Heteronuclear Complexes of Hg(II) and Zn(II) with Sodium Monensinate as a Ligand.

The commercial veterinary antibiotic sodium monensinate (MonNa) binds mercury(II) or zinc(II) cations as thiocyanate [Hg(MonNa)2(SCN)2] (1) or isothiocyanate [Zn(MonNa)2(NCS)2] (2) neutral coordination compounds. The structure and physicochemical properties of 1 and 2 were evaluated by the methods of single crystal and/or powder X-ray diffraction, infrared, nuclear magnetic resonance, X-ray photoelectron spectroscopies, and electrospray-mass spectrometry. The primary cores of the two complexes comprise HgS2O2 (1) and ZnN2O2 (2) coordination motifs, respectively, due to the ambidentate binding modes of the SCN-ligands. The directly bound oxygen atoms originate from the carboxylate function of the parent antibiotic. Sodium cations remain in the hydrophilic cavity of monensin and cannot be replaced by the competing divalent metal ions. Zinc(II) binding does not influence the monensin efficacy in the case of Bacillus cereus and Staphylococcus aureus whereas the antimicrobial assay reveals the potential of complex 2 as a therapeutic candidate for the treatment of infections caused by Bacillus subtilis, Kocuria rhizophila, and Staphylococcus saprophyticus.

Experimental and DFT Study of Monensinate and Salinomycinate Complexes Containing {Fe3(µ3-O)}7+ Core.

Two trinuclear oxo-centred iron(III) coordination compounds of monensic and salinomycinic acids (HL) were synthesized and their spectral properties were studied using physicochemical/thermal methods (FT-IR, TG-DTA, TG-MS, EPR, Mössbauer spectroscopy, powder XRD) and elemental analysis. The data suggested the formation of [Fe3(µ3-O)L3(OH)4] and the probable complex structures were modelled using the DFT method. The computed spectral parameters of the optimized constructs were compared to the experimentally measured ones. In each complex, three metal centres were joined together at the axial position by a µ3-O unit to form a {Fe3O}7+ core. The antibiotics monoanions served as bidentate ligands through the carboxylate and hydroxyl groups located at the termini. The carboxylate moieties played a dual role bridging each two metal centres. Hydroxide anions secured the overall neutral character of the coordination species. Mössbauer spectra displayed asymmetric quadrupole doublets that were consistent with the existence of two types of high-spin iron(III) sites with different environments-two Fe[O5] and one Fe[O6] centres. The solid-state EPR studies confirmed the +3 oxidation state of iron with a total spin St = 5/2 per trinuclear cluster. The studied complexes are the first iron(III) coordination compounds of monensin and salinomycin reported so far.

Novel Cerium(IV) Coordination Compounds of Monensin and Salinomycin.

The largely uncharted complexation chemistry of the veterinary polyether ionophores, monensic and salinomycinic acids (HL) with metal ions of type M4+ and the known antiproliferative potential of antibiotics has provoked our interest in exploring the coordination processes between MonH/SalH and ions of Ce4+. (1) Methods: Novel monensinate and salinomycinate cerium(IV)-based complexes were synthesized and structurally characterized by elemental analysis, a plethora of physicochemical methods, density functional theory, molecular dynamics, and biological assays. (2) Results: The formation of coordination species of a general composition [CeL2(OH)2] and [CeL(NO3)2(OH)], depending on reaction conditions, was proven both experimentally and theoretically. The metal(IV) complexes [CeL(NO3)2(OH)] possess promising cytotoxic activity against the human tumor uterine cervix (HeLa) cell line, being highly selective (non-tumor embryo Lep-3 vs. HeLa) compared to cisplatin, oxaliplatin, and epirubicin.

Dinuclear vs. Mononuclear Copper(II) Coordination Species of Tylosin and Tilmicosin in Non-Aqueous Solutions.

The veterinary 16-membered macrolide antibiotics tylosin (HTyl, 1a) and tilmicosin (HTilm, 1b) react with copper(II) ions in acetone at metal-to-ligand molar ratio of 1:2 to form blue (2) or green (3) metal(II) coordination species, containing nitrate or chloride anions, respectively. The complexation processes and the properties of 2-3 were studied by an assortment of physicochemical techniques (UV-Vis, EPR, NMR, FTIR, elemental analysis). The experimental data revealed that the main portion of copper(II) ions are bound as neutral EPR-silent dinuclear complexes of composition [Cu2(µ-NO3)2L2] (2a-b) and [Cu2(µ-Cl)2Cl2(HL)2] (3a-b), containing impurities of EPR-active mono-species [Cu(NO3)L] (2a'-b') and [CuCl2(HL)] (3a'-b'). The possible structural variants of the dinuclear- and mono-complexes were modeled by the DFT method, and the computed spectroscopic parameters of the optimized constructs were compared to those measured experimentally. Using such a combined approach, the main coordination unit of the macrolides, involved in the complex formation, was defined to be their mycaminosyl substituent, which acts as a terminal ligand in a bidentate mode through the tertiary nitrogen atom and the oxygen from a deprotonated (2) or non-dissociated (3) hydroxyl group, respectively.

