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Our calculation suggested that syntheses of elusive (cAAC-E)2(N2) (1-2; Si, Ge) species may be possible with cAAC ligands having bulky substitutions adjacent to the CcAAC atom by preventing the homo-dimerization of two (cAAC)(E) units which can lead to the formation of (cAAC-E)2. The formation of E[double bond, length as m-dash]E bond is thermodynamically more favourable (E = Si, Ge) over binding energy of N2 inbetween two cAAC-E units.In this work, we report a high-yield one-pot synthesis of polyrotaxane (PR), composed of (2-hydroxypropyl)-α-cyclodextrin (hpCD) and polyethylene glycol (PEG), with well-defined hpCD threading ratios controllable across a wide range from 0.64% to 10%. In hpCD/PEG aqueous solutions, hpCDs are well dispersed and threaded spontaneously into hpCDs to form a pseudo-PR (pPR) structure. The homogeneous dispersion of hpCDs results in a well-defined threading ratio of hpCDs on PEG, which is suggested by the fact that the dispersity of the molecular weight distribution of PR is almost the same as that of pure PEG. The well-defined hpCD threading ratio of the PRs can be controlled over a wide range by tuning the hpCD concentration in the pPR solutions.The electrochemical behaviors of CuCl, SnCl2 and a CuCl-SnCl2 mixture were investigated by cyclic voltammetry (CV) and square wave voltammetry (SWV). The reduction potentials of Cu(i) and Sn(ii) on CV curves are -0.49 and -0.36 V, respectively, while the reduction potentials of Cu(i)-Sn(ii) in the CuCl-SnCl2 mixture almost overlap. The co-chlorination reaction progress between CuCl-SnCl2 and Zr was also studied by monitoring the concentration changes of Cu(i), Sn(ii) and Zr(iv) ions in situ by CV, SWV and inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analyses. The results indicate that during the reaction, the concentration of Zr(iv) ions increases gradually, while those of Cu(i) and Sn(ii) decrease rapidly until they disappear. When the molar ratios of Cu(i) to Sn(ii) are 1  1 and 1  0.5, the reaction between Cu(i) and Zr is faster but cannot exceed twice that of Sn(ii) and Zr in a short time. When the theoretical product of ZrCl4 is a constant, and with the proportion of CuCl to SnCl2 decreasing from 1  0 to 0  1, the chlorination reaction time periods increase from 40 to 170 min. Chloride products such as Cu x Sn y , Sn x Zr y , and Cu x Zr y , are formed with different molar ratios. The coupling effect caused by the formation of alloys will promote the chlorination reaction when the ratios of CuCl to SnCl2 are 0.66  0.17 and 0.5  0.25. The results provide a theoretical basis for the electrolytic refinement of zirconium.We present a detailed study on the physical properties of La0.6Ba0.2Sr0.2Mn1-x Ni x O3 samples (x = 0.00, 0.05 and 0.1). The ceramics were fabricated using the sol-gel route. Structural refinement, employing the Rietveld method, disclosed a rhombohedral R3̄c phase. The magnetization vs. temperature plots show a paramagnetic-ferromagnetic (PM-FM) transition phase at the T C (Curie temperature), which decreases from 354 K to 301 K. From the Arrott diagrams M 2 vs. Grazoprevir μ 0 H/M, we can conclude the phase transition is of the second order. Based on measurements of the isothermal magnetization around T C, the magnetocaloric effects (MCEs) have been calculated. The entropy maximum change (-ΔS M) values are 7.40 J kg-1 K-1, 5.6 J kg-1 K-1 and 4.48 J kg-1 K-1, whereas the relative cooling power (RCP) values are 232 J kg-1, 230 J kg-1 and 156 J kg-1 for x = 0.00, 0.05 and 0.10, respectively, under an external field (μ 0 H) of 5 T. Through these results, the La0.6Ba0.2Sr0.2Mn1-x Ni x O3 (0 ≤ x ≤ 0.1) samples can be suggested for use in magnetic refrigeration technology above room temperature. The electrical resistivity (ρ) vs. temperature plots exhibit a transition from metallic behavior to semiconductor behavior in the vicinity of T M-SC. The adiabatic small polaron hopping (ASPH) model is applied in the PM-semiconducting part (T > T MS). Throughout the temperature range, ρ is adjusted by the percolation model. This model is based on the phase segregation of FM-metal clusters and PM-insulating regions.Iron(ii) and iron(iii) salts of strong acids form iron glycerolates on heating at 180 °C with glycerol in the presence of an equivalent amount of alkali. Individual iron(iii) glycerolate was obtained for the first time. When Fe3O4 magnetic nanoparticles were heated with glycerol, an iron(iii) glycerolate shell was formed on their surface.The development of effective drug delivery vehicles is essential for the targeted administration and/or controlled release of drugs. Using first-principles calculations, the potential of alkali metal (AM = Li, Na, and K) decorated C60 fullerenes for delivery of 5-fluorouracil (5FU) is explored. The adsorption energies of the 5FU on a single AM atom decorated C60 are -19.33, -16.58, and -14.07 kcal mol-1 for AM = Li, Na, and K, respectively. The results, on the other hand, show that up to 12 Li and 6 Na or K atoms can be anchored on the exterior surface of the C60 fullerene simultaneously, each of which can interact with a 5FU molecule. Because of the moderate adsorption energies and charge-transfer values, the 5FU can be simply separated from the fullerene at ambient temperature. Furthermore, the results show that the 5FU may be easily protonated in the target cancerous tissues, which facilitates the release of the drug from the fullerene. The inclusion of solvent effects tends to decrease the 5FU adsorption energies in all 5FU-fullerene complexes. This is the first report on the high capability of AM decorated fullerenes for delivery of multiple 5FU molecules utilizing a C60 host