Characterization of gold-thiol-8-hydroxyquinoline self-assembled monolayers for selective recognition of aluminum ion using voltammetry and electrochemical impedance spectroscopy

Gold electrode surface is modified via covalent attachment of a synthesized thiol functionalized with 8-hydroxyquinoline, p-((8-hydroxyquinoline)azo) benzenethiol (SHQ), for the first time. The behavior of the nanostructured electrode surface (Au–SHQ) is characterized by electrochemical techniques including cyclic and differential pulse voltammetry (CV and DPV), and electrochemical impedance spectroscopy (EIS). The modified surface is stable in a wide range of potentials and pHs. A surface pK_a of 6.0 ± 0.1 is obtained for Au–SHQ electrode using surface acid/base titration curves constructed by CV and EIS measurements as a function of pH. These results helped to determine the charge state of the surface as a function of pH. The gold modified electrode surface showed good affinity for sensing the Al(III) ion at pH 5.5. The sensing process is based on (i) accumulation and complex formation between Al(III) from the solution phase and 8HQ function on the Au electrode surface (recognition step) and (ii) monitoring the impedance of the Au–SHQ–Al(III) complex against redox reaction rate of parabenzoquinone (PBQ) (signal transduction step). The PBQ is found to be a more suitable probe for this purpose, after testing several others. Thus, the sensor was tested for quantitative determination of Al(III) from the solution phase. At the optimized conditions, a linear response, from 1.0 × 10⁻¹¹ to 1.2 × 10⁻⁵ M Al(III) in semi-logarithmic scale, with a detection limit of 8.32 × 10⁻¹² M and mean relative standard deviation of 3.2% for n = 3 at 1.0 × 10⁻⁷ M Al(III) is obtained. Possible interferences from coexisting cations and anions are also studied. The results show that many ions do not interfere significantly with the sensor response for Al(III). Validity of the method and applicability of the sensor are successfully tested by determination of Al(III) in human blood serum samples.     

Isolation and synthesis of N-acyladenine and adenosine alkaloids from a southern Australian marine sponge, Phoriospongia sp.

Chemical fractionation of the southern Australian marine sponge Phoriospongia sp. (CMB-03107) yielded phorioadenine A (1) as a nematocidal agent and the first reported example of a 6-N-acyladenine natural product. The structure of 1 was confirmed by spectroscopic analysis and the chemical synthesis of racemic (1a) and enantiomeric (1b) analogues. HPLC–ESIMS analysis of the crude sponge extract with comparisons to the synthetic 6-N-acyladenosine 2a provided evidence that the biosynthetically related adenosine, phorioadenosine A (2), was present as a trace co-metabolite. The rare starfish metabolite asterubine (3) was also isolated as a co-metabolite, and its structure confirmed by spectroscopic analysis and chemical synthesis. Biological investigations confirmed that natural products 1–3 and synthetic analogues 1a–e and 2a were not cytotoxic to multiple mammalian cancer cell lines, or Gram-positive or -negative bacteria. Nematocidal activity (inhibition of larval development of Haemonchus contortus) detected in the Phoriospongia sp. extract was attributed to 1 (LD₉₉ 31 μg/mL), with preliminary structure–activity relationship investigations confirming the importance of the N-acyl side chain.     

Atomistic kinetic Monte Carlo study of atomic layer deposition derived from density functional theory

To describe the atomic layer deposition (ALD) reactions of HfO₂ from Hf(N(CH₃)₂)₄ and H₂O, a three‐dimensional on‐lattice kinetic Monte‐Carlo model is developed. In this model, all atomistic reaction pathways in density functional theory (DFT) are implemented as reaction events on the lattice. This contains all steps, from the early stage of adsorption of each ALD precursor, kinetics of the surface protons, interaction between the remaining precursors (steric effect), influence of remaining fragments on adsorption sites (blocking), densification of each ALD precursor, migration of each ALD precursors, and cooperation between the remaining precursors to adsorb H₂O (cooperative effect). The essential chemistry of the ALD reactions depends on the local environment at the surface. The coordination number and a neighbor list are used to implement the dependencies. The validity and necessity of the proposed reaction pathways are statistically established at the mesoscale. The formation of one monolayer of precursor fragments is shown at the end of the metal pulse. Adsorption and dissociation of the H₂O precursor onto that layer is described, leading to the delivery of oxygen and protons to the surface during the H₂O pulse. Through these processes, the remaining precursor fragments desorb from the surface, leaving the surface with bulk‐like and OH‐terminated HfO₂, ready for the next cycle. The migration of the low coordinated remaining precursor fragments is also proposed. This process introduces a slow reordering motion (crawling) at the mesoscale, leading to the smooth and conformal thin film that is characteristic of ALD. © 2013 Wiley Periodicals, Inc.     

Synthesis and evaluation of antiproliferative activity of substituted N-(9-oxo-9H-xanthen-4-yl)benzenesulfonamides

Several novel N-(9-oxo-9H-xanthen-4-yl)benzenesulfonamide derivatives were prepared as potential antiproliferative agents. The in vitro antiproliferative activity of the synthesized compounds was investigated against a panel of tumor cell lines including breast cancer cell lines (MDA-MB-231, T-47D) and neuroblastoma cell line (SK-N-MC) using MTT colorimetric assay. Etoposide, a well-known anticancer drug, was used as a positive standard drug. Among synthesized compounds, 4-methoxy-N-(9-oxo-9H-xanthen-4-yl)benzenesulfonamide (5i) showed the highest antiproliferative activity against MDA-MB-231, T-47D, and SK-N-MC cells. Furthermore, pentafluoro derivatives 5a and 6a exhibited higher antiproliferative activity than doxorubicin against human leukemia cell line (CCRF-CEM) and breast adenocarcinoma (MDA-MB-468) cells. Structure–activity relationship studies revealed that xanthone benzenesulfonamide hybrid compounds can be used for the development of new lead anticancer agents.     

