A simple and very sensitive spectrophotometric method for the direct determination of copper ions

A sensitive spectrophotometric method for the direct determination of copper in aqueous samples without a preconcentration step has been developed. It is based on the formation of a yellow complex with the chromogenic reagent di-2-pyridyl ketone benzoylhydrazone (dPKBH) in an alkaline medium. The complex stoichiometry was 1:2 (Cu:dPKBH) and presents maximum absorbance at 370 nm. The influence of chemical variables affecting the behaviour of the system such as pH, concentration of dPKBH, buffer solution and ethanol, order of addition of the reagents and stability of the complex, were evaluated. The molar absorptivity (epsilon) was 3.92x10(4) L mol(-1) cm(-1), and Beer's law was obeyed up to 3 mg L(-1) of copper. The relative standard deviation was 0.46% (n=11) for a sample containing 1 mg L(-1) Cu(II). The limit of detection was 2.5 micro g L(-1) and was therefore more sensitive than the direct methods reported previously. Finally, the method was successfully validated by analysing several real samples with different matrices, such as tap water, natural water or copper alloys, with an average relative error of 2.46%.     

Thermal and mechanical-induced phase transformations during YAG and alumina–YAG syntheses

The preparation of pure Y₃Al₅O₁₂ (YAG) and 50 vol% Al₂O₃–YAG composite powders by a wet chemical route is presented. The role of the synthesis temperature during reverse-strike precipitation has been investigated, showing its relevant effect on the purity and homogeneity of YAG powder. The composite material was prepared by comparing two different synthesis routes. A composite powder was synthesized via reverse-strike temperature-controlled co-precipitation. In the latter case, a pure-alumina precursor was firstly reverse-strike precipitated and then doped with an yttrium salt solution. For both syntheses, the role of thermal and mechanical pre-treatments on the phase development was demonstrated.     

Additional peaks in the cluster size distribution of amphiphile + water systems: a clue for shape/phase transition or statistical uncertainty

In some works on the lattice Monte Carlo simulation of amphiphilic systems additional peaks in the cluster size distribution has been interpreted as a clue for the phase or shape transition of micellar aggregates. On the other hand, some other works showed that the additional peaks are a result of finite size of the lattice box. In this paper using calculating energy-auto-correlation function and statistical error in correlated data, it is shown that how these apparently contradictory results are the same. To do this, we have simulated a pure system containing amphiphile and water molecules. A simple model of potential containing the main feature for these systems (the hydrophobicity of surfactant molecules) that cause the aggregates to be formed is considered to avoid any synthetic results due to additional non-real parameters. To relax the initial configuration faster, configurational bias Monte Carlo move is used in addition to reptation move. Periodic boundary condition and self-avoiding walks are used as former published works in this field. It is shown that the additional peaks is a result of the statistical errors for averaged cluster size distribution and can not be interpreted as a clue for shape or phase transition.     

Kinetics of Oxidation of 4-Oxoacids by <Emphasis Type="Italic">N</Emphasis>-Chlorosaccharin in Aqueous Acetic Acid Medium

The oxidation kinetics of substituted and unsubstituted 4-oxoacids (S) by N-chlorosaccharin (NCSA) have been studied in aqueous acetic acid media. The reaction follows first-order kinetics in each of the 4-oxoacids, NCSA and H⁺. The effect of changes in the electronic nature of the substrate reveals that positive charge develops in the transition state. Based on the kinetic results and product analysis, a suitable mechanism has been proposed for the reaction of NCSA with 4-oxoacids.     

Copolymers and two-layered composites of poly(<Emphasis Type="Italic">o</Emphasis>-aminophenol) and polyaniline

Electroactive conducting copolymers of aniline (ANI) and o-aminophenol (OAP) and two-layered poly(o-aminophenol) (POAP)/polyaniline (PANI) composites were prepared in aqueous acidic solution by electrode potential cycling. Copolymerization was carried out at different feed concentrations of OAP and ANI on a gold electrode. A strong inhibition of electropolymerization was found at a high molar fraction of OAP in the feed. The copolymers showed good adherence on the electrode surface and gave a redox response up to pH=10.0. Two transitions were observed in the in situ conductivities of the copolymers (as with PANI), but the conductivities were lower by 2.5–3 orders of magnitude as compared to PANI. Electrosynthesis of PANI on POAP modified electrodes showed copolymer formation after reaction initiation and finally formation of a PANI layer at the copolymer/solution interface. The ‘memory effect’ of the bilayer structures of both polymers was discussed in terms of protonation/deprotonation and anion consumption taking place during redox processes of both polymers.     

