Synthesis, characterization and photophysical properties of benzidine-based compounds

The N-alkylation of the 3,3′-diaminobenzidine with innocent substituents leads to unusual properties. The emission of the benzidine core can be fine-tuned by subtle modifications, and the N-substitution with benzylic groups results in photoinduced exciplexes with distinct and increased emission. This compound constitutes the first example of intramolecular exciplex containing benzidine unit. We also show that these photoinduced processes could be modulated by proton input, and that the diprotonation of the benzidine core disrupted the intramolecular communication in the excited states with a concomitant inhibition of the ligand-centred fluorescence. Furthermore, upon photo-irradiation at 254 nm, semiquinone imine and quinone diimine systems are produced in CH₂Cl₂ of which the photolysis generates Cl radicals, which rapidly oxidize the tetraamine compounds.     

A new biosynthesis of CuCo2S4 nanoparticles as a high-performance supercapacitor electrode and excellent non-enzymatic hydrazine sensor

In this work, we report the biosynthesis of CuCo₂S₄ nanoparticles (Bio-NPs) via hydrothermal method. The synthetized Bio-NPs-CuCo₂S₄ was studied as an active material of working electrode for electrochemical supercapacitor and non-enzymatic hydrazine sensor. The Bio.NPs-CuCo₂S₄/ITO electrode has a specific capacitance of 264 F/g at a current density of 1 A/g. Meanwhile, the electrode exhibits excellent electrochemical performances, such as an energy density of 33 Wh/Kg and a power density of 900 W/Kg. The Bio.NPs-CuCo₂S₄/ITO electrode for non-enzymatic hydrazine sensor exhibits a very high sensitivity of 2400 μA.mM⁻¹.cm⁻², a wide linear range from 0.001 to 1.400 mM and shows an excellent selectivity.     

Reactivity of molecular dioxygen towards a series of isostructural dichloroiron(III) complexes with tripodal tetraamine ligands: general access to mu-oxodiiron(III) complexes and effect of alpha-fluorination on the reaction kinetics

We have synthesized the mono, di-, and tri-alpha-fluoro ligands in the tris(2-pyridylmethyl)amine (TPA) series, namely, FTPA, F(2)TPA and F(3)TPA, respectively. Fluorination at the alpha-position of these nitrogen-containing tripods shifts the oxidation potential of the ligand by 45-70 mV per added fluorine atom. The crystal structures of the dichloroiron(II) complexes with FTPA and F(2)TPA reveal that the iron center lies in a distorted octahedral geometry comparable to that already found in TPAFeCl(2). All spectroscopic data indicate that the geometry is retained in solution. These three isostructural complexes all react with molecular dioxygen to yield stable mu-oxodiiron(III) complexes. Crystal structure analyses are reported for each of these three mu-oxo compounds. With TPA, a symmetrical structure is obtained for a dicationic compound with the tripod coordinated in the kappa(4)N coordination mode. With FTPA, the compound is a neutral mu-oxodiiron(III) complex with a kappa(3)N coordination mode of the ligand. Oxygenation of the F(2)TPA complex gave a neutral unsymmetrical compound, the structure of which is reminiscent of that already found with the trifluorinated ligand. On reduction, all mu-oxodiiron(III) complexes revert to the starting iron(II) species. The oxygenation reaction parallels the well-known formation of mu-oxo derivatives from dioxygen in the chemistry of porphyrins reported almost three decades ago. The striking feature of the series of iron(II) precursors is the effect of the ligand on the kinetics of oxygenation of the complexes. Whereas the parent complex undergoes 90 % conversion over 40 h, the monofluorinated ligand provides a complex that has fully reacted after 30 h, whereas the reaction time for the complex with the difluorinated ligand is only 10 h. Analysis of the spectroscopic data reveals that formation of the mu-oxo complexes proceeds in two distinct reversible kinetic steps with k(1) approximately 10 k(2). For TPAFeCl(2) and FTPAFeCl(2) only small variations in the k(1) and k(2) values are observed. By contrast, F(2)TPAFeCl(2) exhibits k(1) and k(2) values that are ten times higher. These differences in kinetics are interpreted in the light of structural and electronic effects, especially the Lewis acidity at the metal center. Our results suggest coordination of dioxygen as an initial step in the process leading to formation of mu-oxodiiron(III) compounds, by contrast with an unlikely outer-sphere reduction of dioxygen, which generally occurs at negative potentials.     

