/HA-Ti), which enables the sustained release of the natural antimicrobial peptide human β-defensin 3 (HBD-3) and bone morphogenetic protein-2 (BMP-2). Due to the poriferous nano-sized structure of the HA coating with a 20-30 μm thickness, the HBD + BMP/HA-Ti material had a high encapsulation efficiency (>74%) and exhibited synchronized slow release of HBD-3 and BMP-2. In an antibacterial test, HBD + BMP/HA-Ti prevented the growth of bacteria in an inoculated medium, and its surface remained free from viable bacteria after a continuous incubation with Gram-negative and Gram-positive strains for 7 days.

Exploitation of Environment-Sensitive Luminophores in the Design of Sydnone-Based Bioorthogonal Imaging Reagents.

Although the strain-promoted sydnone-alkyne cycloaddition reaction has been utilized for bioconjugation, its potential applications in bioorthogonal labeling and imaging in live cells have not been explored. This communication reports novel bioorthogonal imaging reagents with environment-sensitive emission properties through the modification of sydnone with cyclometalated iridium(III) polypyridine complexes. These complexes displayed significant emission enhancement and lifetime elongation upon reaction with strained alkyne derivatives, and were utilized to label cyclooctyne-modified proteins and ceramide molecules in live cells.

Suspended polyhydroxyalkanoate microspheres as 3D carriers for mammalian cell growth.

Different forms of biopolyester PHBVHHx microspheres were prepared so as to compare the mammalian cell behaviors in suspension cultivation system. Based on a microbial terpolyester PHBVHHx consisting of 3-hydroxybutyrate (HB), 3-hydroxyvalerate (HV), and 3-hydroxyhexanoate (HHx), solid microspheres (SMSs), hollow microspheres (HMSs), and porous microspheres (PMS) were successfully prepared by a modified solvent evaporation method involving gas-in-oil-in-water (G1/O/W2) double emulsion, water-in-oil-in-water (W1/O/W2) double emulsion and oil-in-water (O/W) single emulsion, respectively. Generally, PMSs have diameters ranging from 330 to 400 μm with pore sizes of 10 to 60 μm.

ERK/MAPK and PI3K/AKT signal channels simultaneously activated in nerve cell and axon after facial nerve injury.

Background: The in-vitro study indicated that ERK/MAPK and PI3K/AKT signal channels may play an important role in reparative regeneration process after peripheral nerve injury. But, relevant in-vivo study was infrequent. In particular, there has been no report on simultaneous activation of ERK/MAPK and PI3K/AKT signal channels in facial nerve cell and axon after facial nerve injury.

Proteomic analysis of Bombyx mori molting fluid: Insights into the molting process.

Unlabelled: Molting is an essential biological process occurring multiple times throughout the life cycle of most Ecdysozoa. Molting fluids accumulate and function in the exuvial space during the molting process. In this study, we used liquid chromatography-tandem mass spectrometry to investigate the molting fluids to analyze the molecular mechanisms of molting in the silkworm, Bombyx mori.