Electrochemical study of β-diketonatobis(triphenylphosphite)rhodium(I) complexes

The electrochemical behaviour of the series of ten [Rh(RCOCHCOR′)(P(OPh)₃)₂] complexes with R, R′ = CF₃, CF₃ (1), CF₃, CH₃ (2), CF₃, Ph (C₆H₅) (3), CF₃, Fc (ferrocenyl = (C₅H₅)Fe(C₅H₄)) (4), CH₃, Ph (5), CH₃, CH₃ (6), Ph, Ph (7), Fc, CH₃ (8), Fc, Ph (9) and Fc, Fc (10) were studied in acetonitrile containing 0.100 mol dm⁻³ tetra-n-butylammonium hexafluorophosphate as supporting electrolyte utilizing a glassy carbon working electrode. Results are consistent with Rh(I) being first oxidized in an electrochemically irreversible two-electron transfer process at peak anodic potentials ranging E_pa(Rh) = 0.124–0.881 V vs. Fc/Fc⁺. For the ferrocene-containing complexes (4), and (8)–(10) the rhodium oxidation was followed by the electrochemically reversible oxidation of the ferrocenyl group in a one-electron transfer process at a slightly more positive potential. Relationships were established between the electrochemical quantity E_pa(Rh) and kinetic parameter log k₂ as well the sum of experimental group electronegativities (Gordy Scale) of the R and R′ groups (χ_R + χ_R′), the Hammett σ values (σ_R + σ_R′) and the Lever ligand parameter E_L for the [Rh(RCOCHCOR′)(P(OPh)₃)₂] complexes: E_pa(Rh) (vs. Fc/Fc⁺/V) = 0.31 (χ_R + χ_R′)–1.09 = 0.56 (σ_R + σ_R′) + 0.28 = S_M (ΣE_L) + (I_M − 0.66 V) = −0.23 log k₂ − 0.03 (k₂ = second order rate constant for the oxidative addition of methyl iodide to rhodium). A profound shift of E_pa(Rh) to a more positive potential was observed for Rh(I) substrates containing β-diketonato ligands with increasing electronegative substituents R and R′. An exponential dependence of E_pa(Rh) on the pK_a of the β-diketone was obtained.     

Understanding the Potential In Vitro Modes of Action of Bis(β-diketonato) Oxovanadium(IV) Complexes

To understand the potential in vitro modes of action of bis(β-diketonato) oxovanadium(IV) complexes, nine compounds of varying functionality have been screened using a range of biological techniques. The antiproliferative activity against a range of cancerous and normal cell lines has been determined, and show these complexes are particularly sensitive against the lung carcinoma cell line, A549. Annexin V (apoptosis) and Caspase-3/7 assays were studied to confirm these complexes induce programmed cell death. While gel electrophoresis was used to determine DNA cleavage activity and production of reactive oxygen species (ROS), the Comet assay was used to determine induced genomic DNA damage. Additionally, Förster resonance energy transfer (FRET)-based DNA melting and fluorescent intercalation displacement assays have been used to determine the interaction of the complexes with double strand (DS) DNA and to establish preferential DNA base-pair binding (AT versus GC).     

Hydrogen adsorption on M-ZSM-12 zeolite clusters (M = K,Na and Li): a density functional theory study

The molecular adsorption of hydrogen has been studied theoretically via DFT on additional framework with alkali metal atoms (K, Na and Li) in ZSM-12 zeolite. A 14T channel zeolite cluster model was used. Lewis acidity of alkali metals decreases with increasing atomic radius of alkali metal and H₂ adsorption. Adsorption enthalpy values were computed to be ?7.4 and ?5.1 kJ/mol on Li- and Na-ZSM-12 clusters, respectively. Hydrogen adsorption enthalpy values for Li- and Na-cases are meaningfully larger than the liquefaction enthalpy of hydrogen molecule. This designates that Li- and Na-ZSM-12 zeolites are potential cryoadsorbent materials for hydrogen storage.     

