Dipolar donor-acceptor-substituted schiff base complexes with large off-diagonal second-order nonlinear optical tensor components

The synthesis, characterization, and two-dimensional second-order nonlinear optical (NLO) response of a dipolar NiII donor- acceptor Schiff base complex and the related ligand are reported. Electric-field-induced second-harmonic generation and harmonic light (hyper-Rayleigh) scattering techniques, in combination with INDO/SCI-SOS theoretical calculations, were used to investigate the vector part of the hyperpolarizability tensor and the two-dimensional character of the molecular nonlinearity, respectively. Off-diagonal hyperpolarizability tensors can be related to charge-transfer transitions that are polarized perpendicular to the molecular dipolar axis, while parallel transitions account for the diagonal hyperpolarizability tensor. The role of the metal center in enhancing the two-dimensional NLO response of such molecules is twofold since it acts both as the donor and the bridging moiety of the planar donor-(pi-conjugate-bridge)-acceptor system. These dipolar two-dimensional molecules are interesting candidates from the perspective of polarization-independent NLO materials.     

Extreme values and a Gaussian central limit theorem

Summary We examine the central limit theorem with Gaussian limit law for a sequence of independent, identically distributed, vector valued random variables whose partial sums can be centered and normalized to be tight with non-degenerate limit laws. These results apply to the situation when the sequence is in the domain of attraction of a non-degenerate stable law of indexp(0,2], and are achieved by eliminating the extreme values from the partial sums.Supported in part by NSF Grant MCS-8219742Work done while visiting the University of Wisconsin, Madison, with partial support by NSF Grant MCS-8219742     

Numeration methods for targeting photoactive materials in the UV-A photocatalytic removal of microorganisms

This tutorial review reports on the different numeration methods for evaluating the efficiency of the photocatalytic action on microorganisms. Here we put forward the advantages and drawbacks of the standard methods such as the plate count, the fluorescence techniques and the Most Probable Number method for determining the biocidal photocatalytic activity and thus selecting efficient photocatalytic materials among complex systems. We highlight that bacterial spores are a representative and suitable tool for meeting the restrictive requirements resulting from the complex use of living matter instead of chemical targets.     

Homogeneous dispersion of gadolinium oxide nanoparticles into a non-aqueous-based polymer by two surface treatments

Gadolinium oxide nanoparticles are more and more used. They can notably provide interesting fluorescence properties. Herein they are incorporated into a non-aqueous-based polymer, the poly(methyl methacrylate). Their dispersion within the polymer matrix is the key to improve the composite properties. As-received gadolinium oxide nanopowders cannot be homogeneously dispersed in such a polymer matrix. Two surface treatments are, therefore, detailed and compared to achieve a good stability of the nanoparticles in a non-aqueous solvent such as the 2-butanone. Then, once the liquid suspensions have been stabilized, they are used to prepare nanocomposites with homogeneous particles dispersion. The two approaches proposed are an hybrid approach based on the growth of a silica shell around the gadolinium oxide nanoparticles, and followed by a suitable silane functionalization; and a non-hybrid approach based on the use of surfactants. The surface treatments and formulations involved in both methods are detailed, adjusted and compared. Thanks to optical methods and in particular to the use of a ??home made?? confocal microscope, the dispersion homogeneity within the polymer can be assessed. Both methods provide promising and conclusive results.     

Monitoring the chemical vapor deposition growth of multiwalled carbon nanotubes by tapered element oscillating microbalance

The growth of multiwalled carbon nanotubes (MWCNTs) produced by a catalytic chemical vapor deposition (CCVD) process has been monitored using a tapered element oscillating microbalance (TEOM) probe. This technique displays a high sensitivity (<1 microg). Growths in the TEOM microreactor are investigated with catalytic particles (Fe, Ni) dispersed on different supports. First, high surface area FeAl2O3 or Fe (Ni) exchanged on zeolite powders is used. Second, growths are performed on array of nickel dots or FeSi-nc particles dispersed on large holes patterned on Si(100) substrates. An accurate monitoring of the early stages of growth permits a precise evaluation of the growth rates and shows substantial differences between these samples which greatly differ by the surface area. On catalysts dispersed on Si(100) the mass uptake is linear throughout the process. On high surface area catalysts, however, a saturation of the mass uptake is indifferently observed. This saturation is explained either by diffusion limitation by the growing MWCNTs or by internal diffusion through the pores or external diffusion through the grains of the catalyst. The kinetic dependence with partial pressure of the incoming C2H6:H2 gas mixture is then explored on the FeAl2O3 catalyst. A linear dependence of the MWCNT growth an (P(C2H6)/P(H2))(1/2) is found. A simple model is then developed that accounts for this dependence only if an associative and competitive adsorption of ethane is the rate determining step of the overall process. These results thus bring insight to improve and control the CCVD growth kinetics of MWCNTs.     

Direct Synthesis of Hexagonal NaGdF4 Nanocrystals from a Single‐Source Precursor: Upconverting NaGdF4:Yb3+,Tm3+ and Its Composites with TiO2 for Near‐IR‐Driven Photocatalysis

A novel single‐source precursor NaGd(TFA)₄(diglyme) (TFA=trifluoroacetate) was synthesized, characterized thoroughly, and used to obtain the hexagonal phase of NaGdF₄ nanoparticles as an efficient matrix for lanthanide‐doped upconverting nanocrystals (NCs) that convert near‐infrared radiation into shorter‐wavelength UV/visible light. These NCs were then used to prepare well‐characterized TiO₂@NaGdF₄:Yb³⁺,Tm³⁺ nanocomposites to extend the absorption range of the TiO₂ photocatalyst from the UV to the IR region. While the visible/near IR part of the photoluminescent spectra remains almost unaffected by the presence of TiO₂, the UV part is strongly quenched due to the absorption of TiO₂ above its gap at approximately 380 nm by energy transfer or FRET. Preliminary results on the photocatalytic activity of the above obtained nanocomposites are presented.     

Tuning the Dipolar Second‐Order Nonlinear Optical Properties of Cyclometalated Platinum(II) Complexes with Tridentate N^C^N Binding Ligands

Appropriate functionalization of the cyclometalated ligand, L , and the choice of the ancillary ligand, X, allows the dipolar second‐order nonlinear optical response of luminescent [Pt L X] complexes—in which L is an N^C^N‐coordinated 1,3‐di(2‐pyridyl)benzene ligand and X is a monodentate halide or acetylide ligand—to be controlled. The complementary use of electric‐field‐induced second‐harmonic (EFISH) generation and harmonic light scattering (HLS) measurements demonstrates how the quadratic hyperpolarizability of this appealing family of multifunctional chromophores, characterized by a good transparency throughout much of the visible region, is dominated by an octupolar contribution.