Benchmarking of Density Functionals for the Description of Optical Properties of Newly Synthesized π-Conjugated TADF Blue Emitters.

Computational modeling of the optical characteristics of organic molecules with potential for thermally activated delayed fluorescence (TADF) may assist markedly the development of more efficient emitting materials for organic light-emitting diodes. Recent theoretical studies in this area employ mostly methods from density functional theory (DFT). In order to obtain accurate predictions within this approach, the choice of a proper functional is crucial. In the current study, we focus on testing the performance of a set of DFT functionals for estimation of the excitation and emission energy and the excited singlet-triplet energy gap of three newly synthesized compounds with capacity for TADF. The emitters are designed specifically to enable charge transfer by π-electron conjugation, at the same time possessing high-energy excited triplet states. The functionals chosen for testing are from various groups ranging from gradient-corrected through global hybrids to range-separated ones. The results show that the monitored optical properties are especially sensitive to how the long-range part of the exchange energy is treated within the functional. The accurate functional should also be able to provide well balanced distribution of the π-electrons among the molecular fragments. Global hybrids with moderate (less than 0.4) share of exact exchange (B3LYP, PBE0) and the meta-GGA HSE06 are outlined as the best performing methods for the systems under study. They can predict all important optical parameters correctly, both qualitatively and quantitatively.

Lysosome-targeting pH indicator based on peri-fused naphthalene monoimide with superior stability for long term live cell imaging.

Lysosomes, the acidic degradation compartments of eukaryotic cells, play an essential role in many physiological processes. Their dysfunction is associated with a number of diseases, which are often related to an altered localization or luminal pH. Thus, the in-depth characterization of lysosomes within the intact eukaryotic cell is of utmost interest. For microscopic evaluation of lysosomal distribution and acidity, a number of labels have been developed, but many showed poor organelle specificity or rapid clearing from lysosomes, rendering them unsuitable for long-term observations. Here, we describe the synthesis and spectroscopic properties of a novel small molecule marker for lysosomes based on naphthalene monoimide with reversible, pH-dependent spectral shifts in both the absorption and the emission spectrum and acidity-associated changes in fluorescence lifetime. The dye can be excited either with single- or two-photon excitation and appears to be very stably associated with lysosomes for several days. We used this chromophore to detect chemically-induced changes of lysosomal pH in HeLa cells by ratiometric and FLIM imaging.

Detection of ultra-low protein concentrations with the simplest possible field effect transistor.

Silicon nanowire (Si NW) sensors have attracted great attention due to their ability to provide fast, low-cost, label-free, real-time detection of chemical and biological species. Usually configured as field effect transistors (FETs), they have already demonstrated remarkable sensitivity with high selectivity (through appropriate functionalisation) towards a large number of analytes in both liquid and gas phases. Despite these excellent results, Si NW FET sensors have not yet been successfully employed to detect single molecules of either a chemical or biological target species. Here we show that sensors based on silicon junctionless nanowire transistors (JNTs), the simplest possible transistors, are capable of detecting the protein streptavidin at a concentration as low as 580 zM closely approaching the single molecule level. This ultrahigh detection sensitivity is due to the intrinsic advantages of junctionless devices over conventional FETs. Apart from their superior functionality, JNTs are much easier to fabricate by standard microelectronic processes than transistors containing p-n junctions. The ability of JNT sensors to detect ultra-low concentrations (in the zeptomolar range) of target species, and their potential for low-cost mass production, will permit their deployment in numerous environments, including life sciences, biotechnology, medicine, pharmacology, product safety, environmental monitoring and security.

Contacting ZnO Individual Crystal Facets by Direct Write Lithography.

