New Fluorescent Dye for the Detection of Zn2+ in Living Cells and Fixed Sections of the Rat Pancreas.

We report the synthesis and characterization of a new 4-methoxyphenyl-2,2'-bipyridine-based ligand, such as 12, bearing dipicolylaminomethyl core as a receptor unit, as a probe for the fluorescence "turn-on" detection of Zn2+. Thus, in the presence of Zn2+ the probe 12 exhibited a fluorescence enhancement with a Stokes shift of ~ 180 nm and photoluminescence quantum yields value of ~ 1.0. In addition, 12 exhibited higher binding constant for Zn2+ (~ 2 × 105 M-1) with the LOD reaching the nanomolar level (~ 0.1 × 10-9 M) compare to the previously reported probe 1. The stoichiometry and structure of the [Zn(12)]2+ and [Zn(1)]2+ complexes were supported by XRD analysis, DFT calculations and 1H NMR experiments. It was postulated that, as a result of binding of Zn2+, the sample exhibited a bright "on" state via the PET-ICT processes. Molecular docking studies and confocal fluorescence microscopy experiments demonstrated that the probe 12 could be used for the fluorescence detection of Zn2+ not only in artificially enriched with zinc salts live cells, but also in fixed tissues with cations are in a bound state. The high binding constant of compound 12 to Zn2+ cation allows it to be used for the accurate localization of pancreatic beta cells (islets of Langerhans).

Structures and Stability of Mixed Main Group Hydrides [PBEH6]n (E = C, Si, Ge; n = 1-4) and Donor-Acceptor Stabilization of Monomeric Chain Isomers.

Structures and stability of mixed group 13-14-15 element hydrides PBEH6 (E = C, Si, Ge), their oligomers, and complexes with Lewis acids and Lewis base are computationally studied at the B3LYP-D3/def2-TZVP level of theory. Unsubstituted chain hydrides are unstable and are expected to form cyclic oligomers. Cyclization can be prevented by the donor-acceptor complex formation. For complexes of chain hydrides with Lewis acid in many cases additional reactivity beyond the donor-acceptor complex formation is observed: cyclization and migration of terminal group from the group 13 Lewis acid to the boron or group 14 terminal atoms of the hydride. The most promising compounds for the experimental studies have been identified. Joint stabilization by both W(CO)5 and trimethylamine provides a synergetic effect, allowing stabilization of 13-14-15 chain compounds.

Life Cycle Assessment of River Sand and Aggregates Alternatives in Concrete.

Urbanization processes in Asia are still ongoing; thus, aggregate demand is expected to increase in following years. Even though construction and demolition waste is a source for secondary building materials in industrialized countries, it is not yet an alternative construction material source in Vietnam as the urbanization process is still ongoing. Thus, there is a need for river sand and aggregates alternatives in concrete, namely manufactured sand (m-sand) from primary solid rock materials and secondary waste materials. The focus in the present study for Vietnam was on m-sand sand as alternative for river sand, and different ashes as alternatives for cement in concrete. The investigations comprised concrete lab tests according to the formulations of concrete strength class C 25/30 in accordance with DIN EN 206, followed by a lifecycle assessment study in order to identify the environmental impact of the alternatives. In total 84 samples were investigated, consisting of 3 reference samples, 18 samples with primary substitutes, 18 samples with secondary substitutes, and 45 samples with cement substitutes. This kind of holistic investigation approach comprising material alternatives and accompanying LCA was the first study for Vietnam, and even for Asia, and represents a substantial added value for future policy development in order to cope with resource scarcity. The results show that with the exception of metamorphic rocks, all m-sands meet the requirements for quality concrete. In terms of cement replacement, the mixes showed that a higher percentage of ash reduces the compressive strength. The compressive strength values of the mixes with up to 10% coal filter ash or rice husk ash were equivalent to the C25/30 standard concrete formulation. Higher ash contents up to 30% lead to the reduction of the concrete quality. The LCA study's results highlighted the better environmental footprints across environmental impact categories in the 10% substitution material in comparison to the use of primary materials. The LCA analysis results showed that cement as a component in concrete holds the highest footprint. The use of secondary waste as alternative for cement provides significant environmental advantage.

