ChemInform Abstract: Unusual Inorganic Biradicals: A Theoretical Analysis.

Quantum chemical calculations at the CASSCF level of theory on the O₃‐homologous molecules CX₂^2‐, NX₂^‐, X₃, OX₂, and FX₂⁺ (X: O, S, Se, Te, Po) indicate that the triatomic inorganic biradicals in the FX₂⁺ series have unusually high biradical character.     

Existence of solutions for fractional differential equations with nonlocal and average type integral boundary conditions

In this paper, we establish sufficient conditions for the existence and uniqueness of solutions for a boundary value problem of fractional differential equations with nonlocal and average type integral boundary conditions. The Leray–Schauder nonlinear alternative, Krasnoselskii’s fixed point theorem and Banach’s fixed point theorem together with Hölder inequality are applied to construct proofs for the main results. Examples illustrating the obtained results are also presented.     

Uniform nanoparticles by flame-assisted spray pyrolysis (FASP) of low cost precursors

A new flame-assisted spray pyrolysis (FASP) reactor design is presented, which allows the use of inexpensive precursors and solvents (e.g., ethanol) for synthesis of nanoparticles (10–20 nm) with uniform characteristics. In this reactor design, a gas-assisted atomizer generates the precursor solution spray that is mixed and combusted with externally fed inexpensive fuel gases (acetylene or methane) at a defined height above the atomizing nozzle. The gaseous fuel feed can be varied to control the combustion enthalpy content of the flame and onset of particle formation. This way, the enthalpy density of the flame is decoupled from the precursor solution composition. Low enthalpy content precursor solutions are prone to synthesis of non-uniform particles (e.g., bimodal particle size distribution) by standard flame spray pyrolysis (FSP) processes. For example, metal nitrates in ethanol typically produce nanosized particles by gas-to-particle conversion along with larger particles by droplet-to-particle conversion. The present FASP design facilitates the use of such low enthalpy precursor solutions for synthesis of homogeneous nanopowders by increasing the combustion enthalpy density of the flame with low-cost, gaseous fuels. The effect of flame enthalpy density on product properties in the FASP configuration is explored by the example of Bi₂O₃ nanoparticles produced from bismuth nitrate in ethanol. Product powders were characterized by nitrogen adsorption, X-ray diffraction, X-ray disk centrifuge, and transmission electron microscopy. Homogeneous Bi₂O₃ nanopowders were produced both by increasing the gaseous fuel content and, most notably, by cutting the air entrainment prior to ignition of the spray.     

A study of higher-order nonlinear ordinary differential equations with four-point nonlocal integral boundary conditions

This paper investigates some new existence results for an nth-order nonlinear differential equation with four-point nonlocal integral boundary conditions (strip/slit like conditions). Our results are based on some standard fixed point theorems and Leray-Schauder degree theory.     

Modular polymer biosensors by solvent immersion imprint lithography

We recently demonstrated Solvent Immersion Imprint Lithography (SIIL), a rapid benchtop microsystem prototyping technique, including polymer functionalization, imprinting and bonding. Here, we focus on the realization of planar polymer sensors using SIIL through simple solvent immersion without imprinting. We describe SIIL's impregnation characteristics, including an inherent mechanism that not only achieves practical doping concentrations, but their unexpected 2‐fold enhancement compared to the immersion solution. Subsequently, we developed and characterized optical sensors for detecting molecular O₂. To this end, a substantially high dynamic range is reported, including its control through the immersion duration, a manifestation of SIIL's modularity. Overall, SIIL exhibits the potential of improving the operating characteristics of polymer sensors, while significantly accelerating their prototyping, as it requires a few seconds of processing and no need for substrates or dedicated instrumentation. These are critical for O₂ sensing as probed by way of example here, as well as any polymer permeable reactant. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 98–103     

High-pressure liquid dispersion and fragmentation of flame-made silica agglomerates

