Unbridged bidentate aluminum complexes supported by diaroylhydrazone ligands: Synthesis,structure and catalysis in polymerization of ε-caprolactone and lactides

A series of novel diaroylhydrazone aluminum complexes have been synthesized and well-defined structurally, and their catalytic performance in the polymerization of ε-caprolactone and lactides have also been evaluated. Complexes [(L^1–4)₂AlMe] ( 1 – 4 ) {[L¹ = (3,5-^tBu₂–2-OMe-C₆H₂)CH=NNCOC₆H₅], [L² = (3,5-^tBu₂–2-OMe-C₆H₂)CH=NNCO(C₆H₄–4-OCH₃)], [L³ = (3,5-^tBu₂–2-OMe-C₆H₂)CH=NNCO(C₆H₄–4-Br)] and [L⁴ = (2-OMe-C₆H₄)CH=NNCO(C₆H₄–4-^tBu)]} were prepared through treatment of AlMe₃ with the corresponding proligands L^1–4H in molar ratios of 1: 1 or 1: 2. Chemical structures of all the complexes were well-defined by elemental analysis, NMR spectra as well as single-crystal X-ray study. Complexes [(L^1–4)₂AlMe] ( 1 – 4 ) in this work represent the first examples of aluminum complexes of aroylhydrazone ligands with crystallographic characterization. Specifically, they are all in monomeric form with a penta-coordinated aluminum center, including two approximately co-planar five-membered metallacycles with aluminum. Introduced bulky tert-butyl substituents in aroylhydrazone ligands could affect the geometry around the central metal which is a distorted square-based pyramid in complexes 1 – 3 while being a trigonal bipyramidal in complex 4 , thus affecting their catalytic behaviors. The complexes can successfully catalyze the ring-opening polymerization of ε-caprolactone and _L-lactide under mild conditions without any activator. In addition, complexes 1 – 4 could also polymerize rac-lactide, affording atactic polylactides with high conversions and good controllability in relatively short reaction time.     

Ultrafine PtRu Dilute Alloy Nanodendrites for Enhanced Electrocatalytic Methanol Oxidation

Dilute alloy nanostructures have been demonstrated to possess distinct catalytic properties. Noble-metal-induced reduction is one effective synthesis strategy to construct dilute alloys and modify the catalytic performance of the host metal. Herein, we report the synthesis of ultrafine PtRu dilute alloy nanodendrites (PtRu NDs, molar ratio Ru/Pt is 1:199) by the reduction of Ru^III ions induced by Pt metal. For the methanol oxidation reaction, PtRu NDs showed the highest forward peak current density (2.66 mA cm⁻², 1.14 A/mg_Pt) and the best stability compared to those of pure-Pt nanodendrites (pure-Pt NDs), commercial PtRu/C and commercial Pt/C catalysts.     

How the Physicochemical Properties of the Bulk Material Affect the Ablation Crater Profile,Mass Balance,and Bubble Dynamics During Single-Pulse,Nanosecond Laser Ablation in Water

Understanding the key steps that drive the laser-based synthesis of colloids is a prerequisite for learning how to optimize the ablation process in terms of nanoparticle output and functional design of the nanomaterials. Even though many studies focus on cavitation bubble formation using single-pulse ablation conditions, the ablation efficiency and nanoparticle properties are typically investigated under prolonged ablation conditions with repetition rate lasers. Linking single-pulse and multiple-pulse ablation is difficult due to limitations induced by gas formation cross-effects, which occur on longer timescales and depend on the target materials’ oxidation-sensitivity. Therefore, this study investigates the ablation and cavitation bubble dynamics under nanosecond, single laser pulse conditions for six different bulk materials (Au, Ag, Cu, Fe, Ti, and Al). Also, the effective threshold fluences, ablation volumes, and penetration depths are quantified for these materials. The thermal and chemical properties of the corresponding bulk materials not only favor the formation of larger spot sizes but also lead to the highest molar ablation efficiencies for low melting materials such as aluminum. Furthermore, the concept of the cavitation bubble growth linked with the oxidation sensitivity of the ablated material is discussed. With this, evidence is provided that intensive chemical reactions occurring during the very early timescale of ablation are significantly enhanced by the bubble collapse.     

Approximant crystals of icosahedral Mg–(Ga,Al)–Zn alloys

The zero field cooled (ZFC) and field cooled (FC) low-field magnetic moment m of a dense frozen ferrofluid containing Fe₅₅Co₄₅ particles of size 4.6nm in hexane exhibits irreversibility at temperatures T?T _b≈ 30?K. FC in μ ₀ H ≤ 1?T gives rise to shifted minor hysteresis loops below T _b. At T _c≈ 10?K, sharp peaks of m ^ZFC and of the ac susceptibility χ ′, a kink of the thermoremanent magnetic moment m ^TRM, a sizeable reduction of the coercive field H _c, and the appearance of a spontaneous moment m ^SFM indicate a phase transition with near mean-field critical behaviour of both m ^SFM and χ ′ . These features are explained within a core-shell model of nanoparticles, whose strongly disordered shells gradually become blocked below T _b, while their soft ferromagnetic cores couple dipolarly and become superferromagnetic (SFM) below T _c.     