Ligand influence on the electrochemical behavior of some copper(II) thiosemicarbazone complexes

The redox properties of the title mono- and binuclear copper(II) chelates have been investigated by cyclic voltammetry in DMF at a working platinum electrode. The cathodic reduction and anodic oxidation of the investigated chelates produced the corresponding electrochemical Cu^I and Cu^IIIspecies stable only in the voltammetric time scale, The effects of substituents on E_1/2, redox properties and stability towards oxidation of the complexes were related to the electron-withdrawing or releasing ability of the substituents on the C=N¹[H, CH₃ or C₆H₅] and/or N⁴H [H, C₂H₅, C₆H₅ or pClC₆H₄] groups, The electron attracting substituents stabilize the Cu(II) complexes while electron-donating groups favor oxidation to Cu(III). Changes in the E_1/2 for the complexes due to remote substituent effects could be related to changes in basicity of N⁴H.Thus, variation in N⁴1-J has more influence on E_1/2 than changes in C=N¹. The correlation between E_1/2 of the complexes and pK_a of the ligands has been attributed to the spherical potential generated by the electron density of the donor atoms at the antibonding d orbitals.     

Graphs to chemical structures. 4: Combinatorial enumeration of planted three-dimensional trees as stereochemical models of monosubstituted alkanes

Planted three-dimensional (3D) trees, which are defined as a 3D version of planted trees, are enumerated by means of Fujita’s proligand method formulated in Parts 1–3 of this series [Fujita in Theor Chem Acc 113:73–79, 80–86, 2005; Fujita in Theor Chem Acc 115:37–53, 2006]. By starting from the concepts of proligand and promolecule introduced previously [Fujita in Tetrahedron 47:31–46, 1991], a planted promolecule is defined as a 3D object in which the substitution positions of a given 3D skeleton are occupied by a root and proligands. Then, such planted promolecules are introduced as models of planted 3D-trees. Because each of the proligands in a given planted promolecule is regarded as another intermediate planted promolecule in a nested fashion, the given planted promolecule is recursively constructed by a set of such intermediates planted promolecules. The recursive nature of such intermediate planted promolecules is used to derive generating functions for enumerating planted promolecules or planted 3D-trees. The generating functions are based on cycle indices with chirality fittingness (CI-CFs), which are composed of three kinds of sphericity indices (SIs), i.e., a _d for homospheric cycles, c _d for enantiospheric cycles, and b _d for hemispheric cycles. For the purpose of evaluating c _d recursively, the concept of diploid is proposed, where the nested nature of c _d is demonstrated clearly. The SIs are applied to derive functional equations for recursive calculations, i.e., a(x), c(x ²), and b(x). Thereby, planted 3D-trees or equivalently monosubstituted alkanes as stereoisomers are enumerated recursively by counting planted promolecules. The resulting values are collected up to 20 carbon content in a tabular form. Now, the enumeration problem initiated by mathematician Cayley [Philos Mag 47(4):444–446, 1874] has been solved in such a systematic and integrated manner as satisfying both mathematical and chemical requirements.     

Effects of thioamide substitutions on the conformation and stability of alpha- and 3(10)-helices

Thiopeptides, formed by replacing the amide oxygen atom with a sp(2) sulfur atom, are useful in protein engineering and drug design because they confer resistance to enzymatic degradation and are predicted to be more rigid. This report describes our free molecular dynamics simulations with explicit water and free energy calculations on the effects of thio substitutions on the conformation of alpha-helices, 3(10)-helices, and their relative stability. The most prominent structural effect of thio substitution is the increase in the hydrogen bond distance from 2.1 A for normal peptides to 2.7 A for thiopeptides. To accommodate for the longer C[double bond]S...H-N hydrogen bond, the (phi, psi) dihedral angles of the alpha-helix changed from (-66 degrees, -42 degrees) to (-68 degrees, -38 degrees), and the rise per turn increased from 5.5 to 6.3 A. For 3(10)-helices, the (phi, psi) dihedral angles (-60 degrees, -20 degrees) and rise per turn (6.0 A) changed to (-66 degrees, -12 degrees) and 6.8 A, respectively. In terms of relative stability, the most prominent change upon thio substitution is the decrease in the free energy difference, Delta A(alpha --> 3(10)), from 14 to 3.5 kcal/mol. Therefore, normal peptides are less likely to form 3(10)-helix than are thiopeptides. Component analysis of the Delta A(alpha --> 3(10)) reviews that the entropy advantage of the 3(10)-helix for both Ac-Ala(10)-NHMe and Act-Alat(10)-NHMe is attributed to the 3(10)-helix being more flexible than the alpha-helix. Interestingly, upon thio substitution, this differential flexibility is even more apparent because the alpha-helix conformation of Act-Alat(10)-NHMe becomes more rigid due to the bulkier sulfur atom.     

Cellulose microfibrils from banana farming residues: isolation and characterization

Cellulose microfibrils have been prepared from banana rachis using a combination of chemical and mechanical treatments. The morphology and structure of the samples were characterized using transmission electron microscopy, atomic force microscopy, and X-ray diffraction. Fourier-transformed infrared spectroscopy (FTIR) was used to characterize the chemical modifications of the samples after each treatment. Suspensions of bundled or individualized 5-nm-wide microfibrils were obtained after homogenization (PH) whereas an organosolv (PO) treatment resulted in shorter aggregates of parallel cellulose microcrystallites. The sharper rings in the X-ray diffraction pattern of the PO-treated sample suggest a higher crystallinity due to a more efficient removal of hemicelluloses and dissolution of amorphous zones by the acid treatment. Both microfibrils and microcrystals prepared by both methods can be used as reinforcing filler in nanocomposite materials.