Design and evaluation of polymer matrices for the encapsulation of CdSe/ZnS quantum dots in photonic nanocomposite thin films

A systematic approach and a new scheme for the evaluation of the as–is encapsulation of CdSe/ZnS core/shell quantum dots into polymer matrices is proposed, aiming to the implementation of thin film photonic integrated structures. Work focuses on quantum dots capped by hexadecylamine and trioctylphosphine oxide with no ligand exchange or other intermediate processing steps involved. The polymers studied include poly(methyl–methacrylate) (PMMA), polystyrene and acrylic polymers incorporating long alkyl chains, which are expected to promote the compatibility of the quantum dot ligands to that of the polymer chains. In this approach, the variation of photoluminescence properties of the nanocomposite thin films is measured versus increased concentration of the quantum dots, so as to evaluate the suitability of each polymer structure as an efficient host. Furthermore, the refractive index of the quantum dots/polymer nanocomposite thin films are also estimated using white light reflectance spectroscopy data, as appropriate for the integration of photonic devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 552–560     

Amphiphilic diblock copolymer‐based multiagent photonic sensing scheme

Efficient functionalization of polymer optical fibers' (POF) surface by a novel block copolymer material toward the development of low‐cost multiagent sensors is presented. The employed poly(styrene sulfonate‐b‐tert‐butylstyrene) (SPS‐b‐PtBS) diblock copolymer possesses two blocks of distinctively different polarity and charge, the hydrophilic SPS which is sensitive to polar substances and the hydrophobic PtBS which is sensitive to organic solvents. The coexistence of two different blocks allows for the detection of a wide variety of agents, ranging from ammonia, and organic solvents, to biomolecules like lysozyme, at room temperature as opposed to alternative usually more complicated techniques, all with the sole use of one sensing medium. Copolymers' high glass transition temperature enables the formation of stable and environmentally robust overlayers. The sensing performance of the material is evaluated experimentally on the customizable platform of POFs, demonstrating fast response, high operational reversibility, and also reusability in successively different testing agents. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 46–54     

Statistical copolymers of methyl methacrylate and 2‐methacryloyloxyethyl ferrocenecarboxylate: Monomer reactivity ratios,thermal and electrochemical properties

Statistical copolymers of methyl methacrylate (MMA) with 2‐methacryloyloxyethyl ferrocenecarboxylate (MAEFC) were prepared by free radical polymerization. The reactivity ratios were estimated using the Fineman‐Ross, inverted Fineman‐Ross, Kelen‐Tüdos, and extended Kelen‐Tüdos graphical methods. Structural parameters of the copolymers were obtained by calculating the dyad monomer sequence fractions and the mean sequence length. The glass‐transition temperature (T_g) values of the copolymers were measured and examined by means of several theoretical equations, allowing the prediction of these T_g values. The thermal degradation behavior of the copolymers was also studied and compared with the respective homopolymers. Cyclic voltammetry was employed to study the electrochemical properties of the copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Assembly of quantum dots on peptide nanostructures and their spectroscopic properties

We present a chemical process for the decoration of self-assembled two-dimensional peptide fibrils with two different sizes of CdSe@ZnS core–shell quantum dots (Qdots) capped with trioctylphosphine oxide molecules. The attachment of the semiconducting nanoparticles to the fibrils is directed via disulfide bond between the quantum dot and cysteine aminoacids that are deliberately impeded in the peptide structures. A significant red shift in the emission spectra of the quantum dots is observed and attributed to the synergistic interaction between adjacent nanoparticles arranged on peptide film templates extending over hundreds of nanometers.     

Plasmonic response of ordered arrays of gold nanorods immersed within a nematic liquid crystal

We study theoretically the optical properties of a two-dimensional lattice of metallic (gold) nanorods immersed within a nematic liquid crystal (NLC) strongly anchored to the surface of the nanorods. The distribution of the director field of the NLC is found by minimising the corresponding total free energy via simulated annealing. Optical properties such as transmittance, reflectance and absorbance of the structure are found by employing a hybrid discrete-dipole approximation/layer-multiple-scattering technique. We show, in particular, that when the NLC is strongly anchored to the nanorods, light absorbance is more efficient compared to the case where the liquid crystal (LC) is aligned by application of an external field. Also, the alignment of the LC molecules via an external field leads to a significant shift of the surface-plasmon resonance of the gold nanorods relative to the strong-anchoring case, an effect which can be exploited in switching applications. We also report that the rate of light absorption is a non-monotonic function of the height of nanorods due to the guiding of EM waves taking place for long enough nanorods.     