A density functional theory study of the effects of metal cations on the Brøsted acidity of H-ZSM-5

Density functional theory calculations have been carried out to establish the influence of mono- and polyvalent cations on the Brønsted acidity of H-ZSM-5. The zeolite was modeled as a cluster containing 41-45 atoms, in the center of which is an Al⁽¹⁾(OH)SiOAl⁽²⁾(OM)unit, where M⁺ = H⁺, Li⁺, Na⁺, K⁺, Ca(OH)⁺, AlO⁺, Al(OH)⁺ ₂. The local geometry of the Brønsted acid site is affected by the nature of M⁺ and this in turn causes a change in the value of the proton affinity (PA) for the site. The highest value of PA is 330 kcal/mol for M⁺ = H⁺ and the lowest value of PA is 305 kcal/mol for M⁺ = AlO⁺. No correlation was found between the value of PA and the Mulliken charge on Al⁽¹⁾. With the exception of the case where M⁺ = AlO⁺ the binding energy of CO with the Brøsted acid proton is approximately 8.8 kcal/mol, independent of the nature of M⁺. When M⁺ = AlO⁺, the binding energy for CO is 11.1 kcal/mol. The present calculations suggest that different factors affect proton affinity and the binding energy for CO adsorption.     

Identification of important chemical features of 11β-hydroxysteroid dehydrogenase type1 inhibitors: application of ligand based virtual screening and density functional theory

11β-Hydroxysteroid dehydrogenase type1 (11βHSD1) regulates the conversion from inactive cortisone to active cortisol. Increased cortisol results in diabetes, hence quelling the activity of 11βHSD1 has been thought of as an effective approach for the treatment of diabetes. Quantitative hypotheses were developed and validated to identify the critical chemical features with reliable geometric constraints that contribute to the inhibition of 11βHSD1 function. The best hypothesis, Hypo1, which contains one-HBA; one-Hy-Ali, and two-RA features, was validated using Fischer's randomization method, a test and a decoy set. The well validated, Hypo1, was used as 3D query to perform a virtual screening of three different chemical databases. Compounds selected by Hypo1 in the virtual screening were filtered by applying Lipinski's rule of five, ADMET, and molecular docking. Finally, five hit compounds were selected as virtual novel hit molecules for 11βHSD1 based on their electronic properties calculated by Density functional theory.     

Correlations between microstructural characterization and thermal properties of well defined poly(ε-caprolactone) samples by ring opening polymerization with neutral and cationic bis(2,4,6-triisopropylphenyl)tin(IV) compounds

In this paper a study of correlations between the microstructure of well defined poly(ε-caprolactone) (PCL) samples and their physical properties such as thermal degradation, crystallization kinetics and melting behavior is described. The PCL samples were obtained in the presence of the compound benzyl-methoxy-bis(2,4,6-triisopropylphenyl)tin (1), acting as single-site and living initiator, as well as in the presence of compounds Tip₂SnRR′ [Tip = 2,4,6-triisopropylbenzene; R = R′ = CHCH₂ (2); R = CH₂Ph, R′ = Br (3)] activated by ionizing agents. PCL samples having different end groups, molecular weight and molecular weight distribution were obtained. The samples were fully characterized by GPC and NMR. The thermal degradation of the synthesized samples were studied by thermogravimetric analysis (TGA) in air flow. The experimental results suggested that the presence of ester chain end groups has a beneficial effect on the thermal stability of the PCL samples, independently on the molecular weights and molecular weight distribution. The crystallization behavior was studied in isothermal conditions at 37 °C, 40 °C, and 43 °C through differential scanning calorimetry (DSC). In this case, either the molecular weight (M_w) or the polydispersivity index (PDI) have a significant effect on the kinetics of crystallization of PCLs.     

Morphology and Thermal Properties of Poly[bis(β-phenoxyethoxy)phosphazene]

The structure and thermal properties of poly[bis(-phenoxyethoxy)phosphazene)] (PBPEP) newly synthesized by us were investigated. The crystallization from the melt, the volumetric relaxation in the amorphous phase in the upper vicinity of the glass transition temperature (T _g) and the enthalpy of relaxation of the glass in the lower vicinity of the T _g were shown to be very slow. These slow rates may be related to the low chain mobility due to the bulky side chain. Two kinds of crystal forms, called and forms were found in the melt-crystallized sample. These forms were clearly seen as individual types of spherulites by optical microscopy. The melting temperature of these crystals were analyzed by the Hoffmann–Weeks plot. The so-called T(1) transition that had often been detected in many crystalline polyphosphazenes as the transition from the crystal phase to the mesophase was not observed by x-ray diffraction at elevated temperatures.     

