Chemoselectivity control in the reaction of a dinuclear chloro-bridged cyclopalladated complex with potassium diphenylphosphide

Reactions of KPPh₂ with the dimeric cyclopalladated complex {Pd(N∩C)(μ-Cl)}₂1 derived from N,N-dimethylbenzylamine were studied using different reagent ratios, temperature, reaction time, concentrations and solvents. Complex 3, the μ-Cl-μ-PPh₂ analog of 1, was obtained in 76% yield in the one-hour reaction using the 1:1 ratio of dimer 1 and KPPh₂ in THF at rt. ortho-(Diphenylphosphino)benzylamine 4 was synthesized in 58% yield by reacting complex 1 with 4.5 equiv. of KPPh₂ in THF at rt. A possible mechanism of the aminophosphine formation is proposed on the basis of the experimental data including ³¹P{¹H} NMR spectra of reaction mixtures.     

Preparation and characterization of a reduced chromium complex via vinyl oxidative coupling: formation of a self-activating catalyst for selective ethylene trimerization

Reaction of the divalent [(t-Bu)NP(Ph)(2)N(t-Bu)]CrCl(2)Li(THF)(2) (1) with 1 equiv of vinyl Grignard (CH(2)=CH)MgCl reproducibly afforded the triangulo {π-[(t-Bu)N-P(Ph)(2)-N(t-Bu)]Cr}(2)(μ,μ',η(4),η(4)'-C(4)H(4)){σ-[(t-Bu)N-P(Ph)(2)-N(t-Bu)]Cr} (2) containing a σ-/π-bonded butadiene-diyl unit. The diene-diyl moiety was generated by an oxidative coupling and deprotonation of two vinyl anions. The crystal structure revealed that of the three chromium atoms, each bearing one NPN ligand, two are perpendicularly bonded to the two sides of the π-system of the butadiene-diyl residue in a sort of inverted sandwich type of structure. The third is instead coplanar with the doubly deprotonated C(4) unit and σ-bonded to the two terminal carbon atoms. Despite the appearance as a Cr(II)/Cr(I) mixed valence species, DFT calculations have revealed that the structure of 2 consists of three divalent chromium atoms, while the additional electron resides on the π-system of the bridging organic residue. Complex 2 behaves as a single component selective catalyst for ethylene trimerization.     

Cucurbit[6]uril nanocavity as an enhanced spectrofluorimetric method for the determination of pyrene

The effect of the addition of macrocyclic host cucurbit[6]uril (CB6) on the photophysical properties of polycyclic aromatic hydrocarbon pyrene (PYR) was analyzed. The fluorescence emission spectra of the aromatic compound were determined at 25.0 °C in different acidic media (HCl 18%, w/v, or HCOOH 55%, w/v) with and without CB6. A significant enhancement in the fluorescence signals in the presence of CB6 was observed. The average values of the association constant (K_A) for the 1:1 stoichiometry complex and the relative fluorescence quantum yield ratio between the complexed and free PYR (?^PYR–CB6/?^PYR) in acidic media were (4.0 ± 0.5) × 10² M⁻¹ and (5.7 ± 0.2), respectively.The analytical parameters improved in the presence of CB6. The relative decrease in the limit of detection was 92%. The matrix effect was evaluated in fortified samples of tap water and tea extracts. Apparent recoveries obtained by the proposed method in tap water and tea extracts were (82–103)% and (89–99)%, respectively. Selectivity studies with inorganic and organic species were performed. The method is rapid, direct, selective and simple.     

The Mean-Field Limit for Solid Particles in a Navier-Stokes Flow

We propose a mathematical derivation of Brinkman’s force for a cloud of particles immersed in an incompressible viscous fluid. Specifically, we consider the Stokes or steady Navier-Stokes equations in a bounded domain Ω⊂ℝ³ for the velocity field u of an incompressible fluid with kinematic viscosity ν and density 1. Brinkman’s force consists of a source term 6π ν j where j is the current density of the particles, and of a friction term 6π ν ρ u where ρ is the number density of particles. These additional terms in the motion equation for the fluid are obtained from the Stokes or steady Navier-Stokes equations set in Ω minus the disjoint union of N balls of radius ε=1/N in the large N limit with no-slip boundary condition. The number density ρ and current density j are obtained from the limiting phase space empirical measure , where x _k is the center of the k-th ball and v _k its instantaneous velocity. This can be seen as a generalization of Allaire’s result in [Arch. Ration. Mech. Anal. 113:209–259, [1991]] who considered the case of periodically distributed x _k s with v _k =0, and our proof is based on slightly simpler though similar homogenization arguments. Similar equations are used for describing the fluid phase in various models for sprays.     

Phase transitions and magnetoelectric coupling in BiFe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3</Subscript> multiferroics

Multiferroic BiFe_1?xZn _x O₃ ceramics were prepared by solution combustion method. Their structure, magnetoelectric, dielectric, magnetic, thermal characteristics were studied. The magnetic M(T) and heat capacity C _p (T) measurements demonstrate an antiferromagnetic to paramagnetic phase transition (T _N ) around 635 K. The anomaly on the temperature dependence of the dielectric constant near T _N was observed, which could be induced by the magnetoelectric coupling between electric and magnetic ordering. The magnetoelectric behavior was also confirmed by the linear relation between Δε and M², which is in the agreement of the Ginzburg-Landau theory for the second-order phase transition.     

