Spectroscopic study of luminescence and energy transfer of binary and ternary complexes of rare earth with aromatic carboxylic acids and 1,10-phenanthroline

A series of rare earth (Gd, Eu, Tb) complexes with different substituent group carboxylic acids (ortho-hydroxylbenzioc acid, ortho-aminobenzoic acid and ortho-methoxy benzoic acid) and 1,10-phenanthroline were synthesized. The spectroscopic studies of the photophysical properties such as luminescence properties, energy match and intramolecular energy transfer were carried out. The lowest triplet state energies of ligands and the intramolecular energy transfer efficiencies were determined with the measurement of low phosphorescence spectra and lifetimes of Gd complexes.

Purification of imidazolium ionic liquids for spectroscopic applications

Ionic liquids are often contaminated by colored impurities. These impurities can be problematic for spectroscopic studies or for monitoring organic reactions by UV/Vis spectroscopy. The effect of different purification methods on the optical quality of colored ionic liquids was studied and compared. Yellowish ionic liquids can partially be decolorized by treatment with active charcoal or by recrystallization. Our experiments show column liquid chromatography is not always a good technique to prepare spectrograde imidazolium halide ionic liquids. Colorless and UV-transparent ionic liquids were synthesized by a method that can exclude the need for further purification steps. (c) 2005 Elsevier B.V. All rights reserved.

Quantum chemistry studies on electronic properties of CN adsorbed on silver electrodes

The electronic properties of CN adsorbed on Ag electrodes at different potentials have been studied by using the method of self-consistent-charge discrete variational Xa (SCC-DV-Xa) cluster calculations. It is shown that the binding of NCAg is dominated by both electrostatic and polarization effects derived from the charge of CN, and that the transfer of s charge from CN to silver is the largest donation contribution. The electrode potential influences this charge transfer process and the interaction between CN adsorbate and silver electrode. The results of quantum chemistry calculations fit well with the experimental data of in situ spectroscopic studies on the CN/Ag electrode systems. © 1991.

Tunable diode Laser Absorption Spectroscopy ,Nir Overtone and Life Studies of Some Organic Compound

The present work is mainly concentrated on setting up a NIR tunable diode laser absorption (TDLA) spectrometer for high-resolution molecular spectroscopic studies. For successfully recording the high-resolution tunable diode laser spectrum, various experimental considerations are to be taken into account like the setup should be free from mechanical vibrations, sample should be kept at a low pressure, laser should be in a single mode operation etc. The present experimental set up considers all these factors. It is to be mentioned here that the setting up of a high resolution NIR TDLA spectrometer is a novel experiment requiring much effort and patience. The analysis of near infrared (NIR) vibrational overtone spectra of some substituted benzene compounds using local mode model forms another part of the present work. An attempt is made to record the pulsed laser induced fluorescence/Raman spectra of some organic compounds. A Q-switched Nd:YAG laser is used as the excitation source. A TRIAX monochromator and CCD detector is used for the spectral recording. The observed fluorescence emission for carbon disulphide is centered at 680 nm; this is assigned as due to the n, p* transition. Aniline also shows a broad fluorescence emission centered at 725 nm, which is due to the p,p* transition. The pulsed laser Raman spectra of some organic compounds are also recorded using the same experimental setup. The calibration of the set up is done using the laser Raman spectra of carbon tetrachloride and carbon disulphide. The observed laser Raman spectra for aniline, o-chloroaniline and m-chlorotoluene show peaks characteristics of the aromatic ring in common and the characteristics peaks due to the substitutuent groups. Some new peaks corresponding to low-lying vibrations of these molecules are also assigned

Laser induced thermal lens and near infrared absorption studies of ch overtones in some organic compounds

Vibrational overtone spectroscopy of X-H (X=C,N,O) containing molecules is an area of recent interest. The spectroscopic studies of higher vibrational levels yield valuable informations, regarding,the molecular structure, intra- and inter-molecular interactions, radiationless transitions, intra-molecular vibrational relaxations, multiphoton excitations and chemical reactivities, which cannot be z obtained by other spectroscopic methods. This thesis presents the results of experimental investigations on the overtone spectra of some organic compounds in the liquid phase for the characterization of CH bonds. The spectra in the fifth overtone region (1fiV=6) are recorded using a dual beam thermal lens setup and the lower overtones (.AV=2-5) are recorded spectrophotometrically.The thesis is presented in six chapters.