Many advanced electronic devices take advantage of properties developed at the surface facets of grown crystals with submicrometer dimensions. Electrical contacts to individual crystal facets can make possible the investigations of facet-dependent properties such as piezoelectricity in ZnO or III-nitride crystals having noncentrosymmetric structure. However, a lithography-based method for developing contacts to individual crystal facets with submicrometer size has not yet been demonstrated. In this report we study the use of electron beam-induced deposition (EBID), a direct write lithography method, for contacting individual facets of ZnO pillars within an electron microscope. Correlating structural and in situ deposition and electrical data, we examine proximity effects during the EBID and evaluate the process against obtaining electrically insulated contact lines on neighboring and diametrically opposite ZnO facets. Parameters such as incident beam energy geometry and size of the facets were investigated with the view of minimizing unwanted proximity broadening effects. Additionally, we show that the EBID direct write method has the required flexibility, resolution, and minimized proximity deposition for creating prototype devices. The devices were used to observe facet-dependent effects induced by mechanical stress on single ZnO pillar structures.

Ultra-High-Density Arrays of Defect-Free AlN Nanorods: A "Space-Filling" Approach.

Nanostructured semiconductors have a clear potential for improved optoelectronic devices, such as high-efficiency light-emitting diodes (LEDs). However, most arrays of semiconductor nanorods suffer from having relatively low densities (or "fill factors") and a high degree of nonuniformity, especially when produced by self-organized growth. Ideally an array of nanorods for an optoelectronic emitter should have a fill factor close to 100%, with uniform rod diameter and height. In this article we present a "space-filling" approach for forming defect-free arrays of AlN nanorods, whereby the separation between each rod can be controlled to 5 nm due to a self-limiting process. These arrays of pyramidal-topped AlN nanorods formed over wafer-scale areas by metal organic chemical vapor deposition provide a defect-free semipolar top surface, for potential optoelectronic device applications with the highest reported fill factor at 98%.

Organo-arsenic molecular layers on silicon for high-density doping.

This article describes for the first time the controlled monolayer doping (MLD) of bulk and nanostructured crystalline silicon with As at concentrations approaching 2 × 10(20) atoms cm(-3). Characterization of doped structures after the MLD process confirmed that they remained defect- and damage-free, with no indication of increased roughness or a change in morphology. Electrical characterization of the doped substrates and nanowire test structures allowed determination of resistivity, sheet resistance, and active doping levels. Extremely high As-doped Si substrates and nanowire devices could be obtained and controlled using specific capping and annealing steps. Significantly, the As-doped nanowires exhibited resistances several orders of magnitude lower than the predoped materials.

Aligned silicon nanofins via the directed self-assembly of PS-b-P4VP block copolymer and metal oxide enhanced pattern transfer.

'Directing' block copolymer (BCP) patterns is a possible option for future semiconductor device patterning, but pattern transfer of BCP masks is somewhat hindered by the inherently low etch contrast between blocks. Here, we demonstrate a 'fab' friendly methodology for forming well-registered and aligned silicon (Si) nanofins following pattern transfer of robust metal oxide nanowire masks through the directed self-assembly (DSA) of BCPs. A cylindrical forming poly(styrene)-block-poly(4-vinyl-pyridine) (PS-b-P4VP) BCP was employed producing 'fingerprint' line patterns over macroscopic areas following solvent vapor annealing treatment. The directed assembly of PS-b-P4VP line patterns was enabled by electron-beam lithographically defined hydrogen silsequioxane (HSQ) gratings. We developed metal oxide nanowire features using PS-b-P4VP structures which facilitated high quality pattern transfer to the underlying Si substrate. This work highlights the precision at which long range ordered ∼10 nm Si nanofin features with 32 nm pitch can be defined using a cylindrical BCP system for nanolithography application. The results show promise for future nanocircuitry fabrication to access sub-16 nm critical dimensions using cylindrical systems as surface interfaces are easier to tailor than lamellar systems. Additionally, the work helps to demonstrate the extension of these methods to a 'high χ' BCP beyond the size limitations of the more well-studied PS-b-poly(methyl methylacrylate) (PS-b-PMMA) system.

Mesoporous bismuth ferrite with amplified magnetoelectric coupling and electric field-induced ferrimagnetism.

Coupled ferromagnetic and ferroelectric materials, known as multiferroics, are an important class of materials that allow magnetism to be manipulated through the application of electric fields. Bismuth ferrite, BiFeO3, is the most-studied intrinsic magnetoelectric multiferroic because it maintains both ferroelectric and magnetic ordering to well above room temperature. Here we report the use of epitaxy-free wet chemical methods to create strained nanoporous BiFeO3. We find that the strained material shows large changes in saturation magnetization on application of an electric field, changing from 0.04 to 0.84 µb per Fe. For comparison, non-porous films produced using analogous methods change from just 0.002 to 0.01 µb per Fe on application of the same electric field. The results indicate that nanoscale architecture can complement strain-layer epitaxy as a tool to strain engineer magnetoelectric materials.