Density functional theory study on the structure of bis(1,1-diethyl-3-benzoyl-thioureato) copper(II). Planar or distorted tetrahedral CuS2O2 conformation?

Density functional theory calculations at the B3LYP level of theory combined with several basis sets were carried out on the structure of bis(1,1-diethyl-3-benzoyl-thioureato) copper(II). The results obtained clearly show two minima with local cis-CuS₂O₂ geometry, one resembling the X-ray experimental structure, in which the coordination polyhedron is a distorted tetrahedron, and the other with the CuS₂O₂ moiety nearly planar, resembling the corresponding ureato and a similar mercapto-β-diketone. A third minimum was found for a trans-CuS₂O₂ conformation. The calculated energy gap between the three structures is lower than 5 kJ/mol.     

Syntheses,magnetic properties,and reactivity of dinuclear oxovanadium (IV) and copper (II) complexes with (μ-diphenylphosphinato)-bridges

Novel dinuclear oxovanadium (IV) complexes having the formula [(VO)₂(dpp)₃(bpy)₂]NO₃·2H₂O (1), [(VO)₂(dpp)₃(phen)₂]-NO₃·H₂O (2), [(VO)₂(bmp)₃(bpy)₂]NO₃·H₂O (3), and [(VO)₂(bmp)₃(phen)₂]NO₃·H₂O (4), and copper (II) complexes having the formula [Cu₂(bmp)₂(phen)₂](NO₃)₂·MeOH·H₂O (5), and [Cu₂(bmp)₂(bpy)₂](NO₃)₂ (6) (where Hdpp=diphenylphosphinic acid, Hbmp=bis(4-methoxyphenyl)phosphinic acid, bpy=2,2^′-bipyridine, and phen=1,10-phenanthroline) with (μ-phosphinato)-bridges, 1–6, have been prepared and characterized. Crystal structure of complex 2 reveals that two vanadium ions are linked by tris(μ-phosphinato)-bridges. The magnetic susceptibility data for 1–3, and 6 conform to the usual dimer equation with −2J values of 16–24 cm⁻¹, indicating a weak antiferromagnetic interaction between vanadium(IV) ions.The oxidation of cinnamyl alcohol was studied using complexes 1–6 as catalyst and molecular oxygen as an oxidant. In the presence of complex 3 as a catalyst, cinnamyl alcohol was oxidized to cinnamaldehyde 61% yield in 7 h. Consequently, complex 3 activates oxygen, and then alcohol was quite efficiently oxidized by activated oxygen.     

Oxovanadium(IV) complexes as homogeneous catalyst—aerobic epoxidation of olefins

The novel N₂O₂ unsymmetrical tetradentate Schiff bases complexes are used as catalysts for the selective aerobic oxidation of cyclohexene. In general, conversion percentages decrease with increasing ΔE_p and decreasing $E_{\text{redox}}^{0^{\prime }}$. Catalytic activity increases with decrease of the number of electron-donating groups and the catalytic selectivity varies according to the types of substituents in the ligands. The catalytic system described here is an inexpensive method for selective oxidation of olefins, with advantages of high activity, selectivity, re-usability and short reaction times. Analysing GC and redox potential results shows a moderate correlation between selectivity and activity.     

Fabrication and characterization of neat and aluminium-doped titanium (IV) oxide fibers prepared by combined sol–gel and electrospinning techniques

Sol–gel and electrospinning techniques were incorporated to produce polyvinylpyrrolidone (PVP)/titanium (IV) oxide composite fibers from solutions containing PVP and titanium tetraisopropoxide, with or without aluminium nitrate as the source of aluminium dopant. Upon the calcination of the as-spun fibers, the neat and the aluminium-doped titania fibers were obtained. Increasing the calcination temperature resulted in the decrease in the fraction of anatase phase within the fibers, as well as the increase in titania crystallite sizes. The presence of aluminium dopant, however, was found to greatly affect both physical and chemical properties of the synthesized titania fibers. Aluminium nitrate accelerated condensation of titanium oxide species during the sol–gel process, which resulted in increased viscosity of the spinning solution and consequently affected the diameters of the as-spun fibers. Aluminium dopant also played the major roles in both regulating the nucleation rate during crystallization of titania and controlling the growth mechanism of titania crystallites. As a result, the aluminium dopant caused the crystallite size of titania to decrease and retarded phase transformation from anatase to rutile.     

