β-diketonate versus β-ketoiminate:the importance of a ferrocenyl moiety on improving the anticancer potency

Herein we present a library of fully characterized beta-diketonate and beta-ketoiminate compounds that are functionalized with a ferrocenyl moiety. Their cytotoxic potential has been determined by screening against human breast adenocarcinomas (MCF-7 and MDA-MB-231), human colorectal carcinoma p53 wild type (HCT116 p53(+/+)) and normal human prostate (PNT2) cell lines. The ferrocenyl beta-diketonate compounds are more than 18 times more cytotoxic than the ferrocenyl beta-ketoiminate analogues. Against MCF-7, compounds functionalized at the meta position are up to nine times more cytotoxic than when functionalized at the para position. The ferrocenyl beta-diketonate compounds have increased selectivity towards MCF-7 and MDA-MB-231, with several complexes having selectivity index (SI) values that are more than nine times (MCF-7) and more than six times (MDA-MB-231) that of carboplatin. The stability of these compounds in dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) has been assessed by NMR spectroscopy and mass spectrometry studies, and the compounds show no oxidation of the iron center from Fe-II to Fe-III. Cytotoxicity screening was performed in both DMSO and DMF, with no significant differences observedin their potency

Half metallic digital ferromagnetic heterostructure composed of a δ\delta-doped layer of Mn in Si

We propose and investigate the properties of a digital ferromagnetic heterostructure (DFH) consisting of a $\delta$-doped layer of Mn in Si, using \textit{ab initio} electronic-structure methods. We find that (i) ferromagnetic order of the Mn layer is energetically favorable relative to antiferromagnetic, and (ii) the heterostructure is a two-dimensional half metallic system. The metallic behavior is contributed by three majority-spin bands originating from hybridized Mn-$d$ and nearest-neighbor Si-$p$ states, and the corresponding carriers are responsible for the ferromagnetic order in the Mn layer. The minority-spin channel has a calculated semiconducting gap of 0.25 eV. Analysis of the total and partial densities of states, band structure, Fermi surfaces and associated charge density reveals the marked two-dimensional nature of the half metallicity. The band lineup is found to be favorable for retaining the half metal character to near the Curie temperature ($T_{C}$). Being Si based and possibly having a high $T_{C}$ as suggested by an experiment on dilutely doped Mn in Si, the heterostructure may be of special interest for integration into mature Si technologies for spintronic applications.Comment: 4 pages, 4 figures, Revised version, to appear in Phys. Rev. Let

Wavelets and graph C∗C^*-algebras

Here we give an overview on the connection between wavelet theory and representation theory for graph $C^{\ast}$-algebras, including the higher-rank graph $C^*$-algebras of A. Kumjian and D. Pask. Many authors have studied different aspects of this connection over the last 20 years, and we begin this paper with a survey of the known results. We then discuss several new ways to generalize these results and obtain wavelets associated to representations of higher-rank graphs. In \cite{FGKP}, we introduced the "cubical wavelets" associated to a higher-rank graph. Here, we generalize this construction to build wavelets of arbitrary shapes. We also present a different but related construction of wavelets associated to a higher-rank graph, which we anticipate will have applications to traffic analysis on networks. Finally, we generalize the spectral graph wavelets of \cite{hammond} to higher-rank graphs, giving a third family of wavelets associated to higher-rank graphs

Cytotoxic Hydrogen Bridged Ruthenium Quinaldamide Complexes Showing Induced Cancer Cell Death by Apoptosis

This report presents the first known p-cymene ruthenium quinaldamide complexes which are stablized by a hydrogenbridging atom, [[{(p-cym)RuIIX(N,N)}{H+ }{(N,N)XRuII(p-cym)}][PF6] (N,N = functionalised quinaldamide and X = Cl or Br). These complexes are formed by a reaction of [p-cymRu(-X)2]2 with a functionalised quinaldamide ligand. When filtered over NH4PF6, and under aerobic conditions the equilibrium of NH4PF6 NH3 + HPF6 enables incorporation of HPF6 and the stabilisation of two monomeric ruthenium complexes by a bridging H+ , which are counter-balanced by a PF6 counterion. Xray crystallographic analysis is presented for six new structures with O···O distances of 2.430(3)-2.444(17) Å, which is significant for strong hydrogen bonds. Chemosensitivity studies against HCT116, A2780 and cisplatin-resistant A2780cis human cancer cells showed the ruthenium complexes with a bromide ancillary ligand to be more potent than those with a chloride ligand. The 4'-fluoro compounds show a reduction in potency for both chloride and bromide complexes against all cell lines, but an increase in selectivity towards cancer cells compared to non-cancer ARPE-19 cells, with a selectivity index > 1. Mechanistic studies showed a clear correlation between IC50 values and induction of cell death by apoptosis

Non-Equilibrium Electron Transport in Two-Dimensional Nano-Structures Modeled by Green's Functions and the Finite-Element Method

