Photochemical reactions of M(CO)6 (M = Cr,Mo, W) with Ph2P(S)P(S)Ph2

New complexes {M(CO)₄[Ph₂P(S)P(S)Ph₂]} (M = Cr, Mo and W), (1a)–(3a), [(1a), M = Cr; (2a), M = Mo; (3a), M = W] and {M₂(CO)₁₀[-Ph₂P(S)P(S)Ph₂]} (M = Cr, Mo, W), [(1b)–(3b) [(1b), M = Cr; (2b), M = Mo; (3b), M = W]] have been prepared by the photochemical reaction of M(CO)₆ with Ph₂P(S)P(S)Ph₂ and characterized by elemental analyses, f.t.-i.r. and ³¹P-(¹H)-n.m.r. spectroscopy and by FAB-mass spectrometry. The spectra suggest cis-chelate bidentate coordination of the ligand in {M(CO)₄[Ph₂P(S)P(S)Ph₂]} and cis-bridging bidentate coordination of the ligand between two metals in (M = Cr, Mo and W).     

Synergistic extraction of Ce(III), Eu(III) and Tm(III) with a mixture of picrolonic acid and benzo-15-crown-5 in chloroform

Summary The synergistic mixture comprising picrolonic acid (HPA) and benzo-15-crown-5 (B15C5) in chloroform has been used for the extraction of Ce(III), Eu(III) and Tm(III) as representatives of lanthanide(III) ions from pH 1-2 solutions having ionic strength of 0.1 mol^. dm^-3(K⁺/H⁺, Cl^-). The composition of the extracted species has been determined as M(PA)₃^. nB15C5 where M is Ce, Eu and Tm and n=1 or 2. The influence of various anions and cations on the extraction of these ions has also been studied and only oxalate, cyanide and tartrate have some deleterious effect. The extraction equilibrium constants have been evaluated and discussed.     

Photochemical reactions of metal carbonyls [M(CO)6 (M = Cr,Mo and W), Re(CO)5Br,Mn(CO)3Cp] with 2-hydroxyacetophenone methanesulfonylhydrazone (apmsh)

Five new complexes, [M(CO)₅(apmsh)] [M = Cr; (1), Mo; (2), W; (3)], [Re(CO)₄Br(apmsh)] (4) and [Mn(CO)₃(apmsh)] (5) have been synthesized by the photochemical reaction of metal carbonyls [M(CO)₆] (M = Cr, Mo and W), [Re(CO)₅Br], and [Mn(CO)₃Cp] with 2-hydroxyacetophenone methanesulfonylhydrazone (apmsh). The complexes have been characterized by elemental analysis, mass spectrometry, f.t.-i.r. and ¹H spectroscopy. Spectroscopic studies show that apmsh behaves as a monodentate ligand coordinating via the imine N donor atom in [M(CO)₅(apmsh)] (1–4) and as a tridentate ligand in (5).     

Which Extraction Solvents and Methods Are More Effective in Terms of Chemical Composition and Biological Activity of Alcea fasciculiflora from Turkey?

The bioactive content, antioxidant properties, and enzyme inhibition properties of extracts of Alcea fasciculiflora from Turkey prepared with different solvents (water, methanol, ethyl acetate) and extraction methods (maceration, soxhlet, homogenizer assisted extraction, and ultrasound assisted extraction) were examined in this study. UHPLC-HRMS analysis detected or annotated a total of 50 compounds in A. fasciculiflora extracts, including 18 hydroxybenzoic and hydroxycinnamic acids, 7 Hexaric acids, 7 Coumarins, 15 Flavonoids, and 3 hydroxycinnamic acid amides. The extracts had phenolic and flavonoid levels ranging from 14.25 to 24.87 mg GAE/g and 1.68 to 25.26 mg RE/g, respectively, in the analysis. Both DPPH and ABTS tests revealed radical scavenging capabilities (between 2.63 and 35.33 mg TE/g and between 13.46 and 76.27 mg TE/g, respectively). The extracts had reducing properties (CUPRAC: 40.38–78 TE/g and FRAP: 17.51–42.58 TE/g). The extracts showed metal chelating activity (18.28–46.71 mg EDTAE/g) as well as total antioxidant capacity (phosphomolybdenum test) (0.90–2.12 mmol TE/g). DPPH, ABTS, FRAP, and metal chelating tests indicated the water extracts to be the best antioxidants, while the ethyl acetate extracts had the highest overall antioxidant capacity regardless of the extraction technique. Furthermore, anti-acetylcholinesterase activity was identified in all extracts (0.17–2.80 mg GALAE/g). The water extracts and the ultrasound-assisted ethyl acetate extract were inert against butyrylcholinesterase, but the other extracts showed anti-butyrylcholinesterase activity (1.17–5.80 mg GALAE/g). Tyrosine inhibitory action was identified in all extracts (1.79–58.93 mg KAE/g), with the most effective methanolic extracts. Only the ethyl acetate and methanolic extracts produced by maceration and homogenizer aided extraction showed glucosidase inhibition (0.11–1.11 mmol ACAE/g). These findings showed the overall bioactivity of the different extracts of A. fasciculiflora and provided an overview of the combination of solvent type and extraction method that could yield bioactive profile and pharmacological properties of interest and hence, could be a useful reference for future studies on this species.     