New TEMPO-Appended 2,2'-Bipyridine-Based Eu(III), Tb(III), Gd(III) and Sm(III) Complexes: Synthesis, Photophysical Studies and Testing Photoluminescence-Based Bioimaging Abilities.

Linked to Alzheimer's disease (AD), amyloids and tau-protein are known to contain a large number of cysteine (Cys) residues. In addition, certain levels of some common biogenic thiols (cysteine (Cys), homocysteine (Hcy), glutathione (GSH), etc.) in biological fluids are closely related to AD as well as other diseases. Therefore, probes with a selective interaction with the above-mentioned thiols can be used for the monitoring and visualizing changes of (bio)thiols in the biological fluids as well as in the brain of animal models of Alzheimer's disease. In this study, new Eu(III), Tb(III), Gd(III) and Sm(III) complexes of 2,2'-bipyridine ligands containing TEMPO fragments as receptor units for (bio)thiols are reported. The presence of free radical fragments of the ligand in the complexes was proved by using the electronic paramagnetic resonance (EPR) method. Among all the complexes, the Eu(III) complex turned out to be the most promising one as luminescence- and spin-probe for the detection of biogenic thiols. The EPR and fluorescent titration methods showed the interaction of the resulting complex with free Cys and GSH in solution. To study the practical applicability of the probes for the monitoring of AD in-vivo, by using the above-mentioned Eu(III)-based probe, the staining of the brain of mice with amyloidosis and Vero cell cultures supplemented with the cysteine-enriched medium was studied as well as the fluorescence titration of Bovine Serum Albumin, BSA (as the model for the thiol moieties containing protein), was carried out. Based on the results of fluorescence titration, the formation of a non-covalent inclusion complex between the above-mentioned Eu(III) complex and BSA was suggested.

Powerful Potential of Polyfluoroalkyl-Containing 4-Arylhydrazinylidenepyrazol-3-ones for Pharmaceuticals.

4-Arylhydrazinylidene-5-(polyfluoroalkyl)pyrazol-3-ones (4-AHPs) were found to be obtained by the regiospecific cyclization of 2-arylhydrazinylidene-3-(polyfluoroalkyl)-3-oxoesters with hydrazines, by the azo coupling of 4-nonsubstituted pyrazol-5-oles with aryldiazonium chlorides or by the firstly discovered acid-promoted self-condensation of 2-arylhydrazinylidene-3-oxoesters. All the 4-AHPs had an acceptable ADME profile. Varying the substituents in 4-AHPs promoted the switching or combining of their biological activity. The polyfluoroalkyl residue in 4-AHPs led to the appearance of an anticarboxylesterase action in the micromolar range. An NH-fragment and/or methyl group instead of the polyfluoroalkyl one in the 4-AHPs promoted antioxidant properties in the ABTS, FRAP and ORAC tests, as well as anti-cancer activity against HeLa that was at the Doxorubicin level coupled with lower cytotoxicity against normal human fibroblasts. Some Ph-N-substituted 4-AHPs could inhibit the growth of N. gonorrhoeae bacteria at MIC 0.9 µg/mL. The possibility of using 4-AHPs for cell visualization was shown. Most of the 4-AHPs exhibited a pronounced analgesic effect in a hot plate test in vivo at and above the diclofenac and metamizole levels except for the ones with two chlorine atoms in the aryl group. The methylsulfonyl residue was proved to raise the anti-inflammatory effect also. A mechanism of the antinociceptive action of the 4-AHPs through blocking the TRPV1 receptor was proposed and confirmed using in vitro experiment and molecular docking.

