DETERMINATION OF THE MOLECULAR-ORIENTATION OF A PHTHALOCYANINE DERIVATIVE IN A LANGMUIR-BLODGETT-FILM BY POLARIZED UV VIS SPECTRA

Langmuir-Blodgett (LB) films of (p-carboxyphenoxy)-tri(2,4-di-tert-pentyl phenoxy)phthalocyanine copper(II) (asyCuPc) are prepared; the associated forms of the compound in chloroform solution and the particular orientation of asyCuPc molecular macrocycles in LB films is determined by polarized UV-VIS.

Measuring free ellagic acid: influence of extraction conditions on recovery by studying solubility and UV-Visible spectra

Recent investigations into plant tissues have indicated that the free form of the natural polyphenolic antioxidant, ellagic acid (EA), is much more plentiful than first envisaged; consequently a re-assessment of solvent systems for the extraction of this water-insoluble form is needed. As EA solubility and its UV-Vis spectrum, commonly used for detection and quantification, are both governed by pH, an understanding of this dependence is vital if accurate EA measurements are to be achieved. After evaluating the pH effects on the solubility and UV-Vis spectra of commercial EA, an extraction protocol was devised that promoted similar pH conditions for both standard solutions and plant tissue extracts. The extraction so devised followed by HPLC with photodiode-array detection (DAD) provided a simple, sensitive and validated methodology that determined free EA in a variety of plant extracts. The use of 100 % methanol or a triethanolamine-based mixture as the standard dissolving solvents were the best choices, while these higher pH-generating solvents were more efficient in extracting EA from the plants tested with the final choice allied to the plants’ natural acidity. Two of the native Australian plants anise myrtle (Syzygium anisatum) and Kakadu plum (Terminalia ferdinandiana) exhibited high concentrations of free EA. Furthermore, the dual approach to measuring EA UV-Vis spectra made possible an assessment of the effect of acidified eluent on EA spectra when the DAD was employed.

The synthesis of phenyl-capped trianiline and teraaniline by a modified-pseudo-high dilution technique and their UV-Vis spectral studies

Phenyl-capped trianiline and tetraaniline in the leucoemeraldine oxidation state were synthesized through a modified-pseudo-high-dilution technique. The chemical oxidation process of these compounds were studied by UV-Vis spectra. It was found that phenyl-capped trianiline in the leucoemeraldine oxidation state was oxidized to its EB form and then decomposed, Phenyl-capped tetraaniline was oxidized to its EB form and then to the pernigraniline oxidation state.

NMR and UV-Vis study on phenyl-capped oligoaniline salts

Phenyl-capped oligoanilines in the oxidized state and their salts (by camphor sulfonic acid, CSA) were comparatively studied by UV-Vis and NMR spectroscopy. The UV-Vis spectra revealed a similar electron transfer behaviour and similar structure in the tetraaniline to those in polyaniline. Upon formation of the salt, H-1 NMR CH peaks of the oligomers showed large shifts to lower fields. The longer the molecule of a oligomer is, the more the shift, indicating that the charge brought into the N atoms by the proton was redistributed over the whole molecule. The CH and quaternary carbon peak-shifts support the electron cloud motion route H -->C -->C -->N -->H. This is in agreement with the four ring BQ derivatives model.

Raman, IR, UV-vis and EPR characterization of two copper dioxolene complexes derived from L-dopa and dopamine

The anionic complexes [Cu(L(1-))(3)](1-), L(-) = dopasemiquinone or L-dopasemiqui none, were prepared and characterized. The complexes are stable in aqueous solution showing intense absorption bands at ca. 605 nm for Cu(II)-L-dopasemiquinone and at ca. 595 nm for Cu(II)-dopasemiquinone in the UV-vis spectra, that can be assigned to intraligand transitions. Noradrenaline and adrenaline, under the same reaction conditions, did not yield Cu-complexes, despite the bands in the UV region showing that noradrenaline and adrenaline were oxidized during the process. The complexes display a resonance Raman effect, and the most enhanced bands involve ring modes and particularly the vCC + vCO stretching mode at ca. 1384 cm(-1). The free radical nature of the ligands and the oxidation state of the Cu(II) were confirmed by the EPR spectra that display absorptions assigned to organic radicals with g= 2.0005 and g = 2.0923, and for Cu(II) with g = 2.008 and g = 2.0897 for L-dopasemiquinone and dopasemiquinone, respectively. The possibility that dopamine and L-dopa can form stable and aqueous-soluble copper complexes at neutral pH, whereas noradrenaline and adrenaline cannot, may be important in understanding how Cu(II)-dopamine crosses the cellular membrane as proposed in the literature to explain the role of copper in Wilson disease. (c) 2008 Elsevier B.V. All rights reserved.

