Single molecule spectroscopy as a probe for dye-polymer interactions

Experimental (Single Molecule Spectroscopy) and theoretical (quantum-chemical calculations and Monte Carlo and molecular dynamics simulations) techniques are combined to investigate the behavior and dynamics of a polymer-dye molecule system. It is shown that the dye molecule of interest (1,1'-dioctadecyl-3,3,3',3'-tetramethylindo-dicarbocyanine) adopts two classes of conformations, namely planar and nonplanar ones, when embedded in a poly(styrene) matrix. From an in-depth analysis of the fluorescence lifetime trajectories, the planar conformers can be further classified according to the way their alkyl side chains interact with the surrounding poly(styrene) chains.     

Frequency modulated spectroscopy as a probe of molecular collision dynamics

We describe the application of frequency modulated spectroscopy (FMS) with an external cavity tuneable diode laser to the study of the scalar and vector properties of inelastic collisions. CN X(2)Sigma(+) radicals are produced by polarized photodissociation of ICN at 266 nm, with a sharp velocity and rotational angular momentum distribution. The collisional evolution of the distribution is observed via sub-Doppler FMS on the A(2)Pi-X(2)Sigma(+) (2,0) band. He, Ar, N(2), O(2) and CO(2) were studied as collider gases. Doppler profiles were acquired in different experimental geometries of photolysis and probe laser propagation and polarization, and on different spectroscopic branches. These were combined to give composite Doppler profiles from which the speed distributions and specific speed-dependent vector correlations could be determined. The angular scattering dynamics with species other than He are found to be very similar, dominated by backward scattering which accompanies transfer of energy between rotation and translation. The kinematics of collisions with He are not conducive to the determination of differential scattering and angular momentum polarization correlations. Angular momentum correlations show interesting differences between reactive and non-reactive colliders. We propose that this reflects differences in the potential energy surfaces, in particular, the nature and depth of attractive potential wells.     

Raman spectroscopy as a probe of adsorption on rhodium particles

Raman spectroscopy has been used as a probe of the adsorption of pyridine onto small particles of rhodium. The band energies of the surface phase correspond with those found on roughened silver electrodes. Chemical experiments indicate that the pyridine is stronyly chemisorbed. The similarity with the spectrum of pyridine on Ag presumably means that the predominant surface species is the same on each metal. This work represents the first report of an enhanced Raman spectrum on metallic rhodium.     

Photoelectron spectroscopy as a structural probe of intermediate size clusters

We examine the utility of photoelectron spectroscopy (PES) as a structural probe of Si(n) (-) in the n=20-26 size range by determining isomers and associated photoelectron spectra from first principles calculations. Across the entire size range, we consistently obtain a good agreement between the theory and experiment [Hoffmann et al., Eur. Phys. J. D 16, 9 (2001)]. We find that PES can almost invariably distinguish between structurally distinct isomers at a given cluster size, but that structurally similar isomers usually cannot be reliably distinguished by PES. For many, but not all, sizes the isomer giving the best match to experiment is the lowest-energy one found theoretically. Thus, combining theory with PES experiments emerges as a useful source of structural information even for intermediate size clusters.     

Vibrational spectroscopy of resveratrol

In this article the authors deal with the experimental and theoretical interpretation of the vibrational spectra of trans-resveratrol (3,5,4'-trihydroxy-trans-stilbene) of diverse beneficial biological activity. Infrared and Raman spectra of the compound were recorded; density functional calculations were carried out resulting in the optimized geometry and several properties of the molecule. Based on the calculated force constants, a normal coordinate analysis yielded the character of the vibrational modes and the assignment of the measured spectral bands.     

Vibrational spectroscopy of implants

The results of systematic spectral studies of polymers in ophthalmology are presented. The spectral criteria of selection of intraocular lens (IOL; implants of long service in an organism have been defined for poly(methylphenylsiloxane). Non-inflammatory implantation of IOL, when the manufacturing of lenses is performed under spectral control at several stages, has been realized. New siloxane–polyurethane block copolymers promising for ophthalmology have been studied and passivated surfaces have been obtained.     

Vibrational spectroscopy of N-phenylmaleimide

A combination of infrared, Raman and inelastic neutron scattering (INS) spectroscopies with density functional theory (DFT) calculations is used to provide a complete assignment of the vibrational spectra of N-phenylmaleimide and N-(perdeuterophenyl)maleimide. DFT is shown to give very good results for the frequencies and atomic displacements in the modes. These are used to generate INS spectra which are excellent agreement with the observed. The calculated infrared and Raman spectra are much less reliable, although this may be more of a presentation problem than a real failing.     

Positron lifetime spectroscopy as a probe of nanoporosity of cement-based materials

Hydrating cement pastes prepared with water-to-cement ratio equal to 0.5 in weight were investigated through positron annihilation lifetime spectroscopy over a period of 4 weeks. Two series of samples were prepared using different pre-treatment procedures, in order to assess the influence of sample manipulations on positron annihilation measurements. The technique is sensitive to changes in the pore structure with ageing time. Moreover, from the positron data an estimate of the first two moments of radii distribution of the nanopores was obtained.     

