A new method for obtaining adsorption isotherms on colloidal suspensions via electrokinetic sonic amplitude measurement

The standard methods for obtaining adsorption isotherms on colloidal suspensions are usually very time consuming and involve a large number of steps and assumptions that increase the experimental errors. In this work, an alternative method is proposed to evaluate the adsorption behavior of electrosteric-stabilized systems based on electrokinetic sonic amplitude signal measurements. The new method, entitled "zeta-sorption", is noticeably less time-consuming when compared to conventional procedures but showed great precision and reliability confirmed by comparison with data obtained from conventional routes on alumina-polyacrylate and alumina-citric acid aqueous suspensions. The experimental conditions that restrict the applicability of the new method were identified and justified by discussing the possible ion exchanges.     

Solvent dependent conformational isomerism and ligand oxidation of novel Ru(II) cyclen complexes

The synthesis of cis-[Ru(II)(cyclen)(L)(x)](n+) (cyclen = 1,4,7,10-tetraazacyclododecane and L = 2,2'-bipyridine (bpy), phenanthroline (phen) or 4-cyanopyridinium (4-NCpyH(+))) is reported. The freshly prepared complexes are stable in aprotic solvents and cyclen undergoes oxidative dehydrogenation reaction at high pH. These compounds also present solvent dependent conformational isomerization.     

Influence of increasing zinc contents in brass in the early stages of corrosion investigated by in-situ TM-AFM and SIMS

In-situ tapping mode atomic force microscopy (TM-AFM), a powerful, high-resolution imaging technique for determining the structure of surfaces and ex-situ secondary ion mass spectroscopy (SIMS), a multielement, high-depth-resolution method, were used to examine the influence of increasing zinc contents in brass in the early stages of corrosion. Four different samples (pure Cu, pure Zn, Cu/Zn=90/10 wt% and Cu/Zn=70/30 wt%) were studied in order to determine their chemical behaviour under various atmospheric conditions. The in-situ TM-AFM investigations were carried out in synthetic air with 60% relative humidity (RH) and 80% RH with 250 ppb SO(2). The samples for the ex-situ SIMS experiments were weathered over a period of 60 h in 80% RH and 250 ppb SO(2). The in-situ TM-AFM investigations have shown that an increasing Zn content in brass increases the corrosion rate.     

A synthetic approach to bicyclo[6.2.1]undecane ring systems

A synthesis of a functionalized bicyclo[6.2.1]undecane, N-(7-hydroxymethyl-bicyclo[6.2.1]undeca-3,5,9-trien-2-yl)-4-methyl-benzenesulfonamide, is described. Starting with a [6+4] cycloaddition between cyclopentadiene and cycloheptatrienone, the final product was prepared in five steps with an overall 37% yield. The remarkable resistance to hydrolysis of an intermediate lactam was overcome by tosylating the amide and reducing with LiAlH₄.     

Synthesis and photophysical evaluations of β-fused uracil-porphyrin derivatives

New β-fused uracil-porphyrin conjugates were synthesized by the tetramerization of uracil-pyrroles under acidic conditions. Two different synthetic approaches were systematically studied in order to evaluate their efficiency, as well as the possibility to obtain a single regioisomer. Metallation effects were studied for aggregation in solution, and preliminary photophysical experiments were also performed in order to evaluate the potential of these new compounds.     

Synthesis of the bicyclo[6.2.1]undecane ring system by a solvent-free Diels–Alder reaction

A bicyclo[6.2.1]undecane model compound of the core structure of the biologically active furanoheliangolide sesquiterpene was synthesized. This new and short route was developed by using a solvent-free Diels–Alder reaction between cyclopentadiene and 3-nitro-2-cyclohexenone, followed by simple transformations. Theoretical calculations were performed in order to understand reactivity aspects of the cycloaddition.     

Synthesis of New Chlorin e6 Trimethyl and Protoporphyrin IX Dimethyl Ester Derivatives and Their Photophysical and Electrochemical Characterizations

In view of increasing demands for efficient photosensitizers for photodynamic therapy (PDT), we herein report the synthesis and photophysical characterizations of new chlorin e₆ trimethyl ester and protoporphyrin IX dimethyl ester dyads as free bases and Zn^II complexes. The synthesis of these molecules linked at the β‐pyrrolic positions to pyrano[3,2‐c]coumarin, pyrano[3,2‐c]quinolinone, and pyrano[3,2‐c]naphthoquinone moieties was performed by using the domino Knoevenagel hetero Diels–Alder reaction. The α‐methylenechromanes, α‐methylenequinoline, and ortho‐quinone methides were generated in situ from a Knoevenagel reaction of 4‐hydroxycoumarin, 4‐hydroxy‐6‐methylcoumarin, 4‐hydroxy‐N‐methylquinolinone, and 2‐hydroxy‐1,4‐naphthoquinone, respectively, with paraformaldehyde in dioxane. All the dyads as free bases and as Zn^II complexes were obtained in high yields. All new compounds were fully characterized by 1D and 2D NMR techniques, UV/Vis spectroscopy, and HRMS. Their photophysical properties were evaluated by measuring the fluorescence quantum yield, the singlet oxygen quantum yield by luminescence detection, and also the triplet lifetimes were correlated by flash photolysis and intersystem crossing (ISC) rates. The fluorescence lifetimes were measured by a time‐correlated single photon count (TCSPC) method, fluorescence decay associated spectra (FDAS), and anisotropy measurements. Magnetic circular dichroism (MCD) and circular dichroism (CD) spectra were recorded for one Zn^II complex in order to obtain information, respectively, on the electronic and conformational states, and interpretation of these spectra was enhanced by molecular orbital (MO) calculations. Electrochemical studies of the Zn^II complexes were also carried out to gain insights into their behavior for such applications.     

Tunneling from a 3-dimensional quantum well in an electric field: an analytic solution

We derive the stationary tunneling solution for charged particles moving in a spherical, 3-dimensional zero-range potential plus a constant electric field. From the analytic expression for the wave function we calculate the distribution of the current inside and outside the vacuum barrier. At low field strengths there is a constant spreading of the tunnel current orthogonal to the direction of the applied field. At intermediate field strengths the exact results for the current distribution behave different from the semiclassical predictions.     

Anisotropic scalar field with cosmical time

A static, plane-symmetric scalar field of long range is considered in general relativity, and a one-parameter class of exact solutions with cosmical time is studied in harmonic coordinates. The geodetic equations are solved. A velocity-dependent acceleration field is found, acting attractively on the component of the velocity normal to the plane of symmetry, and repulsively on the component parallel to that plane. The manifold is complete. Test particles at rest are insensitive to it.