Solvent vapor annealing of block copolymers in confined topographies: commensurability considerations for nanolithography.

The directed self-assembly of block copolymer (BCP) materials in topographically patterned substrates (i.e., graphoepitaxy) is a potential methodology for the continued scaling of nanoelectronic device technologies. In this Communication, an unusual feature size variation in BCP nanodomains under confinement with graphoepitaxially aligned cylinder-forming poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) BCP is reported. Graphoepitaxy of PS-b-P4VP BCP line patterns (CII ) is accomplished via topo-graphy in hydrogen silsequioxane (HSQ) modified substrates and solvent vapor annealing (SVA). Interestingly, reduced domain sizes in features close to the HSQ guiding features are observed. The feature size reduction is evident after inclusion of alumina into the P4VP domains followed by pattern transfer to the silicon substrate. It is suggested that this nano-domain size perturbation is due to solvent swelling effects during SVA. It is proposed that using a commensurability value close to the solvent vapor annealed periodicity will alleviate this issue leading to uniform nanofins.

Visualising discrete structural transformations in germanium nanowires during ion beam irradiation and subsequent annealing.

In this article we detail the application of electron microscopy to visualise discrete structural transitions incurring in single crystalline Ge nanowires upon Ga-ion irradiation and subsequent thermal annealing. Sequences of images for nanowires of varying diameters subjected to an incremental increase of the Ga-ion dose were obtained. Intricate transformations dictated by a nanowire's geometry indicate unusual distribution of the cascade recoils in the nanowire volume, in comparison to planar substrates. Following irradiation, the same nanowires were annealed in the TEM and corresponding crystal recovery followed in situ. Visualising the recrystallisation process, we establish that full recovery of defect-free nanowires is difficult to obtain due to defect nucleation and growth. Our findings will have large implications in designing ion beam doping of Ge nanowires for electronic devices but also for other devices that use single crystalline nanostructured Ge materials such as thin membranes, nanoparticles and nanorods.

Absence of evidence ≠ evidence of absence: statistical analysis of inclusions in multiferroic thin films.

Assertions that a new material may offer particularly advantageous properties should always be subjected to careful critical evaluation, especially when those properties can be affected by the presence of inclusions at trace level. This is particularly important for claims relating to new multiferroic compounds, which can easily be confounded by unobserved second phase magnetic inclusions. We demonstrate an original methodology for the detection, localization and quantification of second phase inclusions in thin Aurivillius type films. Additionally, we develop a dedicated statistical model and demonstrate its application to the analysis of Bi(6)Ti(2.8)Fe(1.52)Mn(0.68)O18 (B6TFMO) thin films, that makes it possible to put a high, defined confidence level (e.g. 99.5%) to the statement of 'new single phase multiferroic materials'. While our methodology has been specifically developed for magnetic inclusions, it can easily be adapted to any other material system that can be affected by low level inclusions.

Manipulating the growth kinetics of vapor-liquid-solid propagated Ge nanowires.

This article describes an innovative approach in which bimetallic alloy seeds of AuxAg1-x are used to enhance the growth kinetics of Ge nanowires, via a vapor-liquid-solid (VLS) growth technique. The decreased equilibrium concentration and increased supersaturation of Ge in the liquid alloy seeds, compared to pure Au seeds, results in favorable growth kinetics and the realization of high-aspect ratio millimeter-long Ge nanowires. Also detailed is the manifestation of the Gibbs-Thompson effect resulting in diameter-dependent nanowire growth rates as a function of the Au-Ag-Ge eutectic composition. Significantly, AuxAg1-x alloy seeds lower the critical diameter of the Ge nanowires in this liquid-seeded growth approach. In situ TEM heating experiments established the correlation between the growth kinetics and equilibrium eutectic compositions in the ternary growth systems. The fundamental insights of nanowire growth demonstrated with the ternary eutectic alloys opens up opportunities to engineer the aspect ratio and morphology of a range of semiconductor nanowires.

Impact of surface nano-textured stainless steel prepared by focused ion beam on endothelial cell growth.

The modification of stent surfaces with nano-structures has the potential for limiting late stent restenosis. We report here the patterning of 316L austentitic stainless steel with arrays of nano-pits of two nominal diameters: 120 and 180 nm. These nano-textured surfaces were prepared by focused ion beam milling. The influence of the ion beam current on the nano-features was investigated by scanning electron and atomic force microscopies. The optimum ion beam currents were 280 pA for 120 nm nano-pits and 920 pA for 180 nm nano-pits. The depths of the nano-pits formed were (65 +/- 24) nm (120 nm) and (84 +/- 36) nm (180 nm). This wide distribution of the depths is due to the polycrystalline nature of 316 L stainless steel, which has a strong influence on the milling rates. Endothelial cells were grown in vitro on these substrates for 1, 3 and 5 days. The cells were viable for the duration of the cell culture on the nano-textured substrates. There was no significant difference in the adhesion and the proliferation based on the nano-pit diameter.

