Organophosphine/phosphite‐stabilized silver(I) complexes bearing N‐acetylbenzamide ligand: synthesis,characterization and potential application in metal organic chemical vapor deposition

New N‐silver(I) acetylbenzamide complexes of type L_n?AgNC₉H₈O₂ (L = PPh₃; n = 1, 2a; n = 2, 2b; n = 3, 2c; L = P(OEt)₃; n = 1, 2d; n = 2, 2e; n = 3, 2f) were prepared. These complexes were obtained in high yields and characterized by elemental analysis, ¹H NMR, ¹³C{H} NMR, ³¹P{H} NMR and IR spectroscopy, respectively. The molecular structure of 2b has been determined by X‐ray single‐crystal analysis in which the silver atom is in a distorted tetrahedral geometry and crystallizes as cis–trans. New N‐silver(I) acetylbenzamide complexes have a four‐membered ring, which could influence their chemical and physical properties and modulate volatility. Metal organic chemical vapor deposition experiments were carried out successfully at 400°C and 450°C using 2e as precursor for the deposition of silver films, respectively. The high‐purity silver film obtained at 400°C is dense and homogeneous. Copyright © 2012 John Wiley & Sons, Ltd.     

Copper‐catalyzed Clauson–Kass pyrroles synthesis in aqueous media

An efficient and convenient copper‐catalyzed Clauson–Kass reaction of 2,5‐dimethoxytetrahydrofuran with amines in aqueous media has been developed, providing a wide range of N‐substituted pyrroles in good yields. It is noteworthy that the Clauson–Kass reaction of 2,5‐dimethoxytetrahydrofuran with p‐phenylenediamine or m‐phenylenediamine proceeds smoothly to afford the corresponding monopyrroles and bispyrroles with high selectivity in impressive yields. A plausible mechanism for the formation of N‐substituted pyrroles has been proposed. Copyright © 2012 John Wiley & Sons, Ltd.     

Biological evaluation of novel selenazole‐based compounds as potential thioredoxin reductase inhibitors

Recently, thioredoxin reductase as a target for treatment of tumors has attracted the attention of scientists. 1,2‐[Bis(1,2‐benzisoselenazolone‐3(2 H)‐ketone)]ethane (ethaselen, BBSKE, PCT: CN02/00412), designed and synthesized previously, is an effective thioredoxin reductase inhibitor; presently it is in phase II clinical trials, targeting gastric cancer, lung cancer and colon cancer. To seek more novel and effective anticancer drugs, we have developed many selenazole‐based compounds. Evaluation of the thioredoxin reductase inhibitory effect and investigation of the mechanism of anticancer drugs require abundant thioredoxin reductase, but since commercial thioredoxin reductase is expensive its use is often limited. Therefore, the preparation of thioredoxin reductase is necessary. Base on the above investigation, in this work we have prepared thioredoxin reductase and evaluated selenazole‐based compounds, and found that 44 compounds have high inhibitory effect on thioredoxin reductase with IC₅₀ < 10 µ m , of which 16 compounds have IC₅₀ values below 1 µ m . This is helpful in investigating and elucidating the mechanism of this kind of compound. Copyright © 2012 John Wiley & Sons, Ltd.     

Coordination Chemistry of Gold Catalysts in Solution: A Detailed NMR Study

Coordination chemistry of gold catalysts bearing eight different ligands [L=PPh₃, JohnPhos (L2), Xphos (L3), DTBP, IMes, IPr, dppf, S‐tolBINAP (L8)] has been studied by NMR spectroscopy in solution at room temperature. Cationic or neutral mononuclear complexes LAuX (L=L2, L3, IMes, IPr; X=charged or neutral ligand) underwent simple ligand exchange without giving any higher coordinate complexes. For L2AuX the following ligand strength series was determined: MeOH?hex‐3‐yne <MeCN≈OTf^??Me₂S<2,6‐lutidine<4‐picoline<CF₃CO₂^?≈DMAP<TMTU<PPh₃<OH^?≈Cl^?. Some heteroligand complexes DTBPAuX exist in solution in equilibrium with the corresponding symmetrical species. Binuclear complexes dppf(AuOTf)₂ and S‐tolBINAP(AuOTf)₂ showed different behavior in exchange reactions with ligands depending on the ligand strength. Thus, PPh₃ causes abstraction of one gold atom to give mononuclear complexes LLAuPPh₃⁺ and (Ph₃P)_nAu⁺, but other N and S ligands give ordinary dicationic species LL(AuNu)₂²⁺. In reactions with different bases, LAu⁺ provided new oxonium ions whose chemistry was also studied: (DTBPAu)₃O⁺, (L2Au)₂OH⁺, (L2Au)₃O⁺, (L3Au)₂OH⁺, and (IMesAu)₂OH⁺. Ultimately, formation of gold hydroxide LAuOH (L=L2, L3, IMes) was studied. Ligand‐ or base‐assisted interconversions between (L2Au)₂OH⁺, (L2Au)₃O⁺, and L2AuOH are described. Reactions of dppf(AuOTf)₂ and S‐tolBINAP(AuOTf)₂ with bases provided more interesting oxonium ions, whose molecular composition was found to be [dppf(Au)₂]₃O₂²⁺, L8(Au)₂OH⁺, and [L8(Au)₂]₃O₂²⁺, but their exact structure was not established. Several reactions between different oxonium species were conducted to observe mixed heteroligand oxonium species. Reaction of L2AuNCMe⁺ with S^2? was studied; several new complexes with sulfide are described. For many reversible reactions the corresponding equilibrium constants were determined.     

A vectorial algorithm with finite element method for prediction of powder segregation in metal injection molding

The design of the mold and the choice of the injection parameters for metal injection molding (MIM) is required to maintain homogeneity of the filled mixture. However, powder segregation is unavoidable in MIM because of the significant difference in densities of the metallic powder and the polymer binder. To achieve an effective prediction of segregation effect, a biphasic model based on mixture theory is employed. The viscous behaviors of each phase and the interaction coefficient between the flows of the two phases should be determined. The solution of two coupled Navier–Stokes equations results in a tremendous computation effort. The previous development of an explicit algorithm makes the biphasic simulation much faster than that of the classic methods. However, it is strongly desired to reduce or even eliminate the numerous global solutions for pressure fields at each time step. Hence, a new vectorial algorithm is proposed and developed to perform the simulation only by vectorial operations. It provides the anticipated efficiency in the simulation of biphasic modeling, and the advantage to use the classic elements of equal‐order interpolations. Some results produced by the two algorithms are compared with the experimental values to validate the new vectorial algorithm. Copyright © 2012 John Wiley & Sons, Ltd.     

Instabilities in free-surface electroosmotic flows

Instability of a thin electrolyte film undergoing a direct current electroosmotic flow has been investigated. The film with a compliant electrolyte–air interface is flowing over a rigid charged substrate. Unlike previous studies, inclusion of the Maxwell stresses in the formulation shows the presence of a new finite wavenumber shear-flow mode of instability, alongside the more frequently observed long-wave interfacial mode. The shear mode is found to be the dominant mode of instability when the electrolyte–solid and electrolyte–air interfaces are of opposite charge or of same charge but have very large zeta-potential at the electrolyte–air interface. The conditions for mode-switch (interfacial to shear) and the direction of the travelling waves are discussed through stability diagrams. Interestingly, the analysis shows that when the interfaces are of nearly same zeta potential, the ‘free’ electrolyte–air interface behaves more like a ‘stationary’ wall because of the ion transport in the reverse direction of the flow.