Terahertz pulse imaging of stratified architectural materials for cultural heritage studies

Terahertz pulse imaging (TPI) is a novel noncontact, nondestructive technique for the examination of cultural heritage artifacts. It has the advantage of broadband spectral range, time-of-flight depth resolution, and penetration through optically opaque materials. Fiber-coupled, portable, time-domain terahertz systems have enabled this technique to move out of the laboratory and into the field. Much like the rings of a tree, stratified architectural materials give the chronology of their environmental and aesthetic history. This work concentrates on laboratory models of stratified mosaics and fresco paintings, specimens extracted from a neolithic excavation site in Catalhoyuk, Turkey, and specimens measured at the medieval Eglise de Saint Jean-Baptiste in Vif, France. Preparatory spectroscopic studies of various composite materials, including lime, gypsum and clay plasters are presented to enhance the interpretation of results and with the intent to aid future computer simulations of the TPI of stratified architectural material. The breadth of the sample range is a demonstration of the cultural demand and public interest in the life history of buildings. The results are an illustration of the potential role of TPI in providing both a chronological history of buildings and in the visualization of obscured wall paintings and mosaics.

Spectroscopic characterization of alkali-metal exchanged natrolites

Synchrotron infrared (IR) and micro-Raman spectroscopic studies have been performed on zeolite natrolites as a function of the non-framework composition at ambient conditions. This establishes the spectroscopic characterization of the ion-exchanged natrolites in the alkali-metal series both in the as-prepared hydrated (M-NAT-hyd, M = Li, Na, K, Rb, and Cs) and some stable dehydrated forms (M-NAT-deh, M = Rb and Cs). The former series exhibits non-framework cation-size dependent opening of the helical channels to span ca. 21° range in terms of the chain rotation angle, ? (or ca. 45° range in terms of the chain bridging angle, T-O2-T). For these hydrated phases, both IR and Raman spectra reveal that the degree of the red-shifts in the frequencies of the helical 8-ring channel as well as the 4-ring unit is proportional to the ionic radius of the non-framework cations. Linear fits to the data show negative slopes of -55.7 from Raman and -18.3 from IR in the 8-ring frequencies and ionic radius relationship. The spectroscopic data are also used to identify the modes of the dehydration-induced "collapse" of the helical 8-ring channels as observed in the stable anhydrous Rb-NAT-deh and Cs-NAT-deh. In addition, we demonstrate that the spectroscopic data in the hydrated series can be used to distinguish different water arrangements along the helical channels based on the frequency shifts in the H-O-H bending band and the changes in the O-H stretching vibration modes.

Synthesis, thermal behavior and spectroscopic study of trivalentlanthanide and yttrium(III) α-hydroxyisobutyrates, in solid state

Thermal and spectroscopic studies on solid trivalent lanthanides and yttrium(III) α-hydroxyisobutyrates, Ln(C4H7O 3)3·nH2O were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA), elemental analysis, X-ray diffractometry, complexometry, experimental and theoretical infrared spectroscopy and TG-DSC coupled to FTIR. The dehydration of lanthanum to neodymium and terbium to thulium and yttrium compounds occurs in a single step while for samarium, europium and gadolinium ones it occurs in three consecutives steps. Ytterbium and lutetium compounds were obtained in the anhydrous state. The thermal decomposition of the anhydrous compounds occursin two consecutives steps, except lanthanum (five steps) and cerium (single step), with formation of the respective oxides CeO2, Pr6O 11, Tb4O7 and Ln2O3 (Ln = La, Nd to Lu and Y), as final residue. The resultsalso provided information concerning the composition, thermal behavior, crystallinity and gaseous products evolved during the thermal decomposition. The theoretical and experimental spectroscopic data suggested the possible modes of coordination of the ligand with the lanthanides.© 2013 Elsevier B.V.

The mineralizing fluid in the Piaba gold deposit, São Luís cratonic fragment (NW-Maranhão, Brazil) based on fluid inclusion studies in quartz veins