DNA damage in exfoliated cells and histopathological alterations in the urinary tract of mice exposed to cigarette smoke and treated with chemopreventive agents.

Cigarette smoke (CS) is convincingly carcinogenic in mice when exposure starts at birth. We investigated the induction and modulation of alterations in the kidney and urinary bladder of CS-exposed mice. A total of 484 strain H Swiss mice were either sham-exposed or exposed since birth to mainstream CS (MCS) for 4 months. Dietary agents, including myo-inositol, suberoylanilide hydroxamic acid, bexarotene, pioglitazone and a combination of bexarotene and pioglitazone, were administered after weaning. Comet analyses showed that, after 2 and 4 months, MCS causes DNA damage in exfoliated urothelial cells, which can be prevented by myo-inositol and the peroxisome proliferator-activated receptor-γ ligand pioglitazone. After 7 months, the 17.6% of MCS-exposed male mice exhibited lesions of the urinary tract versus the 6.1% of sham-exposed mice, which emphasizes the role of sex hormones in urinary tract carcinogenesis. Myo-inositol and the RXR-specific retinoid bexarotene did not affect these alterations. The histone deacetylase inhibitor suberoylanilide hydroxamic acid (Vorinostat) increased the incidence of kidney epithelium hyperplasia. Pioglitazone significantly enhanced the incidence of kidney lesions as compared with mice exposed to MCS only, indicating possible adverse effects of this antidiabetic drug, which were lost upon combination with bexarotene according to a combined chemoprevention strategy. RXR is a heterodymeric partner for peroxisome proliferator-activated receptor-γ, thereby modulating the expression of multiple target genes. In conclusion, there is contrast between the ability of pioglitazone to inhibit DNA damage in exfoliated cells and the alterations induced in the urinary tract of MCS-exposed mice, suggesting the occurrence of non-genotoxic mechanisms for this drug.

Selective sidewall wetting of polymer blocks in hydrogen silsesquioxane directed self-assembly of PS-b-PDMS.

We show the importance of sidewall chemistry for the graphoepitaxial alignment of PS-b-PDMS using prepatterns fabricated by electron beam lithography of hydrogen silsesquioxane (HSQ) and by deep ultraviolet (DUV) lithography on SiO(2) thin films. Density multiplication of polystyrene-block-polydimethylsiloxane (PS-b-PDMS) within both prepatterns was achieved by using a room temperature dynamic solvent annealing environment. Selective tuning of PS and PDMS wetting on the HSQ template sidewalls was also achieved through careful functionalization of the template and substrate surface using either brush or a self-assembled trimethylsilyl monolayer. PDMS selectively wets HSQ sidewalls treated with a brush layer of PDMS, whiereas PS is found to selectively wet HSQ sidewalls treated with hexamethyldisilazane (HMDS) to produce a trimethylsilyl-terminated surface. The etch resistance of the aligned polymer was also evaluated to understand the implications of using block copolymer patterns which have high etch resistance, self-forming (PDMS) wetting layers at both interfaces. The results outlined in this work may have direct applications in nanolithography for continued device scaling toward the end-of-roadmap era.

Mechanical constraint and release generates long, ordered horizontal pores in anodic alumina templates.

We describe the formation of long, highly ordered arrays of planar oriented anodic aluminum oxide (AAO) pores during plane parallel anodization of thin aluminum 'finger' microstructures fabricated on thermally oxidized silicon substrates and capped with a silicon oxide layer. The pore morphology was found to be strongly influenced by mechanical constraint imposed by the oxide layers surrounding the Al fingers. Tractions induced by the SiO(2) substrate and capping layer led to frustrated volume expansion and restricted oxide flow along the interface, with extrusion of oxide into the primary pore volume, leading to the formation of dendritic pore structures and meandering pore growth. However, partial relief of the constraint by a delaminating interfacial fracture, with its tip closely following the anodization front, led to pore growth that was highly ordered with regular, hexagonally packed arrays of straight horizontal pores up to 3 µm long. Detailed characterization of both straight and dendritic planar pores over a range of formation conditions using advanced microscopy techniques is reported, including volume reconstruction, enabling high quality 3D visualization of pore formation.