In Situ and Simultaneous UV-vis/SAXS and UV-vis/XAFS Time-Resolved Monitoring of ZnO Quantum Dots Formation and Growth

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Studies on the interaction of porphyrin with antibody with fluorescent spectrum and UV-Vis differential spectra

After meso-tetra (alpha, alpha, alpha, alpha-O-phenylacetyl benzene)porphyrin combined with McAb 1F2, there was a significant hyperchromic effect, indicating that the combination of porphyrin and antibody is rigid and compact, aromatic amino acids exist at the combining sites of antigen in antibody. These aromatic amino acids are Trys and Trps, but the numbers of Trp are more than that found for Trys. The stochiometric ratio of porphyrin to 1F2 is 1:1, the disassociation constant was determined as(2.084+/-0.216) x 10(-10) mol/L by a method of fluorescence quenching, showing that both have a high affinity.

UV-Vis and surface photovoltage spectra of Fe2O3/polystyrene composite microspheres

Fe2O3 sol with the particle diameter of 3-5 nm was flocculated by the addition of SDS, and the flocculate formed was redispersed by the further addition of that surfactant. Thus the surfactant bilayer was formed on the surface of Fe2O3. The emulsion polymerization of styrene (St) adsolubilized oil the surfactant adsorbed bilayer was carried out by initiator potassium persulfate (KPS). The UV-Vis and surface photovoltage spectra (SPS) indicate that the Fe2O3 particles were encapsulated in polystyrene(PSt) successfully.

Properties and one-step synthesis of (2-acetylpyridine)tetraammineruthenium(II), [Ru-II(2-acpy)(NH3)(4)](2+) and tetraammine(2-benzoylpyridine)ruthenium(II), [Ru-II(NH3)(4)(2-bzpy)](2+) Redox potentials, UV-Vis and NMR spectra

A more direct and efficient route to the syntheses of [Ru(NH3)(4)(X-Y)](BF4)(2), where X-Y can be 2-acetylpyridine (2-acpy) or 2-benzoylpyridine (2-bzpy), based on the reactions of [RuCl(NH3)(5)]Cl-2 with these ortho-substituted azines is described. The [Ru(2-acpy)(NH3)(4)](BF4)(2) and [Ru(NH3)(5)(2-bzpy)](BF4)(2) complexes have a molar conductance of 328 and 292 Ohm(-1) cm(2) mol(-1), respectively, corresponding to a 1:2 species in solution. These complexes showed two intense absorption bands around 620-650 and 380 nm, the energies of which are solvent dependent, decreasing with the increase of the Gutman's donor number of the solvent, and were assigned as metal-to-ligand charge transfer (MLCT). The complexes have oxidation potentials (Ru-II/III) of +0.380 V vs. Ag/AgCl (2-acpy) and +0.400 V vs. Ag/AgCl (2-bzpy), and reduction potentials (X-Y0/-) of -1.10 V vs. Ag/AgCl (2-acpy) and -0.950 V vs. Ag/AgCl (2-bzpy) on CF3COOH/NaCF3COO at pH=3.0, scan rate 100 mV s(-1), [Ru]=1.0x10(-3) mol l(-1). Both processes show a coupled chemical reaction. Upon oxidation of the metal center, the MLCT absorption bands are bleached and restored upon subsequent reduction. In order to confirm the structure of the complexes a detailed LH NMR investigation was performed in d(6)-acetone. Further confirmation of the structure was obtained by recording the N-15 NMR spectrum of [Ru(NH3)(4)(2-bzpy)](2+) in d(6)-DMSO using the INEPT pulse sequence improving the sensitivity of N-15 by polarization transfer from the protons to the N-15. The Nuclear Overhauser Effect (NOE) experiments were made qualitatively for [Ru(NH3)(4)(2-acpy)](2+), and showed that H-6 of the pyridine is close to a NH3 proton, which should then be in a cis position, and, hence, confirming that acpy is acting as a bidentate ligand. (C) 1999 Elsevier B.V. Ltd. All rights reserved.

The rearrangements of naphthyinitrenes: UV/Vis and IR spectra of azirines, cyclic ketenimines, and cyclic nitrile ylides

Ar matrix photolysis of 1- and 2-naphthyl azides 3 and 4 at 313 nm initially affords the singlet naphthyl nitrenes, (1)1 and (1)2. Relaxation to the corresponding lower energy, persistent triplet nitrenes (3)1 and (3)2 competes with cyclization to the azirines 15 and 18, which can also be formed photochemically from the triplet nitrenes. On prolonged irradiation, the azirines can be converted to the seven-membered cyclic ketenimines 10 and 13, respectively, as described earlier by Dunkin and Thomson. However, instead of the o-quinoid ketenimines 16 and 19, which are the expected primary ring-opening products of azirines 15 and 18, respectively, we observed their novel bond-shift isomers 17 and 20, which may be formally regarded as cyclic nitrile ylides. The existence of such ylidic heterocumulenes has been predicted previously, but this work provides the first experimental observation of such species. The factors which are responsible for the special stability of the ylidic species 17 and 20 are discussed.