Tailoring the optical and magnetic properties of La-BaM hexaferrites by Ni substitution

We investigate the impact of Ni insertion on the structural,optical,and magnetic properties of Ba_0.8La_0.2Fe_12-xNi_xO₁₉hexaferrites(Ni substituted La-BaM hexaferrites).Samples were prepared using the conventional co-precipitation method and sintered at 1000℃for 4 hours to assist the crystallization process.An analysis of the structure of the samples was carried out using an x-ray diffraction(XRD)spectrometer.The M-type hexagonal structure of all the samples was confirmed using XRD spectra.The lattice parameters a and c were found to be in the ranges of 5.8925±0.001 nm–5.8952±0.001 nm and 23.2123±0.001 nm–23.2219±0.001 nm,respectively.The M-type hexagonal nature of the prepared samples was also indicated by the presence of corresponding FT-IR bands and Raman modes in the FT-IR and Raman spectra,respectively.EDX results confirmed the successful synthesis of the samples according to the required stoichiometric ratio.A UV-vis spectrometer was used to record the absorption spectra of the prepared samples in the wavelength range of 200 nm–1100 nm.The optical energy bandgap of the samples was found to be in the range of 1.21 eV–3.39 eV.The M–H loops of the samples were measured at room temperature at an applied magnetic field range of 0 kOe–60 kOe.A high saturation magnetization of 99.92 emu/g was recorded in the sample with x=0 at a microwave operating frequency of 22.2 GHz.This high value of saturation magnetization is due to the substitution of La3+ions at the spin-up(12k,2a,and 2b)sites.The Ni substitution is proven to be a potential candidate for the tuning of the optical and magnetic parameters of M-type hexaferrites.Therefore,we suggest that the prepared samples are suitable for use in magneto-optic applications.     

A measure of dependence for stable distributions

A distance based measure of dependence is proposed for stable distributions that completely characterizes independence for a bivariate stable distribution. Properties of this measure are analyzed, and contrasted with the covariation and co-difference. A sample analog of the measure is defined and demonstrated on simulated and real data, including time series and distributions in the domain of attraction of a stable law.     

Microstructure and magnetic characterization of the Sm-CoMn co-substituted SrCaM hexagonal ferrites

A series of Sm-CoMn substituted hexagonal ferrites with chemical composition of Sr_0.85-xCa_0.15Sm_xFe_12-y(Co_0.5Mn_0.5)_yO₁₉ (0.00?≤?x?≤?0.60, (0.00?≤?y?≤?0.50) were synthesized by the solid-state reaction method. Microstructure and magnetic properties of the hexaferrites have been investigated by the X-ray diffraction, field emission scanning electron microscopy and a permanent magnetic measuring system. A single magnetoplumbite phase is exhibited in the hexaferrites with the substitutiom of Sm (0.00?≤?x?≤?0.12) and CoMn (0.00?≤?y?≤?0.10) contents. For the hexaferrites containing Sm (x?≥?0.24) and CoMn (y?≥?0.20), impurity phases are observed in the structure. The FESEM micrographs exhibit that the hexaferrites with different Sm-CoMn contents have formed hexagonal structures and the grain size of the hexaferrites remains unchanged with increasing Sm-CoMn content. The remanence (B_r), H_k/H_cj ratios, and maximum energy product [(BH)_max] decrease with increasing Sm-CoMn content (0.00?≤?x?≤?0.60, (0.00?≤?y?≤?0.50). Instrinsic coercivity (H_cj) and magnetic induction coercivity (H_cb) increase with increasing Sm-CoMn content (0.00?≤?x?≤?0.12, 0.00?≤?y?≤?0.10), and then decrease with increasing Sm-CoMn content (0.12?≤?x?≤?0.36, 0.10?≤?y?≤?0.30), while for the hexaferrites with Sm (x?≥?0.36) and CoMn (y?≥?0.30), with increasing Sm-CoMn content, H_cj increases and H_cb decreases.     

New heteroleptic palladium(II) dithiocarbamates: synthesis,characterization, packing and anticancer activity against five different cancer cell lines

Two new heteroleptic palladium(II) complexes have been synthesized by reacting equimolar quantities of palladium(II) chloride, sodium 4‐(2‐methoxyphenyl)piperazine‐1‐carbodithioate and diphenyl‐p‐tolylphosphine ( 1 ) or tri‐p‐tolylphosphine ( 2 ). Complexes 1 and 2 have been characterized using elemental analysis, Fourier transform infrared spectroscopy, multinuclear NMR (¹H, ¹³C and ³¹P) spectroscopy and single‐crystal X‐ray analysis. The latter technique confirms a pseudo square‐planar geometry in which two adjacent positions are occupied by bidentate dithiocarbamate while chloro and substituted triphenylphosphine are present at the remaining two positions. The anticancer activity of both complexes against five different cancer cell lines (LU – human lung carcinoma, established at UIC, Department of Surgical Oncology; MCF7 – human breast adenocarcinoma, ATCC number HTB‐22?; MDA‐MB‐231 – human breast adenocarcinoma, ATCC number HTB‐26?; Hepa‐1c1c7 – mouse liver hepatoma, ATCC number CRL‐2026?; PC‐3 – human prostate adenocarcinoma, ATCC number CRL‐1435?) was determined by MTT assay, revealing 2 has higher activity than 1 . A drug–calf thymus DNA binding study with UV–visible spectroscopy reveals a higher DNA binding affinity of 2 (3.511 × 10⁴ M^?1) than 1 (4.213 × 10³ M^?1). Density functional theory studies confirm the relatively more stable nature of 2 than 1 . Copyright © 2016 John Wiley & Sons, Ltd.