Transparent flexible ZnO/MWCNTs/pbma ternary nanocomposite film with enhanced mechanical properties

Functional organic-inorganic nanocomposites with high transparency show significant potential application in many fields. However, it is still a great challenge to prepare flexible transparent nanocomposites due to the intrinsic stiffness of the nanoparticles and the poor interaction between nanoparticles and organic matrices. In this work, a transparent ternary nanocomposite film with enhanced mechanical performance is fabricated by two-steps. First, the transparent ternary ZnO/MWCNTs/n-butyl methacrylate (BMA) nanodispersion is prepared by mixing the ZnO/BMA and MWCNTs/BMA dispersions directly. Then, the ternary nanocoposites film is fabricated via in-situ bulk polymerization of the above nanodispersions. As a result, the tensile strength of the ZnO/MWCNTs/poly-n-butyl methacrylate (PBMA) ternary film is enhanced by 42% and the elongation at break is three times that of ZnO/PBMA nanocomposite. The hardness of the film increases from 5B to 1H with 40 wt% ZnO. These results indicate that ZnO and MWCNTs can improve the mechanical properties of the composite significantly. Importantly, the ternary nanocomposite film still remains high transparency and exhibit excellent UV-shielding performance. The as-prepared transparent multifunctional nanocomposite films have promising applications in optical materials and devices, such as optical filters, contact lenses and protection packing.     

Samarium(ii) iodide-mediated intramolecular pinacol coupling reactions with cyclopropyl ketones

The first reported intramolecular pinacol coupling of cyclopropyl ketones has been achieved, demonstrating that cyclisation competes favourably with ring-opening of the cyclopropyl ketyl radical.     

Sensitization of europium(III) luminescence by benzophenone-containing ligands: regioisomers, rearrangements and chelate ring size, and their influence on quantum yields

A series of europium(III) complexes based on the macrocyclic azacarboxylate structure, DO3A, have been investigated, incorporating benzophenone appended at N10 of the macrocycle via linkers containing amide bonds (H3DO3A = 1,4,7,10-tetraazacyclododecane-1,4,7-tris-acetic acid). Complexes [EuL(1-3)] incorporate N10-CH2CONH-BP linkers (BP = benzophenone), which allow formation of a five-membered chelate ring containing the metal ion upon chelation of the amide oxygen; these three isomeric complexes differ from one another in the substitution position of the BP unit, namely para, meta, and ortho for L1, L2, and L3 respectively. The quantum yields of europium luminescence sensitized via the chromophore are found to be highly dependent upon the position of substitution, being 20 times smaller for the ortho compared to the para-substituted complex. A related para-substituted BP complex [EuL(4)], prepared by an unusual Michael reaction of the azamacrocycle with a BP-containing acrylamide, incorporates an additional methylene unit in the linker, namely N10-CH2CH2CONH-BP. Despite the longer linker, this complex equals the luminescence quantum yield achieved with [EuL(1)] (Phi(lum) = 0.097 and 0.095, respectively, in H2O at 298 K). Analysis of the pertinent kinetics reveals that the decreased energy transfer efficiency in this complex, arising from the longer donor-acceptor distance, is compensated by an increased radiative rate constant. Under basic conditions, the ortho-substituted complex [EuL(3)] undergoes an intramolecular rearrangement to generate an unprecedented complex [EuL(5)] incorporating a 4-phenyl-2-hydroxyquinoline unit directly bound to the ring nitrogen. Although this complex is a poor emitter, an analogous complex obtained from 2-amino-acetophenone, which generates 4-methyl-2-hydroxyquinoline during the corresponding rearrangement, is an order of magnitude more emissive while still benefiting from relatively long-wavelength absorption. The emission from this complex is pH sensitive, being dramatically quenched under mildly basic conditions.     

Scattering form factors for self-assembled network junctions

The equilibrium microstructures in microemulsions and other self-assembled systems show complex, connected shapes such as symmetric bicontinuous spongelike structures and asymmetric bicontinuous networks formed by cylinders interconnected at junctions. In microemulsions, these cylinder network microstructures may mediate the structural transition from a spherical or globular phase to the bicontinuous microstructure. To understand the structural and statistical properties of such cylinder network microstructures as measured by scattering experiments, models are needed to extract the real-space structure from the scattering data. In this paper, we calculate the scattering functions appropriate for cylinder network microstructures. We focus on such networks that contain a high density of network junctions that connect the cylindrical elements. In this limit, the network microstructure can be regarded as an assembly of randomly oriented, closed packed network junctions (i.e., the cylinder scattering contributions are neglected). Accordingly, the scattering spectrum of the network microstructure can be calculated as the product of the junction number density, the junction form factor, which describes the scattering from the surface of a single junction, and a structure factor, which describes the local correlations of different junctions due to junction interactions (including their excluded volume). This approach is applied to analyze the scattering data from a bicontinuous microemulsion with equal volumes of water and oil. In a second approach, we included the cylinder scattering contribution in the junction form factor by calculating the scattering intensity of Y junctions to which three rods with spherical cross section are attached. The respective theoretical predictions are compared with results of neutron scattering measurements on a water-in-oil microemulsion with a connected microstructure.     

