High-Fidelity,Narcissistic Self-Sorting in the Synthesis of Organometallic Assemblies from Poly-NHC Ligands

Highly selective, narcissistic self-sorting has been observed in the one-pot synthesis of three organometallic molecular cylinders of type [M₃{L-(NHC)₃}₂](PF₆)₃ (M=Ag⁺, Au⁺; L=1,3,5-benzene, triphenylamine, or 1,3,5-triphenylbenzene) from L-(NHC)₃ and silver(I) or gold(I) ions. The molecular cylinders contain only one type of tris-NHC ligand with no crossover products detectable. Transmetalation of the tris-NHC ligands from Ag⁺ to Au⁺ in a one-pot reaction with retention of the supramolecular structures is also demonstrated. High-fidelity self-sorting was also observed in the one-pot reaction of benzene-bridged tris-NHC and tetrakis-NHC ligands with Ag₂O. This study for the first time extends narcissistic self-sorting in metal–ligand interactions from Werner-type complexes to organometallic derivatives.     

A summation‐integral type modification of Szász–Mirakjan operators

In this paper, we introduced a summation‐integral type modification of Szász–Mirakjan operators. Calculation of moments, density in some space, a direct result and a Voronvskaja‐type result, are obtained. Copyright © 2016 John Wiley & Sons, Ltd.     

Diagnosis of Wireless Sensor Networks in Presence of Permanent and Intermittent Faults

In this paper we consider the problem of distributed fault diagnosis in Wireless Sensor Networks (WSNs). The proposed Fault Diagnosis Algorithm (FDA) aims to handle both permanent and intermittent faults. The sensor nodes with permanent communication faults can be diagnosed by using the conventional time-out mechanism. In contrast, it is difficult to detect intermittent faults due to their inherent unpredictable behavior. The FDA is based on the comparison of sensor measurements and residual energy values of neighboring sensor nodes, exploiting their spatial correlations. To handle intermittent faults, the comparisons are made for \(r\) rounds. Two special cases of intermittent faults are considered: one, when an intermittently faulty node sends similar sensor measurement and similar residual energy value to some of its neighbors in all \(r\) rounds; another, when it sends these values, either or both of which deviates significantly from that of some neighbors in all \(r\) rounds. Through extensive simulation and analysis, the proposed scheme is proved to be correct, complete, and efficient to handle intermittent faults and hence, well suited for WSNs.     

Structural, dynamic, and electrostatic properties of fully hydrated DMPC bilayers from molecular dynamics simulations accelerated with graphical processing units (GPUs)

We present results of molecular dynamics simulations of fully hydrated DMPC bilayers performed on graphics processing units (GPUs) using current state-of-the-art non-polarizable force fields and a local GPU-enabled molecular dynamics code named FEN ZI. We treat the conditionally convergent electrostatic interaction energy exactly using the particle mesh Ewald method (PME) for solution of Poisson's Equation for the electrostatic potential under periodic boundary conditions. We discuss elements of our implementation of the PME algorithm on GPUs as well as pertinent performance issues. We proceed to show results of simulations of extended lipid bilayer systems using our program, FEN ZI. We performed simulations of DMPC bilayer systems consisting of 17,004, 68,484, and 273,936 atoms in explicit solvent. We present bilayer structural properties (atomic number densities, electron density profiles), deuterium order parameters (S(CD)), electrostatic properties (dipole potential, water dipole moments), and orientational properties of water. Predicted properties demonstrate excellent agreement with experiment and previous all-atom molecular dynamics simulations. We observe no statistically significant differences in calculated structural or electrostatic properties for different system sizes, suggesting the small bilayer simulations (less than 100 lipid molecules) provide equivalent representation of structural and electrostatic properties associated with significantly larger systems (over 1000 lipid molecules). We stress that the three system size representations will have differences in other properties such as surface capillary wave dynamics or surface tension related effects that are not probed in the current study. The latter properties are inherently dependent on system size. This contribution suggests the suitability of applying emerging GPU technologies to studies of an important class of biological environments, that of lipid bilayers and their associated integral membrane proteins. We envision that this technology will push the boundaries of fully atomic-resolution modeling of these biological systems, thus enabling unprecedented exploration of meso-scale phenomena (mechanisms, kinetics, energetics) with atomic detail at commodity hardware prices.     

