An attempt to understand the observed plateau of the magnetization in tetranuclear iron(II) complexes of thiacalixarene macrocycles

The next-nearest-neighbour (NNN) effect in tetranuclear iron(II) complexes of thiacalixarene macrocycles using the isotropic Heisenberg model has been investigated in order to understand its effects on the observed plateau of magnetization. Although NNN effect is generally very weak in these kinds of systems, it was calculated that its response is quite significant to the external perturbations in certain temperature regions. Using the isotropic Heisenberg exchange Hamiltonian, zero-field energy spectra have been calculated for this particular tetranuclear system. The average magnetic moments with and without next-nearest-neighbour interactions were also calculated. In order to verify the calculations, the results were compared with experimental data taken from the literature, whence, it is suggested that observed magnetic behaviour can be improved by taking into account the NNN effect.     

Synthesis of H‐shaped complex macromolecular structures by combination of atom transfer radical polymerization,photoinduced radical coupling,ring‐opening polymerization,and iniferter processes

Three controlled/living polymerization processes, namely atom transfer radical polymerization (ATRP), ring‐opening polymerization (ROP) and iniferter polymerization, and photoinduced radical coupling reaction were combined for the preparation of ABCBD‐type H‐shaped complex copolymer. First, α‐benzophenone functional polystyrene (BP‐PS) and poly(methyl methacrylate) (BP‐PMMA) were prepared independently by ATRP. The resulting polymers were irradiated to form ketyl radicals by hydrogen abstraction of the excited benzophenone moieties present at each chain end. Coupling of these radicals resulted in the formation of polystyrene‐b‐poly(methyl methacrylate) (PS‐b‐PMMA) with benzpinacole structure at the junction point possessing both hydroxyl and iniferter functionalities. ROP of ε‐caprolactone (CL) by using PS‐b‐PMMA as bifunctional initiator, in the presence of stannous octoate yielded the corresponding tetrablock copolymer, PCL‐PS‐PMMA‐PCL. Finally, the polymerization of tert‐butyl acrylate (tBA) via iniferter process gave the targeted H‐shaped block copolymer. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4601–4607     

Fabrication of SERS active gold nanorods using benzalkonium chloride,and their application to an immunoassay for potato virus X

The authors report on a robust method for the synthesis of gold nanorods (AuNRs) with tunable dimensions and longitudinal surface plasmon resonance. The method relies on seed-mediated particle growth in the presence of benzalkonium chloride (BAC) in place of the widely used surfactant cetyltrimethyl ammonium bromide (CTAB). Uniform AuNRs were obtained by particle growth in solution, and BAC is found to stabilize the AuNRs for >1 year. The SERS activity of the resulting AuNRs is essentially identical to that of CTAB-protected nanorods. The SERS activity of the BAC protected nanorods was applied to the quantitative analysis of potato virus X (PVX). The calibration plot for PVX is linear in the 10 to 750 ng?mL^?1 concentration range, and the detection limit is 2.2 ng?mL^?1.

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Graphical abstract SERS-active gold nanorods (AuNRs) have been prepared by using benzalkonium chloride as stabilization agent. Effects of chemical parameters on AuNRs have been explored and AuNRs were used in quantitative analysis of potato virus X (PVX).

     

Synthesis of main chain polymeric benzophenone photoinitiator via thiol‐ene click chemistry and Its use in free radical polymerization

Main chain polymeric benzophenone photoinitiator (PBP) was synthesized by using “Thiol‐ene Click Chemistry” and characterized with ¹H NMR, FTIR, UV, and phosphorescence spectroscopies. PBP as a polymeric photoinitiator presented excellent absorption properties (ε₂₉₄ = 28,300 mol^?1L^?1cm^?1) compared to the molecular initiator BP (ε₂₅₂ = 16,600 mol^?1L^?1cm^?1). The triplet energy of PBP was obtained from the phosphorescence measurement in 2‐methyl tetrahydrofurane at 77 K as 298.3 kJ/mol and according to phosphorescence lifetime, the lowest triplet state of PBP has an n‐π* nature. Triplet–triplet absorption spectrum of PBP at 550 nm following laser excitation (355 nm) were recorded and triplet lifetime of PBP was found as 250 ns. The photoinitiation efficiency of PBP was determined for the polymerization of Hexanedioldiacrylate (HDDA) with PBP and BP in the presence of a coinitiator namely, N‐methyldiethanolamine (MDEA) by Photo‐DSC. The initiation efficiency of PBP for polymerization of HDDA is much higher than for the formulation consisting of BP. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Thermal Analysis of Micro- and Nano-Lignocellulosic Reinforced Styrene Maleic Anhydride Composite Foams

The aim of this study was to measure the thermal properties of foamed nano/macro filler–reinforced styrene maleic anhydride (SMA) composites. SMA (66%) as a polymer matrix (10% maleic anhydride content) and various fillers including wood flour, starch, α-cellulose, microcrystalline cellulose and cellulose nanofibrils as reinforcing agents (30%) and lubricant (4%) were used to manufacture the composites in a twin-screw extruder. According to the thermogravimetric analysis (TGA) results, thermal degradation of all the foamed composites was found to be lower than that of SMA composites. The storage modulus values were negatively affected with a second time foaming (reprocessing [recycling] the initially processed composites a second time), as were loss modulus and T_g. As a result, second-time-foamed composite modulus values were lower than those of the foamed composites. According to the melt flow index (MFI) results, viscosity of the SMA was found to increase with the addition of fillers.     