Vibrational spectroscopy of stichtite

Raman spectroscopy complimented with infrared spectroscopy has been used to study the mineral stitchtite, a hydrotalcite of formula Mg6Cr2(CO3)(OH)16.4H2O. Two bands are observed at 1087 and 1067 cm(-1) with an intensity ratio of approximately 2.5/1 and are attributed to the symmetric stretching vibrations of the carbonate anion. The observation of two bands is attributed to two species of carbonate in the interlayer, namely weakly hydrogen bonded and strongly hydrogen bonded. Two infrared bands are found at 1457 and 1381 cm(-1) and are assigned to the antisymmetric stretching modes. These bands were not observed in the Raman spectrum. Two infrared bands are observed at 744 and 685 cm(-1) and are assigned to the nu4 bending modes. Two Raman bands were observed at 539 and 531 cm(-1) attributed to the nu2 bending modes. Importantly the band positions of the paragenically related hydrotalcites stitchtite, iowaite, pyroaurite and reevesite all of which contain the carbonate anion occur at different wavenumbers. Consequently, Raman spectroscopy can be used to distinguish these minerals, particularly in the field where many of these hydrotalcites occur simultaneously in ore zones.     

EPR spectroscopy as a probe of metal centres in biological systems

Molecular paramagnetism pervades the bioinorganic chemistry of V, Mn, Fe, Co, Ni, Cu, Mo, W, and of a number of non-biological transition elements. To date we can look back at half a century of fruitful EPR studies on metalloproteins, and against this background evaluate the significance of modern EPR spectroscopy from the perspective of a biochemist, making a distinction between conventional continuous wave X-band spectroscopy as a reliable work horse with broad, established applicability even on crude preparations, vs. a diffuse set of "advanced EPR" technologies whose practical application typically calls for narrowly focused research hypotheses and very high quality samples. The type of knowledge on metalloproteins that is readily obtainable with EPR spectroscopy, is explained with illustrative examples, as is the relation between experimental complexity and the spin value of the system.     

Vibrational CD spectroscopy as a powerful tool for stereochemical study of cyclophynes in solution

Stereochemical study of cyclophynes, which is otherwise rather difficult to perform, can be achieved by vibrational CD spectroscopy.     

Introducing krypton NMR spectroscopy as a probe of void space in solids

A wealth of information about porous materials and their void spaces has been obtained from the chemical shift data in (129)Xe NMR spectroscopy during the past decades. In this contribution, the only NMR active, stable krypton isotope (83)Kr (spin I = (9)/(2)) is explored as a novel probe for porous materials. It is demonstrated that (83)Kr NMR spectroscopy of nanoporous or microporous materials is feasible and straightforward despite the low gyromagnetic ratio and low abundance of the (83)Kr isotope. The (83)Kr line width in most of the studied cases is quadrupolar dominated and field-strength independent. A significant exception was found in calcium-exchanged zeolites where the field dependence of the line width indicates a distribution of isotropic chemical shifts that may be caused by long-range disorder in the zeolite structure. The (83)Kr chemical shifts observed in the investigated materials display a somewhat different behavior than that of their (129)Xe counterparts and should provide a great resource for the verification or refinement of current (129)Xe chemical shift theory. In contrast to xenon, krypton with its smaller atomic radius has been demonstrated to easily penetrate the porous framework of NaA. Chemical shifts and line widths of (83)Kr are moderately dependent on small fluctuations in the krypton loading but differ strongly between some of the studied samples.     

Vibrational spectroscopy of ion-irradiated ices

In the last 20 years we have studied some effects induced by fast ions (E approximately keV-MeV) impinging on solid materials (mainly ices) with a view to their astrophysical relevance. The main techniques used have been infrared and Raman spectroscopy. Here we review some of the results obtained so far concerning, in particular, the formation of new species not present in the original sample. When hydrocarbons are an important constituent of the target ion irradiation gives rise also to a refractory residue which is left over after warming up. In addition we present some preliminary results of a new study, still in progress, on the infrared properties of the organic residue formed after irradiation of an icy mixture with H-, C-, N- and O-bearing species. Furthermore we present the micro-Raman spectra of some fragments of Orgueil a carbonaceous chondrite meteorite. Some astrophysical applications of these laboratory results are also discussed.     

Vibrational spectroscopy of formamide-intercalated kaolinites

The vibrational spectroscopy of low and high defect kaolinites fully and partially intercalated with formamide have been determined using a combination of X-ray diffraction, DRIFT and Raman spectroscopy. Expansion of the high defect kaolinite to 10.09 A resulted in a decrease in the peak width of the d(001) peak attributed to a decrease in defect structures upon intercalation. Changes in the defect structures of the low defect kaolinite were observed. Additional infrared bands were observed for the formamide intercalated kaolinites at 3629 and 3606 cm(-1). The 3629 cm(-1) band is attributed to the hydroxyl stretching frequency of the inner surface hydroxyl group hydrogen bonded to the carboxyl group of the formamide. The 3606 cm(-1) band is ascribed to water in the interlayer. Concomitant changes are observed in both the hydroxyl deformation modes and in the carboxyl bands.     