Characterisation of Ni carbonate-bearing minerals by UV-Vis-NIR spectroscopy

Four nickel carbonate-bearing minerals from Australia have been investigated to study the effect of Ni for Mg substitution. The spectra of nullaginite, zaratite, widgiemoolthalite and takovite show three main features in the range of 26,720–25,855 cm−1 (ν1-band), 15,230–14,740 cm−1 (ν2-band) and 9,200–9,145 cm−1 (ν3-band) which are characteristic of divalent nickel in six-fold coordination. The Crystal Field Stabilization Energy (CFSE) of Ni2+ in the four carbonates is calculated from the observed 3A2g(3F) → 3T2g(3F) transition. CFSE is dependent on mineralogy, crystallinity and chemical composition (Al/Mg-content). The splitting of the ν1- and ν3-bands and non-Gaussian shape of ν3-band in the minerals are the effects of Ni-site distortion from regular octahedral. The effect of structural cation substitutions (Mg2+, Ni2+, Fe2+ and trivalent cations, Al3+, Fe3+) in the carbonate minerals is noticed on band shifts. Thus, electronic bands in the UV–Vis–NIR spectra and the overtones and combination bands of OH and carbonate ion in NIR show shifts to higher wavenumbers, particularly for widgiemoolthalite and takovite.

Formation of polypyrrole and polythiophene within Cu2+- and H+-mordenite hosts studied by EPR and UV-VIS spectroscopy

The reactions of pyrrole and thiophene monomers in copper-exchanged mordenite have been investigated using EPR and UV–VIS absorption spectroscopy. The EPR spectra show a decrease in the intensity of the Cu2+ signal and the appearance of a radical signal due to the formation of oxidatively coupled oligomeric and/or polymeric species in the zeolite host. The reaction ceases when ca. 50% of the copper has reacted and differences in the form of the residual Cu2+ signal between the thiophene and pyrrole reactions suggest a greater degree of penetration of the reaction into the zeolite host for pyrrole, in agreement with previous XPS measurements. The EPR signal intensities show that the average length of the polymer chain that is associated with each radical centre is 15–20 and 5–7 monomer units for polypyrrole and polythiophene, respectively. The widths of the EPR signals suggest that these are at least partly due to small oligomers. The UV–VIS absorption spectra of the thiophene system show bands in three main regions: 2.8–3.0 eV (A), 2.3 eV (B) and 1.6–1.9 eV (D, E, F). Bands A and D–F occur in regions which have previously been observed for small oligomers, 4–6 monomer units in length. Band B is assigned to longer chain polythiophene molecules. We therefore conclude that the reaction between thiophene and copper-loaded mordenite produces a mixture of short oligomers together with some long chain polythiophene. The UV–VIS spectra of the pyrrole system show bands in the regions 3.6 eV (A), 2.7–3.0 eV (B, C) and 1.5–1.9 eV (D, F). Assignments of these bands are less certain than for the thiophene case because of the lack of literature data on the spectra of pyrrole oligomers.

Microwave assisted synthesis and UV-Vis spectroscopic studies of silver nanoparticles synthesized using vanillin as a reducing agent

The present investigation explores the adaptability of a microwave assisted route to obtain silver nanoparticles by the reduction of AgNO3 with vanillin, an environmentally benign material. Anionic surfactants such as AOT and SDS were used separately for encapsulating AgNPs and their role was compared. The UV-Visible absorption spectra present a broad SPR band consisting of two peaks suggesting the formation of silver nanoparticle with bimodal size distribution. The TEM image shows particles with spherical and hexagonal morphologies which confirms the results of UV-Vis studies. The anisotropy in the particle morphology can be attributed to the surface oxidation which in turn produces Ag@Ag2O core-shell nanostructures. Thus an intriguing feature of this system is that the obtained colloid is a mixture of AgNPs with and without Ag2O layers. Studies on the influence of pH on the stability of the synthesized nanoparticles revealed that the presence of excess Ag2O layers has a profound influence on it. Ag2O layers can be removed from AgNPs' surface by changing the solution pH to the acidic regime. The present study attests the enhanced ability of AOT in stabilizing the AgNPs in aqueous media. (C) 2011 Elsevier B.V. All rights reserved.