Mechanistic studies of nickel(II) alkyl agostic cations and alkyl ethylene complexes: investigations of chain propagation and isomerization in (alpha-diimine)Ni(II)-catalyzed ethylene polymerization

The synthesis of a series of (alpha-diimine)NiR(2) (R = Et, (n)Pr) complexes via Grignard alkylation of the corresponding (alpha-diimine)NiBr(2) precursors is presented. Protonation of these species by the oxonium acid [H(OEt(2))(2)](+)[BAr'(4)](-) at low temperatures yields cationic Ni(II) beta-agostic alkyl complexes which model relevant intermediates present in nickel-catalyzed olefin polymerization reactions. The highly dynamic nature of these agostic alkyl cations is quantitatively addressed using NMR line broadening techniques. Trapping of these complexes with ethylene provides cationic Ni alkyl ethylene species, which are used to determine rates of ethylene insertion into primary and secondary carbon centers. The Ni agostic alkyl cations are also trapped by CH(3)CN and Me(2)S to yield Ni(R)(L)(+) (L = CH(3)CN, Me(2)S) complexes, and the dynamic behavior of these species in the presence of varied [L] is discussed. The kinetic data obtained from these experiments are used to present an overall picture of the ethylene polymerization mechanism for (alpha-diimine)Ni catalysts, including effects of reaction temperature and ethylene pressure on catalyst activity, polyethylene branching, and polymer architecture. Detailed comparisons of these systems to the previously presented analogous palladium catalysts are made.     

Transient streaming potential in a finite length microchannel

Pressure-driven flow of an electrolyte solution in a microchannel with charged solid surfaces induces a streaming potential across the microchannel. Such a flow also causes rejection of ions by the microchannel, leading to different concentrations in the feed and permeate reservoirs connecting the capillary, which forms the basis of membrane based separation of electrolytes. Modeling approaches traditionally employed to assess the streaming potential development and ion rejection by capillaries often present a confusing picture of the governing electrochemical transport processes. In this paper, a transient numerical simulation of electrochemical transport process leading to the development of a streaming potential across a finite length circular cylindrical microchannel connecting two infinite reservoirs is presented. The solution based on finite element analysis shows the transient development of ionic concentrations, electric fields, and the streaming potential over the length of the microchannel. The transient analysis presented here resolves several contradictions between the two types of modeling approaches employed in assessing streaming potential development and ion rejection. The simulation results show that the streaming potential across the channel is predominantly set up at the timescale of the developing convective transport, while the equilibrium ion concentrations are developed over a considerably longer duration.     

The dynamics of impacting water droplets on alkanethiol self-assembled monolayers with co-adsorbed CH3 and CO2H terminal groups

The impact of water droplets (diameter 3.6 mm) at a fixed Weber number of 59 on solid surfaces with precisely tailored surface wettabilities was studied experimentally using a high-speed imaging camera at 2500 frames per second. Solid surface wettability was varied using four fractional mixtures of self-assembled monolayers of 1-octadecanethiol and 16-mercaptohexadecanoic acid. The surfaces so obtained are characterized for contact angle and chemical functionality using the axisymmetric drop shape analysis profile (ADSA-P) technique and Fourier transform infrared spectroscopy (FT-IR). Our results correlate the wetting effects of the impacting droplets with the surface energy and contact angle measurements of the tailored surfaces. Literature models for the maximum spreading diameter are employed and compared with those from our experiments. An equation is also proposed for the maximum spreading diameter which makes use of the correct contact angles and results in the least error among the models considered. As a consequence of Young's equation, the correct contact angles to be used for droplet impact dynamics should be the corresponding advancing angles on a smooth substrate of interest. We also conclude that accurate examination of literature models requires careful experimentation on impact dynamic data on well-prepared and characterized surfaces such as those presented here.     

HMDS/KI a simple,a cheap and efficient catalyst for the one-pot synthesis of N-functionalized pyrimidines

The syntheses of N-Alkylpyrimidine derivatives by reacting pyrimidin-2,4-diones with appropriate alkyl halide under microwave irradiation at 400?W were compared to the conventional synthesis route. These methodologies are regioselective and compatible with numerous substrates and furnish the corresponding N-alkylpyrimidines in good yields using a cheap catalyst HMDS/KI in MeCN. A comparison study between these two different modes of heating was investigated.     

Do we know the mass of a black hole? Mass of some cosmological black hole models

Using a cosmological black hole model proposed recently, we have calculated the quasi-local mass of a collapsing structure within a cosmological setting due to different definitions put forward in the last decades to see how similar or different they are. It has been shown that the mass within the horizon follows the familiar Brown–York behavior. It increases, however, outside the horizon again after a short decrease, in contrast to the Schwarzschild case. Further away, near the void, outside the collapsed region, and where the density reaches the background minimum, all the mass definitions roughly coincide. They differ, however, substantially far from it. Generically, we are faced with three different Brown–York mass maxima: near the horizon, around the void between the overdensity region and the background, and another at cosmological distances corresponding to the cosmological horizon. While the latter two maxima are always present, the horizon mass maxima is absent before the onset of the central singularity.     

Synthesis of Naturally Occurring Helminthic Phosphodiesters and Related Analogues

Abstract

Our preliminary findings in the use of 1,3,2-oxazaphospholidin-2-ones (III) as useful synthons in the synthesis of naturally occurring helminthic (worm) phosphodiesters [i.e. Opheline(II, R=Me) and serine ethanolamine phosphate (I, R=NH₂(CO₂H)CHCH₂,R′=H)] and of related compounds are reported. The 1,3,2-oxazaphospholidin-2-ones can be synthesised by routes A and B; once formed these can be ring-opened by acid treatment which causes exclusive N-P bond fission yielding the phosphodiesters (I). Guanidinated phosphodiesters (II) have been made by reacting the corresponding phosphodiesters (I,R′=H) with O-methylisourea.     

Synthesis of oxo-Phosphoranylidene Aminobenzoic Acid Derivatives by a Multicomponent Reaction

2-Aminobenzoic acids or 4-aminobenzoic acid react with dimethyl acetylenedicarboxylate/triphenylphosphine in less than 20 min at 15–25°C to produce new organic phosphorus compounds in good to excellent yields. The conversion occurs with selective N- over O-alkylation of the amino group and isolation of the products is accomplished simply by filtration.     

Fabrication of an Electrochemical L‐Cysteine Sensor Based on Graphene Nanosheets Decorated Manganese Oxide Nanocomposite Modified Glassy Carbon Electrode

The graphene nanosheets/manganese oxide nanoparticles modified glassy carbon electrode (GC/GNSs/MnOx) was simply prepared by casting a thin film of GNSs on the GC electrode surface, followed by performing electrodeposition of MnOx at applied constant potential. The GC/GNSs/MnOx modified electrode shows high catalytic activity toward oxidation of L ‐cysteine. Hydrodynamic amperometry determination of L ‐cysteine gave linear responses over a concentration range up to 120 µM with a detection limit of 75 nM and sensitivity of 27 nA µM^?1. The GC/GNSs/MnOx electrode appears to be a highly efficient platform for the development of sensitive, stable and reproducible L ‐cysteine electrochemical sensors.