Effect of poly(ε-caprolactone) and titanium (IV) dioxide content on the UV and hydrolytic degradation of poly(lactic acid)/poly(ε-caprolactone) blends

The effect of accelerated weathering degradation on the properties of poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) blends and PLA/PCL/titanium (IV) dioxide (TiO₂) nanocomposites are presented in this paper. The results show that both polymers are susceptible to weathering degradation, but their degradation rates are different and are also influenced by the presence of TiO₂ in the samples. Visual, microscopic and atomic force microsocpy observations of the surface after accelerated weathering tests confirmed that degradation occurred faster in the PLA/PCL blends than in the PLA/PCL/TiO₂ nanocomposites. The X-ray diffraction results showed the degradation of PCL in the disappearance of its characteristic peaks over weathering time, and also confirmed that PLA lost its amorphous character and developed crystals from the shorter chains formed as a result of degradative chain scission. It was further observed that the presence of TiO₂ retarded the degradation of both PLA and PCL. These results were supported by the differential scanning calorimetry results. The thermogravimetric analysis results confirmed that that PLA and PCL respectively influenced each other's thermal degradation, and that TiO₂ played a role in the thermal degradation of both PLA and PCL. The tensile properties of both PLA/PCL and PLA/PCL/TiO₂ were significantly reduced through weathering exposure and the incorporation of TiO₂.     

Synthesis of a star-shaped polymer having tris (β-diketonato)chromium(III) at the center core

Summary The metal-centered star-shaped polymer was prepared by coordination of p-(1,3-butanedionyl)-terminated poly(oxyethylene) with Cr(III) ion. The structure was confirmed by GPC analysis and IR spectra. The resulting polymer complex was well-soluble in various organic solvents and water. Received: 1 June 1998/Accepted: 9 July 1998     

Kinetics and Mechanism of Yb(III) Extraction and Separation from Y(III) with Mixtures of bis(2,4,4‐trimethylpentyl)phosphinic acid and2‐ethylhexyl phosphonic acid mono‐2‐ethylhexyl ester

Abstract

The ytterbium(III) extraction kinetics and mechanism with mixtures of bis(2,4,4‐trimethylpentyl)phosphinic acid (Cyanex272) and 2‐ethylhexyl phosphonic acid mono‐2‐ethylhexyl ester (P507) dissolved in heptane have been investigated by constant interfacial cell with laminar flow. The effects of the stirring rate, temperature, extractant concentration, and pH on the extraction with mixtures of Cyanex272 and P507 have been studied. The results are compared with those of the system with Cyanex272 or P507 alone. It is concluded that the Yb(III) extraction rate is enhanced with mixtures extractant of Cyanex272 and P507 according to their values of the extraction rate constant, which is due to decreasing the activation energy of the mixtures. Atthe same time, the mixtures exhibits no synergistic effects for Y(III), which provides better possibilities for Yb(III) and Y(III) separations at a proper conditions than anyone alone. Moreover, thermodynamic extraction separation Yb(III) and Y(III) by the mixtures has been discussed, which agrees with kinetics results. Extraction rate equations have also been obtained, and through the approximate solutions of the flux equation, diffusion parameters and thickness of the diffusion film have been calculated.     

Synthesis,characterization, crystal structure and in vitro anticancer potentials of mono and bimetallic palladium(II)–N–heterocyclic carbene complexes

N–heterocyclic carbene (NHC) complexes of palladium(II) are generally active as catalysts toward various coupling reactions, while their pharmacological efficiencies are seldom explored. A new series of palladium(II) complexes of both, functionalized and non–functionalized NHCs that were active against the human colon cancer (HCT116) cells are reported. Complexes were prepared by the technique of transmetallation using palladium source and in situ prepared silver(I)–NHC complexes in acetonitrile, and all complexes are characterized using spectroscopic and analytical tools. Additionally, the structure of palladium complex 9 was elucidated using single crystal X–ray diffraction method. In vitro anticancer studies revealed that the palladium complexes, 9 and 10, having xylyl–spacers significantly inhibited the HCT116 cell growth, exhibiting IC₅₀ values in low micromolar range in MTT assay.     

