Hydrogen isotope effects on covalent and noncovalent interactions: The case of protonated rare gas clusters

We investigate hydrogen isotope and nuclear quantum effects on geometries and binding energies of small protonated rare gas clusters (Rg $_n$ X $^ +$ , Rg = He,Ne,Ar, X = H,D,T, and $n$ = 1–3) with the any particle molecular orbital (APMO) MP2 level of theory (APMO/MP2). To gain insight on the impact of nuclear quantum effects on the different interactions present in the Rg $_n$ X $^ +$ systems, we propose an APMO/MP2 energy decomposition analysis scheme. For RgH $^ +$ ions, isotopic substitution leads to an increase in the stability of the complex, because polarization and charge transfer contributions increase with the mass of the hydrogen. In the case of Rg $_2$ H $^ +$ complexes, isotopic substitution results in a shortening and weakening of the rare gas‐hydrogen ion bond. For Rg $_3$ X $^ +$ complexes, the isotope effects on the rare gas binding energy are almost negligible. Nevertheless, our results reveal that subtle changes in the charge distribution of the Rg $_2$ X $^ +$ core induced by an isotopic substitution have an impact on the geometry of the Rg $_3$ X $^ +$ complex. © 2012 Wiley Periodicals, Inc.     

Hybrid cell adhesive material for instant dielectrophoretic cell trapping and long-term cell function assessment

Dielectrophoresis (DEP) for cell manipulation has focused, for the most part, on approaches for separation/enrichment of cells of interest. Advancements in cell positioning and immobilization onto substrates for cell culture, either as single cells or as cell aggregates, has benefited from the intensified research efforts in DEP (electrokinetic) manipulation. However, there has yet to be a DEP approach that provides the conditions for cell manipulation while promoting cell function processes such as cell differentiation. Here we present the first demonstration of a system that combines DEP with a hybrid cell adhesive material (hCAM) to allow for cell entrapment and cell function, as demonstrated by cell differentiation into neuronlike cells (NLCs). The hCAM, comprised of polyelectrolytes and fibronectin, was engineered to function as an instantaneous cell adhesive surface after DEP manipulation and to support long-term cell function (cell proliferation, induction, and differentiation). Pluripotent P19 mouse embryonal carcinoma cells flowing within a microchannel were attracted to the DEP electrode surface and remained adhered onto the hCAM coating under a fluid flow field after the DEP forces were removed. Cells remained viable after DEP manipulation for up to 8 d, during which time the P19 cells were induced to differentiate into NLCs. This approach could have further applications in areas such as cell-cell communication, three-dimensional cell aggregates to create cell microenvironments, and cell cocultures.     

Electrical tuning of photonic crystals infilled with liquid crystals

In this paper we perform a complete study of electrical tuning in liquid crystal-infilled two-dimensional (2D) photonic crystals (PCs). The nematic liquid crystal (NLC) is characterized by a full range of bulk and surface elastic parameters. An essentially DC tuning field is applied in the axial direction. By minimizing the total (elastic plus electromagnetic) free energy, the configuration of the NLC directors, as a function of radial distance, is obtained. Three possible configurations are considered: escaped radial, planar radial, and axial. It is found that, in general, the escaped radial configuration is the preferred one. However, for sufficiently large applied fields, a phase transition occurs to the axial configuration. For example, in the case of the NLC 5CB, this transition is realized at about 14 V/μm provided that the cylinder radius is greater than about 50 nm. The configuration of the NLC directors determines the dielectric tensor as function of radial distance and this, in turn, leads to the eigenvalue equation for the PC. We present two such equations: one exact and the other approximate. The exact eigenvalue equation is based on the full anisotropy of the dielectric tensor and does not result in the usual separation of normal modes in a 2D PC. The approximate eigenvalue equation is derived from the average (over the cylinder cross-section) dielectric tensor and leads to modes that are polarized in the directions either parallel (E-mode) or perpendicular (H-mode) to the cylinders. Our calculations of the photonic band structure, by both methods, show that the approximate calculation works very well for the 5CB NLC cylinders in a silicon oxide (silica) host. This allows us to introduce the terminology quasi-E and quasi-H polarizations. We show how the partial photonic band gap in the [1 0 0] direction for these polarizations can be tuned and even completely closed. This behavior could be applied to the design of versatile, tunable polarization filters.     