Electrochemical impedance spectroscopy as a probe for wet chemical silicon oxide characterization

The kinetics of the chemical growth of silicon oxide in H₂O₂-containing ammonia solutions and its break-up by dilute ammonia solutions was investigated using electrochemical techniques and more specifically electrochemical impedance spectroscopy. The recording of the open circuit potential (OCP), complemented by successive impedance diagrams, demonstrates clearly the build-up of a silicon oxide passivating layer when hydrophobic Si surfaces are immersed in NH₃+H₂O₂ solutions. The thickening of the chemical oxide coating mainly results in the decrease of the capacitance value together with the enhancement of the ohmic surface resistance. On the other hand, pure ammonia dilute solutions lead to the progressive destruction of this hydrophilic passivating surface oxide, which is revealed by the simultaneous decay of the real component of the impedance. Finally, we observed the break-up of the passive layer, characterized by a sudden drop of the OCP to a value quite identical to that obtained with a bare Si surface. This process resulted in a dramatic corrosion of the substrate surface. Electronic Publication     

Vibrational spectroscopy as a tool for examination to the secondary structure of metal-labeled trastuzumab immunoconjugates

Infrared and Raman spectroscopy are effective techniques that allow collecting information about secondary structure of proteins, including antibodies. Trastuzumab, antibody used in our study was in a freeze-dried form, conjugated with different bifunctional chelators and linked with the stable isotopes of lutetium and yttrium. The characterization of the final immunoconjugates showed no significant changes in the structure demonstrated by the presence of the amide bands characteristic for a α-helices and β-sheets structures. These methods could be applied during the production of the antibody freeze-dried kit formulations for the labeling with the radioactive isotopes.

     

Dielectric spectroscopy as a probe for the investigation of conformational properties of proteins

In this brief paper, we review recent and significant results obtained in our laboratory by dielectric spectroscopy (DS). This is a multi purpose and very sensitive approach to investigate structural features of biological systems. DS at radiofrequencies is particularly powerful in the study of structural and conformational properties of proteins. We report on results obtained on three well-known proteins: lysozyme, cytochrome-c and metmyoglobin, which represent very useful models for folding/unfolding studies. The influence of pH and temperature as well as presence of trehalose as a co-solvent, was determined by estimation of the effective hydrodynamic radius and electric dipole moment of the protein in solution. In particular, trehalose was shown to affect the alkaline transition of cytochrome. Conformational effects on the three above-mentioned proteins were observed in a temperature range near the physiological ones. Dynamical properties of lysozyme in mixtures water-glycerol are also discussed. Parallel measurements of photon correlation spectroscopy (PCS) and DS indicated that both translational and rotational diffusive behavior are coherent with the Debye-Stokes-Einstein hydrodynamic model.     

15N NMR spectroscopy as a probe for the geometry of diazenido ligands

A useful criterion of linear or bent geometry at N_α of diazenido (-N_αN_βR) ligands is afforded by ¹⁵N NMR. A very large downfield shift (ca. 350 ppm) of the N_α resonance is reported for the “doubly-bent” diazenido ligands in [RhCl₂(¹⁵NNC₆H₄R-4)(PPh₃)₂] (R = H or NO₂) compared with the “singly-bent” diazenido ligands in trans-[MX(¹⁵N₂R¹)(dppe)₂] (M = Mo or W, X = Cl or Br, R¹ = Et or COMe), [ReCl₂(¹⁵N₂COC₆H₅)(C₅H₅N)(PPh₃)₂] and [RuCl₃(¹⁵NNC₆H₅)(PPh₃)₂].     

Vibrational spectroscopy of acid treated vermiculites

The natural vermiculites from different localities (Bulgaria, Brazil, and South Africa) after acid treatment were used for this study. Differently acidified vermiculite samples were prepared from the natural vermiculite sample using different concentrations of hydrochloric acid (0.5 M and 1 M) and different reaction time (2 h and 4 h) at 80 °C. Natural vermiculites and acid treated vermiculites were analyzed by elemental analysis, X-ray diffraction (XRD) analysis and studied using Fourier transform infrared (FTIR) spectroscopy and dispersive Raman spectroscopy. According to the XRD analysis vermiculites are interstratified structures created in the different two-one-zero sheet hydrated phases. Ratio of intensities of spectrally deconvoluted bands at 1075 cm⁻¹ and 1000 cm⁻¹ (stretching vibration of SiO bonds of vermiculites and stretching vibration of SiO bonds of amorphous silica, respectively) was used to determine the content of amorphous silica in acid treated vermiculite samples. Study of the infrared and Raman spectra of the acidified vermiculites enable a comparison of these two spectroscopic data that have not yet been performed.