The influence of primary particle diameter and the degree of agglomeration of flame-made silica agglomerate suspensions in aqueous solutions is studied by high-pressure dispersion (up to 1500 bar) through a nozzle with a 125 microm inner diameter. These particles were produced (4-15 g/h) by oxidation of hexamethyldisiloxane (HMDSO) in a coflow diffusion flame reactor. Their average primary particle size (10-50 nm) and degree of agglomeration were controlled by varying the oxygen and precursor flow rates. The particles were characterized by nitrogen adsorption, electron microscopy, and small-angle X-ray scattering. Hydrodynamic stresses break up soft agglomerates and yield hard agglomerate sizes in the range of 100-180 nm, as characterized by dynamic light scattering. Soft agglomerates exhibited decreasing light scattering diameters with increasing dispersion pressure, while hard agglomerates were insensitive.     

Radiocolorings in periodic planar graphs: PSPACE-completeness and efficient approximations for the optimal range of frequencies

The Frequency Assignment Problem (FAP) in radio networks is the problem of assigning frequencies to transmitters exploiting frequency reuse while keeping signal interference to acceptable levels. The FAP is usually modelled by variations of the graph coloring problem. A Radiocoloring (RC) of a graph G(V,E) is an assignment function such that |Λ(u)−Λ(v)|2, when u,v are neighbors in G, and |Λ(u)−Λ(v)|1 when the distance of u,v in G is two. The discrete number of frequencies used is called order and the range of frequencies used, span. The optimization versions of the Radiocoloring Problem (RCP) are to minimize the span (min span RCP) or the order (min order RCP).In this paper, we deal with an interesting, yet not examined until now, variation of the radiocoloring problem: that of satisfying frequency assignment requests which exhibit some periodic behavior. In this case, the interference graph (modelling interference between transmitters) is some (infinite) periodic graph. Infinite periodic graphs usually model finite networks that accept periodic (in time, e.g. daily) requests for frequency assignment. Alternatively, they can model very large networks produced by the repetition of a small graph.A periodic graph G is defined by an infinite two-way sequence of repetitions of the same finite graph G_i(V_i,E_i). The edge set of G is derived by connecting the vertices of each iteration G_i to some of the vertices of the next iteration G_i+1, the same for all G_i. We focus on planar periodic graphs, because in many cases real networks are planar and also because of their independent mathematical interest.We give two basic results:

• We prove that the min span RCP is PSPACE-complete for periodic planar graphs.

• We provide an O(n(Δ(G_i)+σ)) time algorithm (where|V_i|=n, Δ(G_i) is the maximum degree of the graph G_i and σ is the number of edges connecting each G_i to G_i+1), which obtains a radiocoloring of a periodic planar graph G that approximates the minimum span within a ratio which tends to as Δ(G_i)+σ tends to infinity.

We remark that, any approximation algorithm for the min span RCP of a finite planar graph G, that achieves a span of at most αΔ(G)+constant, for any α and where Δ(G) is the maximum degree of G, can be used as a subroutine in our algorithm to produce an approximation for min span RCP of asymptotic ratio α for periodic planar graphs.

Solid-phase fluoroimmunoassay for the determination of mesotrione--a novel triketone herbicide--in water with direct measurement of the fluorescence onto the solid support

A straightforward, low-cost fluoroimmunoassay (FIA) for the determination of the new triketone herbicide mesotrione has been developed and optimized. The protein-mesotrione conjugate, immobilized on white opaque microtitration wells competes with the mesotrione in the sample or standard for the limited binding sites of a liquid phase anti-mesotrione antibody. The assay is based on the measurement of fluorescence intensity directly onto the solid support, using a fluorescein labeled second antibody and a fluorescence plate reader. To stabilize and enhance the fluorescence signal a glycerine-based treatment of the microtitration wells was included in the protocol. The detection limit of the assay is 40 ng 1(-1) (4 pg per well), the working range extends up to 9 microg l(-1), whereas the within and between run CVs are 0.7-4.2% and 2.1-5.5%, respectively. To evaluate the assay specificity, the cross-reactivities of two mesotrione metabolites: 4-methylsulfonyl-2-nitrobenzoic acid and 2-amino-4-methylsulfonyl-benzoic acid and several other compounds similar in structure to mesotrione such as: fomesafen, prosulfocarb, fluazinam, sulcotrione, 1,2-cyclohexanedione, 1,3-cyclohexanedione, 2-acetyl-1,3-cyclohexanedione were assessed. Most of the substances tested presented very low ( < 0.05%) cross-reactivity values with the exception of sulcotrione that cross-reacted 23% in the mesotrione assay. The assay was used for the determination of mesotrione in bottled natural waters fortified with the analyte and in a commercial herbicide formulation, namely CALLISTO.     