Thermoluminescence response of the larimar rocks

The aim of this paper is to evaluate the thermoluminescent (TL) response of a larimar, a variety of pectolite (NaCa₂Si₃O₈[OH]). It is a blue pectolite only found on the terrestrial crust of the province of Barahona, in the south-western region of the Dominican Republic. The larimar rock used in this study, presented a light-blue color with brown areas. X-ray powder diffractometry (XRD), showed that the light-blue portion of the rock is composed essentially by pectolite and the brown portion is composed by a mixture of minerals. Aliquots of 5 mg of light-blue portions were irradiated with gamma rays with doses from 10 to 10⁴ Gy and the TL glow curves were obtained from 50 to 400 °C. The glow curve showed a broad peak around 150 °C and a peak near 280 °C. Different pre-heat condition were used to remove the broad peak. The TL emission of the main peak appeared in the region of 580 nm. The TL response of the main peak showed a linear behavior up to 2500 Gy and a sub-linear behavior above this dose value. Studies of the 30 day fading effects in TL signal using a pre-heating temperature around 180 °C during 15 min were carried out and fading near 25% was observed.     

Platinum(II)-Based Optical Probes for Imaging Quadruplex DNA Structures via Phosphorescence Lifetime Imaging Microscopy

G-quadruplex DNA is a non-canonical structure that forms in guanine-rich regions of the genome. There is increasing evidence showing that G-quadruplexes have important biological functions, and therefore molecular tools to visualise these structures are important. Herein we report on a series of new cyclometallated platinum(II) complexes which, upon binding to G-quadruplex DNA, display an increase in their phosphorescence, acting as switch-on probes. More importantly, upon binding to G-quadruplexes they display a selective and distinct lengthening of their emission lifetime. We show that this effect can be used to selectively visualise these structures in cells using Phosphorescence Lifetime Imaging Microscopy (PLIM).     

Syntheses,Characterization, and DNA Binding Studies of a Series of Copper(II), Nickel(II), Platinum(II) and Zinc(II) Complexes Derived from Schiff Base Ligands

Three series of metal salophen complexes derived from Zn²⁺, Cu²⁺, Pt²⁺ and Ni²⁺ have been synthesized and their interaction with quadruplex DNA has been evaluated. The compounds differ on the number of ethyl piperidine substituents. They have been characterized by ¹H NMR, IR and UV-visible spectroscopies and by HR-mass spectrometry. Their luminescent properties have been also evaluated and we can observe that, as expected, Zn²⁺ and Pt²⁺ complexes are those displaying more interesting luminescence with an emission band red-shifted with respect to the corresponding uncoordinated ligand. DNA interactions with G4 and duplex DNA were evaluated by FRET melting assays (for the Zn²⁺, Cu²⁺ and Ni²⁺ complexes) and by emission titrations (for one Pt²⁺ complex) which indicated that the disubstituted compounds 2-Ni and 2-Pt are the only ones that display good affinity for G4 DNA structures.     

Novel Synthetic Approach towards Amino-Substituted Polycyclic Aromatic Hydrocarbons through Electrocyclization of Keteniminium Salts

Polycyclic aromatic hydrocarbons (PAHs) are an important family of molecules in science and technology. Amino-substituted PAHs are promising building blocks to create attractive molecules for materials science. However, the synthetic limitations have hampered to produce diverse structures of amino-substituted PAHs. Here we describe a novel efficient synthetic method to access amino-substituted PAHs through the electrocyclization of highly reactive keteniminium species. We demonstrated the synthesis of various amino-substituted PAHs and disclosed some of their photophysical properties. Furthermore, combination with theoretical calculation revealed that the multiple electrocyclization reactions of keteniminium species is a stepwise process and the fusion of additional aromatic ring to the substrate accelerates the electrocyclization.