O depósito aurífero de Piaba tornou-se a primeira mina em operação no fragmento cratônico São Luís, noroeste do Maranhão. Seu ambiente geológico compreende rochas metavulcanossedimentares do Grupo Aurizona e granitoides da Suíte Tromaí, entre outras unidades menores, formadas em ambiente de arcos de ilhas entre 2240 e 2150 Ma, juntamente com outras unidades menores. A mineralização é caracterizada por uma trama stockwork de veios e vênulas de quartzo com seus halos de alteração (clorita + muscovita + carbonato + pirita + calcopirita e ouro) hospedada em um granodiorito granofírico fino (Granófiro Piaba) e em rocha subvulcânica andesítica do Grupo Aurizona. O corpo mineralizado é espacialmente limitado à zona de cisalhamento ENE-WSW rúptil-dúctil (Falha Piaba). Estudos petrográficos, microtermométricos e por espectroscopia microRaman no quartzo definiram inclusões aquo-carbônicas bifásicas e trifásicas, produzidas por aprisionamento heterogêneo durante separação de fases, e fluidos aquosos tardios. A solução mineralizadora corresponde a um fluido aquo-carbônico composto por CO₂ (5 - 24 mol%, densidade de 0,96 - 0,99 g/cm³), H₂O (74 - 93 mol%), N₂ (< 1 mol%), CH₄ (<1mol%) e 5,5 % em peso NaCl equivalente. O minério depositou a 267 - 302ºC e 1,25 - 2,08 kbar, correspondendo a profundidades de 4 a 7 km, em consonância com o regime estrutural. A composição e o intervalo de P-T do fluido mineralizador, combinados com o caráter redutor (log ƒ_O2 -31,3 a -34,3) e a sulfetação da rocha hospedeira, sugerem que o ouro foi transportado como um complexo sulfetado. O minério foi depositado em consequência da separação de fase, redução da atividade de enxofre e da ƒO₂ pela interação fluido-rocha.

Complexation between darunavir ethanolate and beta cyclodextrin: experimental and theoretical studies

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

Spectroscopic study of Bioceramics for Endodontic and Orthopaedics

This thesis was aimed at investigating the physical-chemical properties and the behaviour in physiological environment of two classes of bioceramics: calcium silicate-based dental cements and alumina-based femoral heads for hip joint prostheses. The material characterization was performed using spectroscopic techniques such as that allow to obtain information on the molecular structure of the species and phases present in the analyzed samples. Raman, infrared and fluorescence spectroscopy was principally used. Calcium silicate cements, such as MTA (Mineral Trioxide Aggregate), are hydraulic materials that can set in presence of water: this characteristic makes them suitable for oral surgery and in particular as root-end filling materials. With the aim to improve the properties of commercial MTA cements, several MTA-based experimental formulations have been tested with regard to bioactivity (i.e. apatite forming ability) upon ageing in simulated body fluids. The formation of a bone-like apatite layer may support the integration in bone tissue and represents an essential requirement for osteoconduction and osteoinduction. The spectroscopic studies demonstrated that the experimental materials under study had a good bioactivity and were able to remineralize demineralized dentin. . Bioceramics thanks to their excellent mechanical properties and chemical resistance, are widely used as alternative to polymer (UHMWPE) and metal alloys (Cr-Co) for hip-joint prostesis. In order to investigate the in vivo wear mechanisms of three different generations of commercial bioceramics femoral heads (Biolox®, Biolox® forte, and Biolox® delta), fluorescence and Raman spectroscopy were used to investigate the surface properties and residual stresses of retrieved implants. Spectroscopic results suggested different wear mechanisms in the three sets of retrievals. Since Biolox® delta is a relatively recent material, the Raman results on its retrievals has been reported for the first time allowing to validate the in vitro ageing protocols proposed in the literature to simulate the effects of the in vivo wear.

An in-situ surface electrochemistry approach toward whole-cell studies: Charge transfer between Geobacter sulfurreducens and electrified metal/electrolyte interfaces through linker molecules

Electrochemical reactivity and structure properties of electrogenic bacteria, Geobacter sulfurreducens (Gs) were studied to explore the heterogeneous electron transfer at the bacteria/electrode interface using electrochemical and in-situ spectroscopic techniques. The redox behavior of Gs adsorbed on a gold electrode, which is modified with a ω-functionalized self-assembled monolayer (SAM) of alkanethiols, depends strongly on the terminal group. The latter interacts directly with outermost cytochromes embedded into the outer membrane of the Gs cells. The redox potential of bacterial cells bound electrostatically to a carboxyl-terminated SAM is close to that observed for bacteria attached to a bare gold electrode, revealing a high electronic coupling at the cell/SAM interface. The redox potentials of bacterial cells adsorbed on amino- and pyridyl-terminated SAMs are significantly different suggesting that the outermost cytochromes changes their conformation upon adsorption on these SAMs. No redox activity of Gs was found with CH3-, N(CH3)3+- and OH-terminated SAMs. Complementary in-situ spectroscopic studies on bacteria/SAMs/Au electrode assemblies were carried out to monitor structure changes of the bacterial cells upon polarization. Spectro-electrochemical techniques revealed the electrochemical turnover of the oxidized and reduced states of outer membrane cytochromes (OMCs) in Gs, providing evidence that the OMCs are responsible for the direct electron transfer to metal electrodes, such as gold or silver, during the electricity production. Furthermore, we observed spectroscopic signatures of the native structure of the OMCs and no conformational change during the oxidation/reduction process of the microorganisms. These findings indicate that the carboxyl-anchoring group provides biocompatible conditions for the outermost cytochromes of the Gs, which facilitate the heterogeneous electron transfer at the microorganism/electrode interface.