The electrospun poly(ε‐caprolactone)/fluoridated hydroxyapatite nanocomposite for bone tissue engineering

Biodegradable cell‐incorporated scaffolds can guide the regeneration process of bone defects such as physiological resorption, tooth loss, and trauma which medically, socially, and economically hurt patients. Here, 0, 5, 10, and 15 wt% fluoridated hydroxyapatite (FHA) nanoparticles containing 25 wt% F^? and 75 wt% OH^? were incorporated into poly(ε‐caprolactone) (PCL) matrix to produce PCL/FHA nanocomposite scaffolds using electrospinning method. Then, scanning electron microscopy (SEM), X‐ray diffraction (XRD) pattern, and Fourier transform infrared spectroscopy (FTIR) were used to evaluate the morphology, phase structure, and functional groups of prepared electrospun scaffolds, respectively. Furthermore, the tensile strength and elastic modulus of electrospun scaffolds were investigated using the tensile test. Moreover, the biodegradation behavior of electrospun PCL/FHA scaffolds was studied by the evaluation of weight loss of mats and the alternation of pH in phosphate buffer saline (PBS) up to 30 days of incubation. Then, the biocompatibility of prepared mats was investigated by culturing MG‐63 osteoblast cell line and performing MTT assay. In addition, the adhesion of osteoblast cells on prepared electrospun scaffolds was studied using their SEM images. Results revealed that the fiber diameter of prepared electrospun PCL/FHA scaffolds alters between 700 and 900 nm. The mechanical assay illustrated the mat with 10 wt% FHA nanoparticles revealed the highest tensile strength and elastic modulus. The weight loss alternation of mats determined around 1% to 8% after 30 days of incubation. The biocompatibility and cell adhesion of mats improved by increasing the amounts of FHA nanoparticles.     

Design,synthesis and investigation of the interaction behavior between two acridone derivatives, 8-chloro acridone and nitrile cyanide acridone with calf thymus DNA,by different spectroscopic techniques

Journal of the Iranian Chemical Society - Evaluating the binding interaction between biomacromolecules and various chemical compounds is one of the most biologically researched topics. The present...     

Synthesis and biological evaluation of bile acid dimers linked with 1,2,3-triazole and bis-beta-lactam

We report herein the synthesis and biological evaluation of bile acid dimers linked through 1,2,3-triazole and bis-beta-lactam. The dimers were synthesized using 1,3-dipolar cycloaddition reaction of diazido bis-beta-lactams , and terminal alkynes derived from cholic acid/deoxycholic acid in the presence of Cu(i) catalyst (click chemistry). These novel molecules were evaluated in vitro for their antifungal and antibacterial activity. Most of the compounds exhibited significant antifungal as well as antibacterial activity against all the tested fungal and bacterial strains. Moreover, their in vitro cytotoxicities towards HEK-293 and MCF-7 cells were also established.     

Plasma-assisted nitrogen doping of VACNTs for efficiently enhancing the supercapacitor performance

Nitrogen doping of vertically aligned carbon nanotubes (VACNTs) using plasma-enhanced chemical vapour deposition has been investigated to improve the supercapacitance performance of CNTs. Incorporating electrochemical measurements on the open-ended nitrogen-doped CNTs, showed the achievement of 6 times improvement in the capacitance value. For nitrogen-doped CNTs on silicon substrate, specific capacitance of 60 F g^?1 was obtained in 0.5 M KCl solution, with capacity retention ratio above 90 % after cycled at 0.1 A g^?1 for 5000 cycles. Using this sample, a symmetric supercapacitance was fabricated which showed the power density of 37.5 kW kg^?1. The facile fabrication approach and its excellent capacitance improvement, propose it as an efficient technique for enhancing the supercapacitance performance of the carbon-based electrodes.     

Local Clique Covering of Claw‐Free Graphs

A clique covering of a simple graph G is a collection of cliques of G covering all the edges of G such that each vertex is contained in at most k cliques. The smallest k for which G admits a clique covering is called the local clique cover number of G and is denoted by lcc(G). Local clique cover number can be viewed as the local counterpart of the clique cover number that is equal to the minimum total number of cliques covering all edges. In this article, several aspects of the local clique covering problem are studied and its relationships to other well‐known problems are discussed. In particular, it is proved that the local clique cover number of every claw‐free graph is at most , where Δ is the maximum degree of the graph and c is a constant. It is also shown that the bound is tight, up to a constant factor. Moreover, regarding a conjecture by Chen et al. (Clique covering the edges of a locally cobipartite graph, Discrete Math 219(1–3)(2000), 17–26), we prove that the clique cover number of every connected claw‐free graph on n vertices with the minimum degree δ, is at most , where c is a constant.     

Electronic and Magnetic Properties of Linear and Dimerized Titanium Nanochains Under Compressive and Tensile Strain

The magnetic and electronic properties of both linear and dimerized nanochains of titanium at different atomic distances are calculated within density functional theory with the generalized gradient approximation. Titanium which is a nonmagnetic in its bulk form is shown to become magnetic in its nanochain structure. Also, a close relationship is found between magnetic state and geometry of chain structure and the dependence of electronic properties on the atomic structures of chains is revealed. It is found that, for dimerized nanochains from equilibrium constant, compressive strain leads to a reduction in magnetism. Moreover, characteristics of the systems near the Fermi level are investigated and the charge densities of both nanostructures are studied in the ferromagnetic order. The results show that metallic bonding is mainly responsible for the linear structure; however, for the dimerized structure, the bonding is more directional, i.e. has a more covalent character. With increasing tension along the axis of the nanostructures, a change in the types of bonding is found.