Discrete X-wave formation in nonlinear waveguide arrays

We present experimental evidence for the spontaneous formation of discrete X waves in AlGaAs waveguide arrays. This new family of optical waves has been excited, for the first time, by using the interplay between discrete diffraction and normal temporal dispersion, in the presence of Kerr nonlinearity. Our experimental results are in good agreement with theoretical predictions.     

High-resolution infrared spectroscopy in the 1,200-1,300 cm(-1) region and accurate theoretical estimates for the structure and ring-puckering barrier of perfluorocyclobutane

We present experimental infrared spectra and theoretical electronic structure results for the geometry, anharmonic vibrational frequencies, and accurate estimates of the magnitude and the origin of the ring-puckering barrier in C4F8. High-resolution (0.0015 cm-1) spectra of the nu12 and nu13 parallel bands of perfluorocyclobutane (c-C4F8) were recorded for the first time by expanding a 10% c-C4F8 in helium mixture in a supersonic jet. Both bands are observed to be rotationally resolved in a jet with a rotational temperature of 15 K. The nu12 mode has b2 symmetry under D2d that correlates to a2u symmetry under D4h and consequently has +/- <-- +/- ring-puckering selection rules. A rigid rotor fit of the nu12 band yields the origin at 1292.56031(2) cm-1 with B' = 0.0354137(3) cm-1 and B' ' = 0.0354363(3) cm-1. The nu13 mode is of b2 symmetry under D2d that correlates to b2g under D4h, and in this case, the ring-puckering selection rules are +/- <-- -/+ . Rotational transitions from the ground and first excited torsional states will be separated by the torsional splitting in the ground and excited vibrational states, and indeed, we observe a splitting of each transition into strong and weak intensity components with a separation of approximately 0.0018 cm-1. The strong and weak sets of transitions were fit separately again using a rigid rotor model to give nu13(strong) = 1240.34858(4) cm-1, B' = 0.0354192(7) cm-1, and B' ' = 0.0354355(7) cm-1 and nu13(weak) = 1240.34674(5) cm-1, B' = 0.0354188(9) cm-1, and B' ' = 0.0354360(7) cm-1. High-level electronic structure calculations at the MP2 and CCSD(T) levels of theory with the family of correlation consistent basis sets of quadruple-zeta quality, developed by Dunning and co-workers, yield best estimates for the vibrationally averaged structural parameters r(C-C) = 1.568 A, r(C-F)alpha = 1.340 A, r(C-F)beta = 1.329 A, alpha(F-C-F) = 110.3 degrees , thetaz(C-C-C) = 89.1 degrees , and delta(C-C-C-C) = 14.6 degrees and rotational constants of A = B = 0.03543 cm-1 and C = 0.02898 cm-1, the latter within 0.00002 cm-1 from the experimentally determined values. Anharmonic vibrational frequencies computed using higher energy derivatives at the MP2 level of theory are all within <27 cm-1 (in most cases <5 cm-1) from the experimentally measured fundamentals. Our best estimate for the ring-puckering barrier at the CCSD(T)/CBS (complete basis set) limit is 132 cm-1. Analysis of the C4F8 electron density suggests that the puckering barrier arises principally from the sigmaCC-->sigmaCF hyperconjugative interactions that are more strongly stabilizing in the puckered than in the planar form. These interactions are, however, somewhat weaker in C4F8 than in C4H8, a fact that is consistent with the smaller barrier in the former (132 cm-1) with respect to the latter (498 cm-1).