Characterization and adsorption behavior of newly synthesized sodium bis(2-ethylhexyl) sulfosuccinate–cerium (IV) phosphate (AOT–CeP) cation exchanger

A new cationic exchange material, sodium bis(2-ethylhexyl) sulfosuccinate (AOT) with cerium (IV) phosphate (AOT–CeP) has been synthesized. The characterization of the ion exchanger was performed by using infra red spectroscopy (IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), thermo gravimetric analysis/differential thermo gravimetric analysis (TGA/DTA/DTG) and elemental analysis. The ion exchange properties like ion exchange capacity, elution and concentration behavior of AOT–CeP were determined by taking the material into a column and elution of H⁺ was done by NaNO₃. The thermal stability of the ion exchanger was studied by determining ion exchange capacity after heating to different temperatures for one hour. The adsorption studies on AOT–CeP demonstrated that the material is selective for Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions. AOT–CeP was found to be effective for the separation of Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions in the presence of alkali metals/alkaline earth metals. This cationic exchanger was also effective for the removal of Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions in the presence of acid and other transition metal ions. Thus, AOT–CeP can be used for the removal of these ions from the waste water during its treatment.     

Synthesis of novel poly(ethylene-ter-1-hexene-ter-dicyclopentadiene)s using bis(β-enaminoketonato)titanium catalysts and their applications in preparing polyolefin-graft-poly(?-polycaprolactone)

Novel terpolymers containing ethylene, 1-hexene and dicyclopentadiene (DCPD) were synthesized using bis(β-enaminoketonato)titanium catalysts [PhNC(R₂)CHC(R₁)O]₂TiCl₂ (1a: R₁ = Ph, R₂ = CF₃; 1b: R₁ = CF₃, R₂ = CH₃). In the presence of modified methylaluminoxane, these catalysts afforded terpolymers with a broad range of monomer compositions and unimodal molecular weight distributions. ¹³C NMR spectra reveal the exclusive insertion manner of DCPD maintained under various reaction conditions. DSC results show the melting temperature and the glass transition temperature are very sensitive to the terpolymer composition and the morphology can be easily tuned from semicrystalline state to amorphous state. With ethylene/1-hexene/DCPD molar ratio about 67/28/5, the terpolymer exhibits low glass transition temperature (T_g = −50 °C) and has a great potential to serve as polyolefin elastomer. Additionally, the terpolymer containing 4.3 mol% 1-hexene and 1.6 mol% DCPD was served as the “reactive intermediate polyolefin” for PCL graft reaction. The composition of graft copolymer was well controllable and high graft efficiency was observed. The microscopy studies in conjunction with the tensile tests revealed that PCL graft copolymer is the effective compatibilizer for polyethylene/polar polymer blends by improving the interfacial adhesion between separated phases.     

Synthesis and characterization of 4,4’–(dimethylsilylene) bis( phenyl chloroformate) and 4,4’–(dimethylgermylene)bis(phenyl chloroformate) and their use in the synthesis of poly(urethanes)

Summary The synthesis of 4,4–(dimethylsilylene)bis(phenyl chloroformate) and 4,4–(dimethylgermylene)bis(phenyl chloroformate) is described according to the same route for the synthesis of bisphenol–A bischloroformate. These compounds were characterized using elemental analysis, FT–IR and NMR spectroscopy. Poly(urethanes) derived from these bischlororformates containing silicon or germane in the main chain, were obtained in benzene solution by reaction with 4,4–methylenedianiline in the presence of pyridine. Poly(urethanes) were characterised by spectroscopic methods and the thermal properties (Tg and thermal stability) were compared with the homologue poly(urethane) obtained from bisphenol–A chloroformate.     

Aluminum- and calcium-incorporated MCM-41-type silica as supports for the immobilization of titanium(IV) isopropoxide in ring-opening polymerization of l-lactide and ε-caprolactone

Aluminum- and calcium-incorporated MCM-41-type silica with various Al/Si and Ca/Si ratios were evaluated as catalytic supports for ring-opening polymerization (ROP) of l-lactide and ε-caprolactone. The catalytic centers were generated by grafting titanium(IV) isopropoxide onto the support. All prepared heterogeneous catalysts better restrained the ROP of lactide than the homogeneous analog, titanium(IV) isopropoxide. Compared to siliceous MCM-41, the incorporation of aluminum or calcium in MCM-41 framework improved the molecular weight of the polymers although it lessened the polymerization rate. The more acidic Al-MCM-41 support appeared to be more favorable than the more basic Ca-MCM-41 support for the ROP reactions.