Recruitment of macrophages and bone marrow stem cells to regenerating liver promoted by sodium phthalhydrazide in mice.

Pharmacological interventions which could be hepatoprotective, depending on bioavailability, anti-inflammatory and macrophage-targeting potential of drugs, are still at early preclinical stages. Existing evidence from many animal models of liver injury, as well as from human data, indicate that pharmacological and/or phytochemical interventions have limited impact on liver recovery. Recent studies on stem cell therapies focused on different cell subsets involved in tissue repair, including monocytes/macrophages and bone marrow cells migrating to the injured liver. Partial hepatectomy (PH) resulted in a rapid increase of monocytes/macrophages in bone marrow and liver, which could be further enhanced by prior treatment of animals with sodium phthalhydrazide. Increased number of proliferating Ki67+ hepatocytes, increased total protein and albumin content in regenerating liver, recruitment of CD172a+ macrophages and more differentiated CD45lowCD117+ bone marrow cells, could be further promoted by the treatment of animals with 2 mg/kg b.w. phthalhydrazide, considered immunomodulatory, antioxidant and macrophage-silencing. Phenotypic polarization of macrophages can possibly explain the macrophage reparative capacities, protective against liver injury. Enhanced macrophage cell recruitment from bone marrow to regenerating liver can be possibly one of important events in hepatic recovery.

Fluorescent boron complexes based on new N,O-chelates as promising candidates for flow cytometry.

This study presents the synthesis and optical properties of a new class of bright green-yellow fluorescent dyes with potential applications in bioimaging. A facile synthetic route via the chelation of aryl(hetaryl)aminoacryloylthiophene scaffolds with a BF2 fragment is presented. The photophysical properties of the dyes are attributed to the nature and position of electron-donating and electron-withdrawing substituents. Upon coordination to a BF2 fragment, characteristic emission was observed, with λem ranging from 503 to 543 nm and quantum yields of 0.14-0.42. Compared with parent aryl(hetaryl)aminoacryloylthiophenes, a significant red shift in absorption (up to 480 nm in solution) and emission (up to 543 nm in solution and 610 nm in the solid state) and high chemical stability and photostability were observed. The electron-accepting character of the substituents on the terminal aromatic ring or replacing this fragment with pyridine or pyrazine moieties resulted in increased quantum yields. To gain insight into the electronic structures and optical properties, quantum mechanical calculations were performed. The results of (TD-)DFT calculations supported the structural and spectroscopic data and showed the features of electronic distribution in the frontier molecular orbitals and active electrophilic and nucleophilic sites in the compounds investigated. Synthesized BF2 complexes are promising dyes for cell imaging and flow cytometry owing to their ready penetration and accumulation in cells.

Green Fluorescence of Cytaeis Hydroids Living in Association with Nassarius Gastropods in the Red Sea.

Green Fluorescent Proteins (GFPs) have been reported from a wide diversity of medusae, but only a few observations of green fluorescence have been reported for hydroid colonies. In this study, we report on fluorescence displayed by hydroid polyps of the genus Cytaeis Eschscholtz, 1829 (Hydrozoa: Anthoathecata: Filifera) found at night time in the southern Red Sea (Saudi Arabia) living on shells of the gastropod Nassarius margaritifer (Dunker, 1847) (Neogastropoda: Buccinoidea: Nassariidae). We examined the fluorescence of these polyps and compare with previously reported data. Intensive green fluorescence with a spectral peak at 518 nm was detected in the hypostome of the Cytaeis polyps, unlike in previous reports that reported fluorescence either in the basal parts of polyps or in other locations on hydroid colonies. These results suggest that fluorescence may be widespread not only in medusae, but also in polyps, and also suggests that the patterns of fluorescence localization can vary in closely related species. The fluorescence of polyps may be potentially useful for field identification of cryptic species and study of geographical distributions of such hydroids and their hosts.