Effects of cerium dopant concentration on structural properties and photocatalytic activity of electrospun Ce-doped TiO2 nanofibers

Electrospun \(\hbox {TiO}_2\) and Ce-doped \(\hbox {TiO}_2\) nanofibers were prepared with 0.5, 2.0 and 8.0 % weight Ce. The structural properties and phase composition were characterized using high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction and X-ray absorption near edge spectroscopy (XANES) at the Ti K-edge. The undoped nanofibers are composed of an assembly of \(\hbox {TiO}_2\) nanoparticles and their crystal structure is a mixture of anatase and rutile phases with an anatase:rutile volume ratio close to 3:1. As Ce is introduced, the nanoparticles decrease in size and the rutile phase volume decreases. Ce \(\hbox {L}_3\) -edge XANES probed the local structure of Ce dopants. At 0.5 % Ce, most Ce ions are incorporated in the \(\hbox {Ce}^{3+}\) charge state but, at 2 % Ce, the majority are \(\hbox {Ce}^{4+}\) . Visible light absorption indicated that \(\hbox {Ce}^{3+}\) act as shallow acceptors that only participate in absorption of wavelengths below 420 nm but \(\hbox {Ce}^{4+}\) impurity states are associated with absorption of wavelengths up to 550 nm. Photocatalytic performance of the nanofibers was assessed by measuring the degradation of adsorbed Rhodamine B in aqueous solution under visible and ultraviolet light. The 0.5 % Ce-doped \(\hbox {TiO}_2\) nanofiber showed the best visible-light photocatalytic activity, which is probably due to the majority presence of \(\hbox {Ce}^{3+}\) . At higher Ce concentration, the photocatalytic reaction rate was lower than undoped nanofibers, indicating that recombination at the \(\hbox {Ce}^{4+}\) sites is rate limiting.     

Crystal structure and molecular modeling of 17-DMAG in complex with human Hsp90

Hsp90 is an attractive chemotherapeutic target because it chaperones the folding of proteins found in multiple signal transduction pathways. We describe the 1.75 A resolution crystal structure of human Hsp90 alpha (residues 9-236) complexed with 17-desmethoxy-17-N,N-dimethylaminoethylamino-geldanamycin (17-DMAG). The structure revealed an altered set of interactions between the 17-substituent and the protein compared to geldanamycin and the 17-dimethylaminoethyl moiety pointing into solvent, but otherwise was similar to that reported for the complex with geldanamycin. Targeted molecular dynamics simulations and energetic analysis indicate that geldanamycin undergoes two major conformational changes when it binds Hsp90, with the key step of the conversion being the trans to cis conformational change of the macrocycle amide bond. We speculate that 17-DMAG analogs constrained to a cis-amide in the ground state could provide a significant increase in affinity for Hsp90.     

Modeling traffic flow correlation using DFA and DCCA

An electrical analogue model has been developed based on main leaf hydraulics characteristics and intrinsic geometry. The simulations show good qualitative agreements with specialized literature reports. The constant-phase behavior and the variation with ambient temperature of the frequency response of the leaf impedance are assessed by means of simulation studies.     

Synthesis, structure and reactivity of homobimetallic Rh(I) and Ir(I) complexes of s- and as-indacene-diide

The Rh(COD) and Ir(COD) homobimetallic complexes of s-indacene-diide, 2,6-dimethyl-s-indacene-diide, as-indacene-diide, and 2,7-dimethyl-as-indacene-diide have been synthesized from the di-lithium salts of the dianions and metal dimers [M(μ-Cl)L₂]₂ (M = Rh, Ir; L₂ = COD, NBD, (ethylene)₂, (CO)₂ as mixtures of syn and anti isomers. The syn/anti ratio depends on the nature of the ancillary ligands at the metal and on the s or as geometry of the bridging ligand. In the reaction of the 2,7-dimethyl-as-indacene-diide-[M(COD)]₂ species with CO, the higher reactivity of the syn isomers has been justified on the basis of a greater instability of the ground state due to steric interactions between the COD groups. Bis-η¹ metal-bonded intermediates have been identified in the carbonylation of iridium derivatives; on the other hand, the formation of the bis-η⁵ mixed complexes syn and anti-{2,7-dimethyl-as-indacene-diide-[Rh(COD)][Rh(CO)₂]} and their reactivity strongly support the existence of metal---metal interaction in the rhodium derivatives.     

Self-Assembled Binaphthyl-Bridged Amphiphilic AABB Phthalocyanines: Nanostructures for Efficient Antimicrobial Photodynamic Therapy

Herein, the photodynamic activity of phthalocyanine (pc)-assembled nanoparticles against bacterial strains is demonstrated. The photosensitizers (PS) studied in this work are two chiral Zn^IIPcs ( PS-1 and PS-2 ), with an AABB geometry (where A and B refer to differently substituted isoindole constituents). They contain differently functionalized, chiral binaphthyloxy-linked A isoindole units, which determine the hydrophobicity of the system, and cationic methyl pyridinium moieties in the other two isoindoles to embody hydrophilicity. Both compounds have the ability to self-assemble into nanoparticles in aqueous media and have proved efficient in the photo-inactivation of Staphylococcus aureus and Escherichia coli, selected as models of Gram-positive and Gram-negative bacteria. The average size of the nanoparticles was determined by substitution at the binaphthyl core and, in turn, influences the toxicity of the PS. Thus, PS-1 , presenting a nonsubstituted binaphthyl core, forms larger nanoparticles with a larger cationic surface than the octyl-functionalized PS-2 . Although both PSs present similar structure and photophysical features, the self-assembled nanostructures of PS-1 are more effective at killing both types of strain, showing an outstanding photo-inactivation capacity with the Gram-negative E. coli.     

Esistenza ed unicita’ delle soluzioni di un problema misto per un sistema iperbolico simmetrico con coefficienti discontinui

In this paper we give existence and uniqueness theorems for weak solutions of a mixed initial and boundary value problem with conservative boundary conditions relating to a particular symmetric hyperbolic linear system with discontinuous coefficients. The unicity is proved also for a mixed non linear problem.     

A Generalized Modulation Law for Generating Constant-Envelope Signals Via Frequency Modulation

In this paper we generalize the calculus of the power density spectrum (PDS) of a constant-envelope spread-spectrum (CE-SS) signal obtained by means of a frequency modulation (FM) using a random pulse amplitude modulated (PAM) signal as the modulation law made by a generic pulse function. We choose two possible profile of such pulses aiming to approximate those generated by the analog circuit implementing the chaotic map and we present both analytical and numerical results that show how the pulse shape affect the PDS shape of the modulated signal.