Shape and eccentricity effects in adhesive contacts of rodlike particles

The effects of shape and eccentricity on adhesion and detachment behavior of long, rodlike particles in contact with a half-space are analyzed using contact mechanics. The particles are considered to have cross sections that are squarish, oblate, or prolate rather than circular. Such cross sections are represented very generally by using superellipses. The contact mechanics model allows deduction of closed-form expressions for the contact pressure, load-contact size relation, detachment load, and detachment contact size. It is found that even relatively small deviations in shape from a cylinder have a significant influence on the detachment load. Eccentricity also affects the adhesive behavior, but to a lesser extent, with oblate shapes requiring larger separation loads than prolate shapes. The load-contact size solution reduces to that for a right-circular, cylindrical rod when the appropriate limit is taken. The detachment behavior of right-circular cylinders is also found to be mimicked by an entire family of rod shapes with different cross sections.     

Gold-catalyzed 1,2-difunctionalizations of aminoalkynes using only N- and O-containing oxidants

We report two viable routes for the 1,2-difunctionalization of aminoalkynes using only oxidants. In the presence of a gold catalyst, nitrones enable the oxoamination of aminoalkynes 1 to form 2-aminoamides 2. With a suitable gold catalyst, nitrosobenzenes implement an alkyne/nitroso metathesis of the same substrates to give 2-oxoiminylamides 3. These two novel oxidations also provide 1,2-aminoalcohols with opposite regioselectivity via NaBH(4) reduction in situ.     

Thermally controlled cyclic insertion/ejection of dopant ions and reversible zinc blende/wurtzite phase changes in ZnS nanostructures

We report a reversible phase transformation of platelet-shaped ZnS nanostructures between wurtzite (WZ) and zinc blende (ZB) phases by reversible insertion/ejection of dopant Mn(II) ions induced by a thermocyclic process. In a reaction flask loaded with WZ ZnS platelets and Mn molecular precursors, during heating Mn ions are incorporated and change the phase of the host nanostructures to ZB; during cooling Mn ions are spontaneously ejected, returning the host nanoplatelets to the original WZ phase. These reversible changes are monitored for several cycles with PL, EPR, XRD, and HRTEM. Interestingly, the (0001) WZ platelets transform to (110) ZB following a nucleation and growth process triggered by a local increase/depletion of the Mn(2+) concentration in the nanocrystals.     

3-(Hetero)aryl-4-indolylamino-α-tetralones by diastereoselective internal redox cyclization: an "azaenamine" conjugate addition

(E)-3-(hetero)aryl-1-(2-((E)-(indolin-1-ylimino)methyl)phenyl)prop-2-en-1-ones 1 undergo 6-exo-trig cyclization reactions upon treatment with BF(3)·Me(2)S in dichloromethane at low temperature to give the tetralones 10 in good yield. This cyclization process can be considered to be an intramolecular Michael-type addition which is accompanied by an internal redox reaction as the indoline fragment is oxidized to indole with simultaneous hydrogen shift to nitrogen atom N1 and the α-carbon atom of the Michael system. The reactions at the iminic centers take place via umpolung of the classical carbonyl reactivity. The reaction is diastereoselective and affords exclusively 3,4-disubstituted α-tetralones 10 as trans-diastereomers. According to quantum chemical calculations the reactions take place under kinetic control with the trans-diastereomer being the kinetically favored product as it has the lower activation barrier compared to the cis-diastereomer.     

MRDCI study of the low-lying electronic states of PbSi

Electronic states of the PbSi molecule up to 4 eV have been studied by carrying out ab initio based MRDCI calculations which include relativistic effective core potentials (RECPs) of both the atoms. The use of semicore RECPs of Pb produces better dissociation limits than the full-core one. However, the (3)P(0)-(3)P(1) splitting due to Pb is underestimated by about 4000 cm(-1). At least 25 bound electronic states of the Λ-S symmetry are predicted for PbSi. The computed zero-field-splitting in the ground state is about 544 cm(-1). A strong spin-orbit mixing changes the nature of the potential energy curves of many Ω states. The overall splitting among the spin components of A(3)Π is computed to be 4067 cm(-1). However, the largest spin-orbit splitting is reported for the (3)Δ state. A number of spin-allowed and spin-forbidden transitions are predicted. The partial radiative lifetime for the A(3)Π-X(3)Σ(-) transition is of the order of milliseconds. The computed bond energy in the ground state is 1.68 eV, considering the spin-orbit coupling. The vertical ionization energy for the ionization to the X(4)Σ(-) ground state of PbSi(+) is about 6.93 eV computed at the same level of calculations.