Trends in CE-MS 2005-2006

CE-MS has gained further attention as a multidimensional analytical approach. The number of publications dealing with this technique is still increasing on the level of application as well as method development-oriented approaches. Additionally, 15 reviews were published the last two years focusing on CE-MS. An overview of all papers found to have been published within 2005 and 2006 is given in tabulated form. Additionally, four promising technical trends are chosen to be presented in detail: (i) chip-based CE-MS, (ii) capillary coatings in CE-MS, (iii) new trends in CEC-MS and (iv) the application of 2-D CE-MS.     

Effects of modifications of the heteroatoms on fine-tuning the photophysical proprieties of A-π-D-π-A small molecules for photovoltaic applications

An effective way to enhance the photovoltaic properties of a small molecule is to modify the side groups into donor units. Herein three news small molecules A-π-D-π-A, denoted Dye1-3, have been designed, from experimentally reported one noted (R), by insertion of various heteroatoms (S, O, Se) on the electron-donating benzodithiophene (Donor (D = BDT)) part. From the calculated results, the dihedral angle between BDT and side-chain affects the distribution of density on the ground state, gap energy, and intramolecular charge transfer of Dyes. In particular, the Dye3 compound, with the smaller dihedral angle, shows that the furan groups in the side chain of D, participates in the distribution of density on the ground state and consequently the charge transfer is improved. Additionally, Dye3 has the lower reorganization energy revealing that this material exhibits better charge mobility. Using the Scharber diagram, Dye3-PCBM heterojunction shows a power conversion efficiency of around 7%. Overall, this work suggests that the photovoltaic properties can be affected by the modification of heteroatoms on side groups of donor parts in small molecules.     

Electronic states and pseudo Jahn-Teller distortion of heavy metal-monobenzene complexes: M(C6H6) (M = Y, La, and Lu)

Monobenzene complexes of yttrium (Y), lanthanum (La), and lutetium (Lu), M(C(6)H(6)) (M = Y, La, and Lu), were prepared in a laser-vaporization supersonic molecular beam source and studied by pulsed-field ionization zero electron kinetic energy (ZEKE) spectroscopy and ab initio calculations. The calculations included the second-order perturbation, the coupled cluster with single, double, and perturbative triple excitation, and the complete active space self-consistent field methods. Adiabatic ionization energies and metal-benzene stretching frequencies of these complexes were measured for the first time from the ZEKE spectra. Electronic states of the neutral and ion complexes and benzene ring deformation were determined by combining the spectroscopic measurements with the theoretical calculations. The ionization energies of M(C(6)H(6)) are 5.0908 (6), 4.5651 (6), and 5.5106 (6) eV, and the metal-ligand stretching frequencies of [M(C(6)H(6))](+) are 328, 295, and 270 cm(-1) for M = Y, La, and Lu, respectively. The ground states of M(C(6)H(6)) and [M(C(6)H(6))](+) are (2)A(1) and (1)A(1), respectively, and their molecular structures are in C(2v) point group with a bent benzene ring. The deformation of the benzene ring upon metal coordination is caused by the pseudo Jahn-Teller interaction of (1(2)E(2)+1(2)A(1)+2(2)E(2)) e(2) at C(6v) symmetry. In addition, the study shows that spectroscopic behaviors of Y(C(6)H(6)) and La(C(6)H(6)) are similar to each other, but different from that of Lu(C(6)H(6)).     