Environmental Research for Art Conservation and Assessment of Indoor Conditions Surrounding Cultural Objects

This paper describes the results and conclusions of research directed towards the development and evaluation of a chemical sensor which would provide information on the quality of indoor environments surrounding cultural objects. In our case these objects were paintings housed in major European galleries and the main objective is their preservation through an improved understanding of their microenvironment. The concept was to prepare and expose test tempera paintings which would behave as dosimeters and integrate the environmental response at these locations. Artificial ageing of similar samples was performed to provide a means of calibrating the test paintings. Samples from the test paintings were compared with artificially aged samples and this enabled the sites to be ranked in terms of their suitability for exposure of cultural objects. Additionally, novel methodology involving piezoelectric sensors was designed for monitoring the relative humidity and temperature of the microenvironment of paintings. Dielectric techniques were also used for measuring the effect of relative humidity fluctuations on artists' materials and novel non-invasive dielectric techniques in the microwave region were used for the determination of their moisture content. This revised version was published online in August 2006 with corrections to the Cover Date.     

Kinetics of the reaction of OH radicals with a series of esters under simulated conditions at 295 K

The rate constants of the isopropyl acetate, n-propyl acetate, isopropenyl acetate, n-propenyl acetate, n-butyl acetate, and ethyl butyrate reactions with OH radicals were determined in purified air under atmospheric conditions, at 750 torr and (295 ± 2) K. A relative rate experimental method was used; n-heptane, n-octane, and n-nonane were the reference compounds, with, respectively, rate constants for the reaction with OH of 7.12 × 10⁻¹², 8.42 × 10⁻¹², and 9.70 × 10⁻¹² molecule⁻¹ cm³s⁻¹. The following rate constants were obtained in units of 10⁻¹² molecule⁻¹ cm³s⁻¹; isopropyl acetate, (3.12 ± 0.29); n-propyl acetate, (1.97 ± 0.24); isopropenyl acetate, (62.53 ± 1.24); n-propenyl acetate, (24.57 ± 0.24); n-butyl acetate, (3.29 ± 0.35); and ethyl butyrate, (4.37 ± 0.42). Tertiary butyl acetate has a low reactivity with OH radicals (<1 × 10⁻¹² molecule⁻¹ cm³s⁻¹). © 1996 John Wiley & Sons, Inc.     

Toward high-performance computational chemistry: I. Scalable Fock matrix construction algorithms

Several parallel algorithms for Fock matrix construction are described. The algorithms calculate only the unique integrals, distribute the Fock and density matrices over the processors of a massively parallel computer, use blocking techniques to construct the distributed data structures, and use clustering techniques on each processor to maximize data reuse. Algorithms based on both square and row-blocked distributions of the Fock and density matrices are described and evaluated. Variants of the algorithms are discussed that use either triple-sort or canonical ordering of integrals, and dynamic or static task clustering schemes. The algorithms are shown to adapt to screening, with communication volume scaling down with computation costs. Modeling techniques are used to characterize algorithm performance. Given the characteristics of existing massively parallel computers, all the algorithms are shown to be highly efficient for problems of moderate size. The algorithms using the row-blocked data distribution are the most efficient. © 1996 by John Wiley & Sons, Inc.     

On determining a 1-tailed upper limit for future sample HorRat values

Two formulas were developed for use in computing 1-tailed upper limits for future HorRat values obtained from the collaborative study of materials. One formula is applicable when a future sample HorRat value H [formula: see text] is computed based on a known concentration (e.g., C = spike level and RSD(R) is the sample relative reproducibility standard deviation) and the other formula is applicable when the true concentration (C) is unknown and a future sample HorRat value [formula: see text] is computed using the sample mean (e.g., y, the collaborative study overall mean for an analyte). A Monte Carlo simulation procedure was developed using the Statistical Analysis System (SAS) software to assess the accuracy of the 2 developed formulas. Based on the degree of closeness between the simulated and calculated limits, the formulas for computing upper limits for future sample HorRat values will prove to be useful to Study Directors in determining worst case scenarios concerning a method's reproducibility precision relative to that predicted using the "Horwitz equation". We also define the current empirical HorRat limits as 1-tailed 100p% upper limits to assess the statistical consequence, in a probability sense, of their application as an analytical methods screening tool.     

Mach stem hysteresis: Experiments addressing a novel explanation of clumpy astrophysical jet emission

Recent time-series observations of shock waves in stellar jets taken with the Hubble Space Telescope reveal localized bright knots that persist over nearly 15 years. While some of these features represent shock fronts caused by variable velocities in the flow, others appear at the intersection points between distinct bow shocks. Theoretically, when the angle between two intersecting shocks exceeds a certain critical value, a third shock (Mach stem) should form. Because Mach stems form perpendicular to the direction of flow, incoming particles encounter a normal shock instead of an oblique one, which results in brighter emission at this location. To study this phenomenon in a controlled laboratory setting, we have carried out experiments on the Omega laser aimed at understanding the formation, growth, and destruction of Mach stems in the warm dense plasma regime. Our experimental results indicate how the growth rate depends upon included angle, and numerical simulations indicate that it may be possible to stabilize an already-formed Mach stem below the critical angle when certain conditions are satisfied.     

Ultralow power continuous-wave frequency conversion in hydrogenated amorphous silicon waveguides

We demonstrate wavelength conversion through nonlinear parametric processes in hydrogenated amorphous silicon (a-Si:H) with maximum conversion efficiency of -13 dB at telecommunication data rates (10 GHz) using only 15 mW of pump peak power. Conversion bandwidths as large as 150 nm (20 THz) are measured in continuous-wave regime at telecommunication wavelengths. The nonlinear refractive index of the material is determined by four-wave mixing (FWM) to be n(2)=7.43×10(-13) cm(2)/W, approximately an order of magnitude larger than that of single crystal silicon.