We use the effective-mass approximation and the density-functional theory with the local-density approximation for modeling two-dimensional nano-structures connected phase-coherently to two infinite leads. Using the non-equilibrium Green's function method the electron density and the current are calculated under a bias voltage. The problem of solving for the Green's functions numerically is formulated using the finite-element method (FEM). The Green's functions have non-reflecting open boundary conditions to take care of the infinite size of the system. We show how these boundary conditions are formulated in the FEM. The scheme is tested by calculating transmission probabilities for simple model potentials. The potential of the scheme is demonstrated by determining non-linear current-voltage behaviors of resonant tunneling structures.Comment: 13 pages,15 figure

Rhodium(III) dihalido complexes: The effect of ligand substitution and halido coordination on increasing cancer cell potency

This work presents the synthesis of eight new rhodium(III) dihalido complexes, [RhX2(L)(LH)] (where X = Cl or I), which incorporate two bidentate N-(3-halidophenyl)picolinamide ligands. The ligands have different binding modes in the complexes, whereby one is neutral and bound via N,N (LH) coordination, while the other is anionic and bound via N,O (L) coordination. The solid state and solution studies confirm multiple isomers are present when X = Cl; however, after a halide exchange with potassium iodide (X = I) the complexes exist exclusively as single stable trans isomers. NMR studies reveal the Rh(III) trans diiodido complexes remain stable in aqueous solution with no ligand exchange reported over 96 h. Chemosensitivity data against a range of cancer cell lines show two cytotoxic complexes, where L = N-(3-bromophenyl)picolinamide ligand. The results have been compared to the analogous Ru(III) complexes and overall highlight the Rh(III) trans diiodido complex to be ∼78× more cytotoxic than the analogous Rh(III) dichlorido complex, unlike the Ru(III) complexes which are equitoxic against all cell lines. Additionally, the Rh(III) trans diiodido complex is more selective toward cancerous cells, with selectivity index (SI) values >25-fold higher than cisplatin against colorectal carcinoma

Electronic and magnetic properties of zincblende half-metal superlattices

Zincblende half-metallic compounds such as CrAs, with large magnetic moments and high Curie temperatures, are promising materials for spintronic applications. They explore layered materials, consisting of alternating layers of zincblende half-metals, by first principles calculations, and find that superlattices of (CrAs){sub 1}(MnAs){sub 1} and (CrAs){sub 2}(MnAs){sub 2} are half-metallic with magnetic moments of 7.0{mu}{sub B} and 14.0{mu}{sub B} per unit cell, respectively. They discuss the nature of the bonding and half-metallicity in these materials and, based on the understanding acquired, develop a simple expression for the magnetic moment in such materials. They explore the range of lattice constants over which half-metallicity is manifested, and suggest corresponding substrates for growth in thin film form

Design of Spintronic Materials with Simple Structures

A brief comparison of conventional electronics and spintronics is given. The key features of half metallic binary compounds with the zincblende structure are presented, using MnAs as an example. We discuss the interactions responsible for the half metallic properties. Special properties of superlattices and a digital ferromagnetic heterostructure incorporating zincblende half metals are also discussed

Droplet-based millifluidic synthesis of a proton-conducting sulfonate metal–organic framework

Metal–organic frameworks (MOFs) have emerged as promising candidate materials for proton exchange membranes (PEMs), due to the control of proton transport enabled by functional groups and the structural order within the MOFs. In this work, we report a millifluidic approach for the synthesis of a MOF incorporating both sulfonate and amine groups, termed Cu-SAT, which exhibits a high proton conductivity. The fouling-free multiphase flow reactor synthesis was operated for more than 5 h with no reduction in yield or change in the particle size distribution, demonstrating a sustained space–time yield up to 131.7 kg m−3 day−1 with consistent particle quality. Reaction yield and particle size were controllably tuned by the adjustment of reaction parameters, such as residence/reaction time, temperature, and reagent concentration. The reaction yields from the flow reactor were 10–20% higher than those of corresponding batch syntheses, indicating improved mass and heat transfer in flow. A systematic exploration of synthetic parameters using a factorial design of experiments approach revealed the key correlations between the process parameters and yields and particle size distributions. The proton conductivity of the synthesized Cu-SAT MOF was evaluated in a mixed matrix membrane model PEM with polyvinylpyrrolidone and polyvinylidene fluoride polymers, exhibiting a promising composite conductivity of 1.34 ± 0.05 mS cm−1 at 353 K and 95% relative humidity (RH)

Theoretical investigations of two Si-based spintronic materials

Two Si-based spintronic materials, a Mn-Si digital ferromagnetic heterostructure ({delta}-layer of Mn doped in Si) with defects and dilutely doped Mn{sub x}Si{sub 1-x} alloy are investigated using a density-functional based approach. We model the heterostructure and alloy with a supercell of 64 atoms and examine several configurations of the Mn atoms. We find that 25% substitutional defects without vacancies in the {delta} layer diminishes half metallicity of the DFH substantially. For the alloy, the magnetic moment M ranges from 1.0-9.0 {mu}{sub B}/unit-cell depending on impurity configuration and concentration. Mn impurities introduce a narrow band of localized states near E{sub F}. These alloys are not half metals though their moments are integer. We explain the substantially different magnetic moments