molecule.Complexation of actinides and lanthanides with carboxylic organic ligands is a critical issue affecting radionuclide migration from deep geological disposal systems of spent nuclear fuel. A series of Eu(iii)-aliphatic dicarboxylate compounds, as chemical analogs of radioactive Am(iii) species, Eu2(Ox)3(H2O)6, Eu2(Mal)3(H2O)6, and Eu2(Suc)3(H2O)2, were synthesized and characterized using X-ray crystallography and time-resolved laser fluorescence spectroscopy to examine the ligand-dependent binding modes and the corresponding changes in spectroscopic properties. Powder X-ray crystallography results confirmed that all of the compounds presented a crystalline polymer structure with a trigonal prism square-face tricapped polyhedron geometry centered on Eu(iii) in a nine-coordinate environment involving nine oxygen atoms. This study captures the transition of the coordination modes of aliphatic dicarboxylate ligands from side-on to end-on binding as the carbon chain length increases. This transition is illustrated in malonate bindings involving a combination of side-on and end-on modes. Strongly enhanced luminescence, especially for the hypersensitive peak, indicates a low site symmetry in the formation of solid compounds. The number of remaining bound water molecules was estimated from the resultant increased luminescence lifetimes, which were in good agreement with crystal structures. The excitation-emission matrix spectra of these crystalline polymers suggest that Ox ligands promote the sensitized luminescence of Eu(iii), especially in the UV region. In the case of Mal and Suc ligands, charge transfer occurs in the opposite direction from Eu(iii) to the ligands under UV excitation, resulting in weaker luminescence.An efficient visible light photocatalytic strategy to synthesize thermodynamically less stable Z-arylvinyl halides (with up to >99/1 Z/E ratio and 86% yield) was developed. The reaction combined base-mediated halodecarboxylation of E-arylvinyl acids with N-halosuccinimide and visible light Ir-photocatalyzed isomerization of E-arylvinyl halides in a one pot sequential catalytic process.Treatment options for neurodegenerative conditions such as Parkinson's disease have included the delivery of cells which release dopamine or neurotrophic factors to the brain. Here, we report the development of a novel approach for protecting cells after implantation into the central nervous system (CNS), by developing dual-layer alginate beads that encapsulate therapeutic cells and release an immunomodulatory compound in a sustained manner. An optimal alginate formulation was selected with a view to providing a sustained physical barrier between engrafted cells and host tissue, enabling exchange of small molecules while blocking components of the host immune response. In addition, a potent immunosuppressant, FK506, was incorporated into the outer layer of alginate beads using electrosprayed poly-ε-caprolactone core-shell nanoparticles with prolonged release profiles. The stiffness, porosity, stability and ability of the alginate beads to support and protect encapsulated SH-SY5Y cells was demonstrated, and the release profile of FK506 and its effect on T-cell proliferation in vitro was characterized. Collectively, our results indicate this multi-layer encapsulation technology has the potential to be suitable for use in CNS cell delivery, to protect implanted cells from host immune responses whilst providing permeability to nutrients and released therapeutic molecules.Owing to its presence in several biological processes, Sirt1 acts as a potential therapeutic target for many diseases. Here, we report the structure-based designing and synthesis of two distinct series of novel Sirt1 inhibitors, benzimidazole mono-peptides and amino-acid derived 5-pyrazolyl methylidene rhodanine carboxylic acid. The compounds were evaluated for in vitro enzyme-based and cell-based Sirt1 inhibition assay, and cytotoxic-activity in both liver and breast cancer cells. The tryptophan conjugates i.e.13h (IC50 = 0.66 μM, ΔG bind = -1.1 kcal mol-1) and 7d (IC50 = 0.77 μM, ΔG bind = -4.4 kcal mol-1) demonstrated the maximum efficacy to inhibit Sirt1. The MD simulation unveiled that electrostatic complementarity at the substrate-binding-site through a novel motif "SLxVxP(V/F)A" could be a cause of increased Sirt1 inhibition by 13h and 13l over Sirt2 in cell-based assay, as compared to the control Ex527 and 7d. Finally, this study highlights novel molecules 7d and 13h, along with a new key hot-spot in Sirt1, which could be used as a starting lead to design more potent and selective sirtuin inhibitors as a potential anticancer molecule.Sludge-derived biochar (BS) was prepared by pyrolyzing municipal sludge at different temperatures and was used to recover NH4 +-N and PO4 3--P from urine. The effects of dosage, adsorption time, and urine concentration on the adsorption of NH4 +-N and PO4 3--P were investigated, and the adsorbed BS was used as a fertilizer to study its effect on the growth of pakchoi cabbage. The Elovich model was more consistent with the adsorption processes of NH4 +-N and PO4 3--P. Both the NH4 +-N and PO4 3--P adsorption isotherm model agreed with the Redlich-Peterson model. The Langmuir model showed that the largest adsorption capacity of BS600 for NH4 +-N and PO4 3--P could reach 114.64 mg g-1 and 31.05 mg g-1, respectively. The NH4 +-N adsorption mechanism of BS may have complexation with O-containing functional groups and precipitation reactions, while the removal mechanism of PO4 3--P was co-precipitation. The pot experiment demonstrated that adsorbed BS600 can better promote the growth of pakchoi cabbage with the same amount of addition.
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