Surface-induced self-assembly of dipeptides onto nanotextured surfaces

There is an increasing interest for the utilization of biomolecules for fabricating novel nanostructures due to their ability for specific molecular recognition, biocompatibility, and ease of availability. Among these molecules, diphenylalanine (Phe-Phe) dipeptide is considered as one of the simplest molecules that can generate a family of self-assembly based nanostructures. The properties of the substrate surface, on which the self-assembly process of these peptides occurs, play a critical role. Herein, we demonstrated the influence of surface texture and functionality on the self-assembly of Phe-Phe dipeptides using smooth silicon surfaces, anodized aluminum oxide (AAO) membranes, and poly(chloro-p-xylylene) (PPX) films having columnar and helical morphologies. We found that helical PPX films, AAO, and silicon surfaces induce similar self-assembly processes and the surface hydrophobicity has a direct influence for the final dipeptide structure whether being in an aggregated tubular form or creating a thin film that covers the substrate surface. Moreover, the dye staining data indicates that the surface charge properties and hence the mechanism of the self-assembly process are different for tubular structures as opposed to the peptidic film. We believe that our results may contribute to the control of surface-induced self-assembly of peptide molecules and this control can potentially allow the fabrication of novel peptide based materials with desired morphologies and unique functionalities for different technological applications.     

Electronic and vibrational spectroscopy of intermediates in methane-to-methanol conversion by CoO+

At room temperature, cobalt oxide cations directly convert methane to methanol with high selectivity but very low efficiency. Two potential intermediates of this reaction, the [HO-Co-CH(3)](+) insertion intermediate and [H(2)O-Co=CH(2)](+) aquo-carbene complex are produced in a laser ablation source and characterized by electronic and vibrational spectroscopy. Reaction of laser-ablated cobalt cations with different organic precursors seeded in a carrier gas produces the intermediates, which subsequently expand into vacuum and cool. Ions are extracted into a time-of-flight mass spectrometer and spectra are measured via photofragment spectroscopy. Photodissociation of [HO-Co-CH(3)](+) in the visible and via infrared multiple photon dissociation (IRMPD) makes only Co(+) + CH(3)OH, while photodissociation of [H(2)O-Co=CH(2)](+) produces CoCH(2)(+) + H(2)O. The electronic spectrum of [HO-Co-CH(3)](+) shows progressions in the excited state Co-C stretch (335 cm(-1)) and O-Co-C bend (90 cm(-1)); the IRMPD spectrum gives ν(OH) = 3630 cm(-1). The [HO-Co-CH(3)](+)(Ar) complex has been synthesized and its vibrational spectrum measured in the O-H stretching region. The resulting spectrum is sharper than that obtained via IRMPD and gives ν(OH) = 3642 cm(-1). Also, an improved potential energy surface for the reaction of CoO(+) with methane has been developed using single point energies calculated by the CBS-QB3 method for reactants, intermediates, transition states and products.     

Fluorescence lifetime imaging of molecular rotors to map microviscosity in cells

Fluorescence liftime imaging （FLIM） of modified hydrophobic bodipy dyes that act as fluorescent molecular rotors shows that the fluorescence lifetime of these probes is a function of the microviscosity of their environment. Incubating cells with these dyes, we find a punctate and continuous distribution of the dye in cells. The viscosity value obtained in what appears to be endocytotic vesicles in living cells is around 100 times higher than that of water and of cellular cytoplasm.Time-resolved fluorescence anisotropy measurements also yield rotational correlation times consistent with large microviscosity values. In this way, we successfully develop a practical and versatile approach to map the microviscosity in cells based on imaging fluorescent molecular rotors.     

Development of a macro-scale model from a meso-scale model for cell culture population dynamics

In this paper, we present a novel macro-scale analytical model that allows the prediction of how the population size will change in a cell culture starting from an arbitrary initial value. General biological knowledge and some empirical observations are used to design an agent-based discrete-time model at the meso-scale, which then serves as a simulation environment and provides the necessary insights for the development of the continuous-time, differential equation-based, compact macro-scale model. This model can be parameter-tuned and employed for predicting how the population size changes. The paper gives a procedure for the estimation of parameter values of the macro-scale model via some simple tests to be conducted on the cell culture at hand. The performance of the macro-scale model is validated via simulation results that show how well the macro-scale model captures the population dynamics as obtained from the meso-scale model, while the biological plausibility of the meso-scale model is taken for granted.