A family of hexanuclear Mn(III) single-molecule magnets

In an attempt to employ salicylic acid (HOsalH), 2,6-dihydroxy benzoic acid {(HO)₂PhCO₂H}, and naphthalene-1,8-dicarboxylic acid {1,8-naph(CO₂H)₂} in Mn(III) salicylaldoximate chemistry as a means to alter the structural identity of the hexanucluear clusters usually obtained from this reaction system, we have isolated a family of hexanuclear Mn(III) complexes based on salicyladloxime (saoH₂) and 2-hydroxy-1-naphthaldehyde oxime (naphthsaoH₂). Five hexanuclear clusters, [Mn₆O₂(sao)₆(HOsal)₂(EtOH)₄]·EtOH (1·EtOH), [Mn₆O₂(sao)₆{1,8-naph(CO₂Me)(CO₂)}₂(MeOH)₆]·3MeOH (2·3MeOH), [Mn₆O₂(naphthsao)₆{1,8-naph(CO₂Et)(CO₂)}₂(EtOH)₆] (3·2MeOH), [Mn₆O₂(naphthsao)₆(MeCO₂)₂(EtOH)₄]·2H₂O (4·2H₂O), and [Mn₆O₂(naphthsao)₆{(HO)₂PhCO₂}₂(EtOH)₄]·4EtOH (5·4EtOH), have been synthesized and characterized by single-crystal X-ray crystallography. The magnetic properties of 3, 4, and 5 are discussed.     

Coupled commensurate cation and charge modulation in the tunneled structure, Na(0.40(2))MnO(2)

Na(0.40(2))MnO(2) belongs to a family of mixed Mn(3+) and Mn(4+) porous oxides that contains both octahedral and square pyramidal Mn-O units. Neutron and synchrotron radiation studies identify the presence of both sodium ordering (T(Na) ≈ 310 K) and Mn charge and orbital ordering. Below T(Na), the centrosymmetric Pbam structure adopts an (ab 4c) supercell of Pnnm symmetry that accommodates a coupled commensurate modulation down the c-axis channels of both Na position and occupancy with Mn valence.     

Computational techniques for the analysis and design of dielectric-loaded plasmonic circuitry

The finite element and the beam propagation method, two widely used methods in photonics, are utilized for the analysis of plasmonic components based on the dielectric-loaded plasmonic waveguide. Two components are chosen as examples and are subsequently numerically investigated by employing the aforementioned methods, in order to demonstrate their applicability in plasmonics. Specifically, a microring resonator add-drop filter and a Mach–Zehnder interferometric switch are analyzed by means of the finite element and the beam propagation method, respectively. The formulation adopted is clearly presented in both cases and the case-dependent implementation details are thoroughly discussed.     

1,3-Dipolar cycloadditions of nitrile oxides with 4-carbethoxymethyleno-4,5,6,7-tetrahydro-6,6-dimethylbenzo[c][1,2,5]oxadiazole

The (E)- and (Z)-α,β-unsaturated esters, 3 and 4 are prepared by applying a Wittig reaction on the ketone 1. Stable nitrile oxides are added to the stable (E)-isomer 3 resulting to the formation of the spiro-derivatives 7 , whereas with the unstable nitrile oxides a second stereoisomer 8 is also formed. Mesitonitrile oxide reacts also with the ketone 1 to give the spiro-cycloadduct 10. The assignment of regio-isomers 7 was deduced from their spectral data as well as from some molecular orbital considerations.     

The natural hedge of a gas-fired power plant

Electricity industries worldwide have been restructured in order to introduce competition. As a result, decision makers are exposed to volatile electricity prices, which are positively correlated with those of natural gas in markets with price-setting gas-fired power plants. Consequently, gas-fired plants are said to enjoy a “natural hedge.” We explore the properties of such a built-in hedge for a gas-fired power plant via a stochastic programming approach, which enables characterisation of uncertainty in both electricity and gas prices in deriving optimal hedging and generation decisions. The producer engages in financial hedging by signing forward contracts at the beginning of the month while anticipating uncertainty in spot prices. Using UK energy price data from 2006 to 2011 and daily aggregated dispatch decisions of a typical gas-fired power plant, we find that such a producer does, in fact, enjoy a natural hedge, i.e., it is better off facing uncertain spot prices rather than locking in its generation cost. However, the natural hedge is not a perfect hedge, i.e., even modest risk aversion makes it optimal to use gas forwards partially. Furthermore, greater operational flexibility enhances this natural hedge as generation decisions provide a countervailing response to uncertainty. Conversely, higher energy-conversion efficiency reduces the natural hedge by decreasing the importance of natural gas price volatility and, thus, its correlation with the electricity price.