Ni ion-containing immobilized ionic liquid on magnetic Fe3O4 nanoparticles: An effective catalyst for the Heck reaction

In this work, we synthesized Ni²⁺-containing 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium chloride ionic liquid on magnetic Fe₃O₄ nanoparticles. The catalytic activity of these novel nanocomposites was finally evaluated for the Heck reaction at 100 °C, and can be reused after washing without loss in activity. The immobilized ionic liquid catalysts proved to be effective and easily separated from the reaction media by applying an external magnetic field. This procedure has many obvious advantages compared to those reported in the previous literature, including avoidance of the use of the expensive Pd catalysts, mild reaction conditions, high yields, and simplicity of the methodology.     

Development of diffusive solid phase microextraction method for sampling of epichlorohydrin in air

Epichlorohydrin is used frequently in many industrial processes. Exposure to this pollutant could induce harmful effects. The present work developed a novel solid phase microextraction (SPME) method for time weighted average determination of epichlorohydrin in the air by GC/MS. CAR/PDMS in 0.5?cm retracted mode was selected and the effect of environmental parameters on sampling properties of SPME was examined. Experimental sampling rate for epichlorohydrin (8.89?×?10^?3?cm³/min) was slightly less than theoretical value (9.059?×?10^?3?cm³/min). There was no significant difference among sampling rates at different temperature and velocities but relative humidity had a significant effect on the sampling rate. Limit of detection for SPME method was 0.8?ng per sample, which is good enough in comparison with the NIOSH 1010 method. Comparison of the results between the developed SPME and the NIOSH 1010 method on standard test atmosphere and field showed satisfactory agreement (y?=?1.162x?+?1.8 r ²?=?0.992 and y?=?1.009x+0.76 r ²?=?0.98 respectively).     

Structural,Theoretical, and Spectroscopic Study of Mercury(II) Complexes of two New Unsymmetric Phosphorus Ylides

Abstract

The reaction of Ph₂PCH₂PPh₂ (dppm) with 4-methylphenacyl bromide and 2-(bromoacetyl)naphthalene in chloroform produce the new phosphonium salts [Ph₂PCH₂PPh₂CH₂C(O)C₆H₄Me]Br (1) and [Ph₂PCH₂PPh₂CH₂C(O)C₁₀H₇]Br (2). Further, by reaction of the monophosphonium salts of dppm with the strong base Et₃N the corresponding bidentate phosphorus ylides, Ph₂PCH₂P(Ph)₂ = C(H)C(O)C₆H₄Me (3) and Ph₂PCH₂P(Ph)₂ = C(H)C(O)C₁₀H₇ (4) were obtained. The reaction of these ligands with mercury(II) halides in dry methanol led to the formation of the mononuclear complexes {HgX ₂[(Ph₂PCH₂PPh₂C(H)C(O)C₆H₄Me)]} [X = Cl (5), Br (6), and I (7)] and {HgX ₂[(Ph₂PCH₂PPh₂C(H)C(O)C₁₀H₇)]} [X = Cl (8), Br (9), and I (10)]. Characterization of the obtained compounds was performed by elemental analysis, IR, ¹H, ³¹P, and ¹³C NMR spectra. The structure of compounds 3 and 10 are unequivocally determined by single crystal X-ray diffraction techniques. X-ray analysis of 10 reveals the presence of mononuclear complex containing Hg atom in a distorted tetrahedral environment. In all complexes, the title ylides are coordinated through the ylidic carbon and the phosphine phosphorus. Computational studies on ligand 4 and complexes 8, 9, and 10 at DFT (B3LYP) level of theory are also reported. It was shown that the formation of P,C-coordinated 1+1 complex 10 is energetically more favored than corresponding P,P-coordinated 1+2 product.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the following free supplemental files: Additional figures]     

Synthesis and Multinuclear NMR Study of Benzoyl Methylene Triparatolylphosphorane Ylide and the Reaction of this Ylide with Mercury(II) Halides

The reaction of the title ylide {PhCOCHP(p-tolyl)₃} with Pd(II), Pt(II). Hg(II), and Ag(I) in equimolar ratios using CH₃CN, CH₃OH, and CH₂Cl₂ as solvents have yielded [{(p-tolyl)₃PCHCOC₆H₅} PdCl₂]₂ (I), [{(p-tolyl)₃ PCHCOC₆H₅} PtCl₂]₂(2), [Hg(NO₃)₂ {(p-tolyl)₃ PCHCOC₆H₅}](3), and [Ag{(p-tolyl)₃ PCHCOC₆H₅ < eqid1 > ₂]⁺ (4). The IR, ¹H ¹³C, and ³¹P NMR together with micro analysis data of the products were obtained.     