Temperature‐dependent local atomic structures in the traditional Fe65Ni35 Invar alloy by X‐ray fluorescence holography

Fe and Ni Kα X‐ray fluorescence holography measurements were conducted on a single crystal Fe₆₅Ni₃₅ Invar alloy at 100 and 300 K to investigate the temperature dependence of the 3‐dimensional local structures around the Fe and Ni atoms, respectively. Local structural information was obtained by detailed analyses using a L₁‐regularized linear regression for the experimental data. At 100 K, the local atomic arrangements around both the elements show fcc structures. At 300 K, however, only the image around Fe shows a bcc‐like neighboring arrangement. From these X‐ray fluorescence holography data, we propose a model that with increasing temperature, an Fe atom with the low‐spin state enters at the central position of the fcc lattice and is stabilized. And then, large angular positional fluctuations are induced for the atoms at the face‐centered positions around the central Fe atom only.     

Fluorimetric Analysis of Aluminum in Diluted Hemodialysis Solutions by Using a Novel Schiff Base

A spectrofluorimetric method has been developed for trace amount of aluminum(III) by using a novel Schiff base, N,N′-bis(salicylidene)-1,4-diaminobuthane (BUTAS), and 4-methyl-2-aminophenol (OAP). Since the aluminum complexes are generally fluorescent, aluminum(III) increases the fluorescence intensity of BUTAS-OAP by formation of Al-BUTAS-OAP complex. The fluorescence of the complex is measured at an excitation wavelength of 410 nm with an emission at 526 nm. Aluminum(III) can be detected within a concentration limit of 0.11–1.62 ppb and the lowest detection limit being 0.07 ppb. The proposed method was applied to diluted hemodialysis solution and spectrofluorimetric data was compared with data of standard pharmacopoeia method.     

Corrosion inhibition of ammonium molybdate for AA6061 alloy in NaCl solution and its synergistic effect with calcium gluconate

The corrosion inhibition of ammonium heltamolybdate (AH) and calcium gluconate (CG) for AA6061 alloy in 3% NaCl solution was investigated by the electrochemical measurements. It indicates that AH inhibits the corrosion of AA6061 alloy and acts as an anodic inhibitor. Maximum inhibition efficiency reaches 74.3% at the concentration of 1 × 10^?4 mol.l^?1 AH. The results of the electrochemical studies reveal AH is physically adsorbed on the AA6061 alloy surface and the adsorption follows Langmuir isotherm. The combination of AH and CG enhances the inhibition efficiency to 95.9%. The enhanced inhibition is attributed to the promotion of AH adsorption by CG. The mixture of AH and CG is a mixed‐type inhibitor and renders the corrosion potential to more positive values. Copyright © 2011 John Wiley & Sons, Ltd.     

Insight into Oxide‐Bridged Heterobimetallic Al/Zr Olefin Polymerization Catalysts

Reaction of (TBBP)AlMe ? THF with [Cp*₂Zr(Me)OH] gave [(TBBP)Al(THF)?O?Zr(Me)Cp*₂] (TBBP=3,3’,5,5’‐tetra‐tBu‐2,2'‐biphenolato). Reaction of [DIPPnacnacAl(Me)?O?Zr(Me)Cp₂] with [PhMe₂NH]⁺[B(C₆F₅)₄]^? gave a cationic Al/Zr complex that could be structurally characterized as its THF adduct [(DIPPnacnac)Al(Me)?O?Zr(THF)Cp₂]⁺[B(C₆F₅)₄]^? (DIPPnacnac=HC[(Me)C=N(2,6‐iPr₂?C₆H₃)]₂). The first complex polymerizes ethene in the presence of an alkylaluminum scavenger but in the absence of methylalumoxane (MAO). The adduct cation is inactive under these conditions. Theoretical calculations show very high energy barriers (ΔG=40–47 kcal mol^?1) for ethene insertion with a bridged AlOZr catalyst. This is due to an unfavorable six‐membered‐ring transition state, in which the methyl group bridges the metal and ethene with an obtuse metal‐Me‐C angle that prevents synchronized bond‐breaking and making. A more‐likely pathway is dissociation of the Al‐O‐Zr complex into an aluminate and the active polymerization catalyst [Cp*₂ZrMe]⁺.