Synthesis, photophysical and electrochemical properties of aza-boron-diquinomethene complexes

A series of aza-boron-diquinomethene (aza-BODIQU) complexes with different aryl-substituents (B1–B6) were synthesized and characterized. Their photophysical properties were investigated systematically via spectroscopic and theoretical methods. All complexes exhibit strong 1π–π* absorption bands and intense fluorescent emission bands in the visible spectral region at room temperature. The fluorescence spectra in solution show the mirror image features of the S0→S1 absorption bands, which can be assigned to the 1π–π*/1ICT (intramolecular charge transfer) emitting states. Except for B6, all complexes exhibit high photoluminescence quantum yields (ΦPL = 0.47–0.93). The spectroscopic studies and theoretical calculations indicate that the photophysical properties of these aza-BODIQUs can be tuned by the appended aryl-substituents, which would be useful for rational design of boron–fluorine complexes with high emission quantum yield for organic light-emitting applications.

The crystal structure and vibrational spectroscopy of jarosite and alunite minerals

The alunite supergroup of minerals is a large hydroxy-sulfate mineral group, which has seen renewed interest following their discovery on Mars. Numerous reviews exist concerning nomenclature, formation, and natural occurrence of this mineral group. Sulfate minerals in general are widely studied and their vibrational spectra are well characterized. However, no specific review concerning alunite and jarosite spectroscopy and crystal structure has been forthcoming. This review focuses on the controversial aspects of the crystal structure and vibrational spectroscopy of jarosite and alunite minerals. Inconsistencies regarding band assignments especially in the 1000–400 cm−1 region plague these two mineral groups and result in different band assignments among the various spectroscopic studies. There are significant crystallographic and magnetic structure ambiguities with regards to ammonium and hydronium end-members, namely, the geometry these two ions assume in the structure and the fact that hydronium jarosite is a spin glass. It was also found that the synthetic causes for the super cell in plumbojarosite, minamiite, huangite, and walthierite are not known.

Amino group positions dependent morphology and coverage of electropolymerized metallophthalocyanine (M = Ni and Co) films on electrode surfaces

Electropolymerized films of teraaminometallophthalocyanines (MTAPc; M = Ni and Co) with amino groups at α- (4α-MTAPc) and β- (4β-MTAPc) positions were prepared on glassy carbon (GC) and indium tin oxide (ITO) electrodes. It was found that the electropolymerization growth rate of 4α-MTAPc was less than that of 4β-MTAPc prepared under identical conditions. Further, the surface coverage of the polymerized 4β-MTAPc film was greater than that of 4α-MTAPc polymerized film. Atomic force microscopy (AFM), X-ray diffraction (XRD) and UV–visible spectroscopic studies were carried out for the polymerized films of 4α-NiIITAPc (p-4α-NiIITAPc) and 4β-NiIITAPc (p-4β-NiIITAPc) alone because both Ni(II) and Co(II) polymerized films show similar trend in electropolymerization and surface coverage values. AFM images show that p-4α-NiIITAPc film contains islands and the thickness of this film was nearly three times less than that of p-4β-NiIITAPc. XRD patterns for the two polymerized films reveal that p-4β-NiIITAPc film was relatively more crystalline than p-4α-NiIITAPc film. Further, the compactness of these films was scrutinized from their barrier properties toward [Fe(CN)6]3−/4− redox couple. The differences in the polymerization growth rate of 4α-MTAPc and 4β-MTAPc, and the thicknesses of the resultant polymerized films suggest that unlike 4β-MTAPc one or two amino groups might have not involved in electropolymerization in the case of 4α-MTAPc. Further, the influence of surface coverage on the electrocatalytic properties of the polymerized films was studied by taking p-4β-CoIITAPc and p-4α-CoIITAPc films as examples. The electrocatalytic oxygen reduction current was almost same at both the electrodes suggesting that only the surface species were involved in the electrocatalytic reduction of oxygen.