The role of botrydienediol in the biodegradation of the sesquiterpenoid phytotoxin botrydial by Botrytis cinerea

The biotransformation of botrydienediol (6) labelled with deuterium on carbons C-10 and C-15 has been studied. This has led to modification of some previous assumptions about the biodegradative route of botrydial. The [10-²H,15-²H]-botry-1(9)-4-diendiol (12) was transformed into dehydrobotrydienediol derivatives 13-15 but it was not incorporated into secobotryane skeleton (7). In addition, three new sesquiterpenoids have been isolated, which shed further light on the secondary metabolites of Botrytis cinerea. From the point of view of persistence of these toxins in the food chain, the easy biotransformation and different biodegradative routes of botrydial (1), seem to indicate that the toxin may not persist in the plant for a long time as it will be metabolized by the fungi and the plant.     

High resolution vacuum ultraviolet emission spectrum of D(2) from 78 to 103 nm: The D (1)Pi(u)-->X (1)Sigma(g) (+) and D(') (1)Pi(u) (-)-->X (1)Sigma(g) (+) band systems

The emission spectrum of the D(2) molecule has been studied at high resolution in the vacuum ultraviolet region 78.5-102.7 nm. A detailed analysis of the two D (1)Pi(u)-->X (1)Sigma(g) (+) and D(') (1)Pi(u) (-)-->X (1)Sigma(g) (+) electronic band systems is reported. New and improved values of the level energies of the two upper states have been derived with the help of the program IDEN [V. I. Azarov, Phys. Scr. 44, 528 (1991); 48, 656 (1993)], originally developed for atomic spectral analysis. A detailed comparison is made between the observed energy levels and solutions of coupled equations using the newest ab initio potentials by Wolniewicz and co-workers [J. Chem. Phys. 103, 1792 (1995); 99, 1851 (1993); J. Mol. Spectros. 212, 208 (2002); 220, 45 (2003)] taking into account the nonadiabatic coupling terms for the D (1)Pi(u) state with the lowest electronic states B (1)Sigma(u) (+), C (1)Pi(u), and B(') (1)Sigma(u) (+). A satisfactory agreement has been found for most of the level energies belonging to the D and D(') states. The remaining differences between observation and theory are probably due to nonadiabatic couplings with other higher electronic states which were neglected in the calculations.     

Thermolysis of symmetrical dithiobiurea and thioureidoethylthiourea derivatives

Microwave and thermal heterocyclization of N,N′‐disubstituted hydrazinecarbothioamide 1a,b and substituted thioureidoethylthioureas 2a–c as well as 1‐phenyl‐3[2‐(3‐phenylthio‐ureido)phenyl]thiourea 6 are reported. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:535–541, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10188     

Magnetic Nanoparticle Thermometry via Controlled Diffusion

The process of magnetic nanoparticle heating releases enormous amounts of thermal energy. Through typical calorimetric analyses, the total thermal energy released can be easily quantified; however, knowledge of nanoscale temperature is necessary. Herein, a novel method of nanoscale thermometry by analyzing intra-particle diffusion in core–shell nanoparticles is proposed. Heating the iron cores with an alternating magnetic field in a saline suspension encourages the diffusion of sodium ions into the silica shells of the particles, which is modeled numerically; however, experimental measurements are needed in order to provide accurate diffusivity estimations. After determining the diffusion characteristics from X-ray photoelectron spectroscopy) depth profiling of silica films, energy dispersive analysis with high-resolution transmission electron microscopy measures the sodium ion gradient within single particles before and after heating. When compared directly to the numerical simulations, the results indicate that the temperature gradient between particles and saline suspension reaches significantly higher temperatures than the macro-scale temperature of the solution. By accurately knowing the thermal gradient between nanoparticles and the surrounding medium, nanoparticles can be engineered to limit surface resistances as much as possible and promote high rates of thermal energy transfer.