Second Harmonic Probe of Orientational Arrangement of Xanthene Dye Molecules within the Monolayer at the Air/Water Interface

Orientational arrangement of molecules within the monolayers and ultrathin films is old and still fascinating subject of investigations because a number of processes occurring at surfaces are high sensitive both to the intermolecular distance and to the relative orientation of the molecular dipole moments. In this paper second harmonic generation (SHG) was engaged to analyse how dye molecules orient themselves relative to each other and to the surface.     

Polyextremophilic Chitinolytic Activity by a Marine Strain (IG119) of Clonostachys rosea

The investigation for novel unique extremozymes is a valuable business for which the marine environment has been overlooked. The marine fungus Clonostachys rosea IG119 was tested for growth and chitinolytic enzyme production at different combinations of salinity and pH using response surface methodology. RSM modelling predicted best growth in-between pH 3.0 and 9.0 and at salinity of 0–40‰, and maximum enzyme activity (411.137 IU/L) at pH 6.4 and salinity 0‰; however, quite high production (>390 IU/L) was still predicted at pH 4.5–8.5. The highest growth and activity were obtained, respectively, at pH 4.0 and 8.0, in absence of salt. The crude enzyme was tested at different salinities (0–120‰) and pHs (2.0–13.0). The best activity was achieved at pH 4.0, but it was still high (in-between 3.0 and 12.0) at pH 2.0 and 13.0. Salinity did not affect the activity in all tested conditions. Overall, C. rosea IG119 was able to grow and produce chitinolytic enzymes under polyextremophilic conditions, and its crude enzyme solution showed more evident polyextremophilic features. The promising chitinolytic activity of IG119 and the peculiar characteristics of its chitinolytic enzymes could be suitable for several biotechnological applications (i.e., degradation of salty chitin-rich materials and biocontrol of spoiling organisms, possibly solving some relevant environmental issues).     

On the clathrate structures of syndiotactic poly(m-methylstyrene)

The crystal structures of clathrate forms of syndiotactic poly(m-methylstyrene) containing guest molecules having different steric hindrance (CS₂, benzene and orto-dichlorobenzene) are presented. The structures are all characterized by polymer chains in s (2/1)2 helical conformation and guest molecules packed in an orthorhombic unit cell according to the space group Pcaa. All the presented clathrates belongs to β class indipendently from the dimensions of the guest molecule. In this aspect they differ both from clathrate forms of syndiotactic polystyrene, all belonging to α class, and from clathrate forms of syndiotactic poly(p-methylstyrene) that belong to α or β class according to the steric hindrance of the guest molecule.     

Effect of Pluronic P103 Concentration on the Simple Synthesis of Ag and Au Nanoparticles and Their Application in Anatase-TiO2 Decoration for Its Use in Photocatalysis

Silver and gold nanoparticles were synthesized under environmentally-friendly reaction conditions by using a biodegradable copolymer and water as a solvent. The triblock copolymer Pluronic P103 was utilized as a stabilizing agent or soft template to produce Ag and Au nanoparticles (NPs) of different sizes. Moreover, in the synthesis of Au NPs, the polymer acted as a reducing agent, decreasing the number of reagents used and consequently the residues produced, hence, rendering the procedure less complicated. It was observed that as the concentration of the polymer increased, the size of the metallic NPs augmented as well. However, AgNPs and AuNPs prepared with 1 and 10 wt% Pluronic P103, respectively, showed a significant decrease in particle size due to the presence of polymeric soft templates. The hybrid materials (metal/polymer) were characterized by UV-Vis spectroscopy, DLS, and TEM. The pre-synthesized nanoparticles were employed to decorate anatase-TiO₂, and the composites were characterized by DRS, XRD, BET surface area measurements, the TEM technique with the EDS spectrum, and XPS spectroscopy to demonstrate NPs superficial incorporation. Finally, methylene blue was used as a probe molecule to evidence the effect of NPs decoration in its photocatalytic degradation. The results showed that the presence of the NPs positively affected methylene blue degradation, achieving 96% and 97% removal by utilizing TAg0.1 and TAu10, respectively, in comparison to bare anatase-TiO₂ (77%).     

Group 4 Metallocene Catalysts with Hapto‐Flexible Cyclopentadienyl‐Aryl Ligand

Catalytic precursors Ti(IV) and Zr(IV) complexes bearing cyclopentadienyl and substituted cyclopentadienyl anionic ligands, bonded to phenyl or substituted phenyl through an isopropylidene bridge have been utilized in the polymerization of propene and styrene and in ethylene‐styrene copolymerization. In the presence of trichloro[(1,2,3,4,5‐η)‐1‐(1‐methyl‐1‐phenylethyl)‐2,4‐cyclopentadien‐1‐yl]titanium (LTiCl₃) we have obtained either partially isotactic (chain‐end type) or atactic poly‐(propylene), and either atactic or syndiotactic polystyrene depending on the reaction temperature. [1‐Methyl‐1‐naphthylethyl‐2‐inden‐1‐yl]titanium(IV) behaves like (LTiCl₃) in styrene polymerization, while it affords metal‐controlled partially isotactic poly(propylene), as well as the corresponding zirconium compounds. The experimental data are tentatively explained by the temperature dependence of coordination of the bridged aryl group of the ligand.