Optimized preparation and preliminary evaluation of [64Cu]–DOTA–trastuzumab for targeting ErbB2/Neu expression

Breast cancer radioimmunoscintigraphy targeting HER2/neu expression is a growing field of work in nuclear medicine research. Trastuzumab is a monoclonal antibody that binds with high affinity to HER2/neu, which is over expressed on breast and other tumors. Developing new tracers for the detection of this cancer is of great interest. In this study, trastuzumab was successively labeled with [⁶⁴Cu]CuCl₂ after conjugation with DOTA-NHS-ester. The conjugate was purified by molecular filtration, the average number of DOTA conjugated per mAb was calculated and total concentration was determined by spectrophotometric method. DOTA–trastuzumab was labeled with ⁶⁴Cu produced by ⁶⁸Zn(p,αn)⁶⁴Cu nuclear reaction (30 MeV protons at 180 μA). Radiochemical purity, integrity of protein after radiolabeling and immunoreactivity of radiolabeled mAb trastuzumab with HER2/neu antigen and SkBr3 cell line were performed by RIA. In vitro stability of radiolabeled mAb in human serum was determined by thin layer chromatography. In vitro internalization studies were performed with the SkBr3 cell line and the tissue biodistribution of the ⁶⁴Cu–DOTA–trastuzumab was evaluated in wild-type rat (90 ± 5.5 μCi, 2, 6, 12, 24 h p.i.). The radioimmunoconjugate was prepared with a radiochemical purity of higher than 96 ± 0.5 % (ITLC) and specific activity as high as 5.3 μCi/μg. The average number of chelators per antibody for the conjugate used in this study was 5.8/1. The sample was showed to have similar patterns of migration in the gel electrophoresis. The ⁶⁴Cu–DOTA–trastuzumab showed high immunoreactivity towards HER2/neu antigen and SkBr3 cell line. In vitro stability of the labeled product was found to be more than 94 % in PBS and 82 ± 0.5 % in human serum over 48 h. In vitro internalization studies of the ⁶⁴Cu–DOTA–trastuzumab showed that up to 11.5 % of the radioimmunoconjugate internalized after 10 h. The accumulation of the radiolabeled mAb in liver, skin, intestine, lung, spleen, kidney and other tissues demonstrates a similar pattern to the other radiolabeled anti-HER2 immunoconjugates. ⁶⁴Cu–DOTA–trastuzumab is a potential compound for molecular imaging of PET for diagnosis and treatment studies and follow-up of HER2 expression in oncology.     

Catalyst-free synthesis of functionalized dihydro-2-oxypyrroles by the reaction of enaminones and N,N′-bis(phenylmethylidene)phenylmethane

A catalyst-free and convenient approach for the preparation of substituted dihydro-2-oxypyrrole is described. This three-component reaction between primary amines, dialkyl acetylenedicarboxylate, and N,N′-bis(phenylmethylidene)phenylmethane proceeds in MeOH under reflux conditions in good to excellent yields.     

Four component and solvent‐free synthesis of some new spiro‐1,4‐dihydropyridines on solid support montmorillonite K10

A series of some new spiro‐1,4‐dihydropyridine derivatives have been synthesized in good yields in a four component, and solvent‐free process by condensation of isatins, primary amines, ethyl cyanoacetate and cyclohexanone on solid support montmorillonite K10     

A stereoselective three-component reaction: KAl(SO4)2.12H2O, an efficient and reusable catalyst for the one-pot synthesis of cis-isoquinolonic acids

KAl(SO(4))(2).12H(2)O is found to catalyze efficiently the stereoselective one-pot three-component cyclocondensation of homophthalic anhydride, aldehydes, and amines under mild conditions to afford the corresponding cis-isoquinolonic acids in good yields.     

Integrated production scheduling in large-scale flexible electronic parts manufacturing

This study reports the development of a production scheduling system for the integrated management of production in large-scale, high-volume electronic assembly lines. The development of the system incorporates control and planning considerations by addressing the interaction of various subsystems. Stochastic and deterministic aspects of the problem environment are appropriately handled via relevant simulation and analytic models. By effecting a hierarchical breakdown of the problem environment, the system produces information used in practical decision making for production planning and scheduling. Procedures used encompass and address considerations for management of work-in-process, optimization of the various subsystems' performance, minimization of setup time effect, and inventory carrying costs.     

Mild Oxidation of Oxime Derivatives with KMnO4 in Ionic Liquid Media

In this research, potassium permanganate in the presence of a catalytic amount of [bmim]Br under solvent free conditions is used as an efficient and chemoselective method for oxidative cleavage of some oximes to corresponding carbonyl compounds. This experiment was carried out in mild conditions without any further oxidation of aldehydes to corresponding acids.