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Forward scattering of light, X-rays and neutrons.

The central points of this paper can now be summarized. We consider here, for simplicity only, vanishing particle concentration. In equilibrium sedimentation equation (6) applies. The density increment is a measurable quantity. It can either be introduced into equation (6) to calculate M2, or it can be analysed by equation (7) and (8) to provide additional information on specific volumes and solute interactions. Light scattering is determined by the analogous equation (20). The refractive index increment is also experimentally accessible and its structure (not considered here) is similar to that of the density increment Small angle X-ray scattering is determined by equation (31) and the electron density increment which appears in this equation cannot be directly determined by experiment. Yet it can be obtained in straight-forward fashion from the mass density increment, by equation (34). Similarly, in the case of neutron scattering (equation (38)), the scattering length density increment is obtained from the mass density increment by equation (40), or it may now be directly evaluated by neutron interferometry. It is thus possible to analyse all forward scattering phenomena on the bases of well established fluctuation theory. In this chapter the emphasis has been on forward scattering only, but the considerations should be taken ito account as well at finite values of the scattering vector q. Whereas the role of interparticle interactions diminishes at low concentrations and at short distances (increasing q), the composition of the 'invariant' particle (as required in the analysis of Luzzati & Tardieu, 1980) should, as before, be characterized by the thermodynamic analysis. Additional points discussed have dealt with the connection with the conventional particle contrast parameters (Section 4 and equations (44)-(48)), the effect of heterogeneity in particle composition and systems comprising two homomacromolecules (equations (21)-(24)), the effect of hydrogen-deuterium substitution on mass density and scattering length density increments (equations (42) and (43)). Numerical examples have been worked out for density increments and interaction parameters of CsDNA in CsCl (Table 1, Fig.3) and for properties of this system in hydrogen-deuterium mixtures (Table 2, Figs 4 and 6). The implications of these considerations for other systems have been considered.

Biophysical Phenomena↗

Quantification problems in depth profiling of pwr steels using Ar+ ion sputtering and XPS analysis.

The oxide scales of AISI 304 formed in boric acid solutions at 300 degrees C and pH = 4.5 have been studied using X-ray photoelectron spectroscopy (XPS) depth profiling. The present focus is depth profile quantification both in depth and chemical composition on a molecular level. The roughness of the samples is studied by atomic force microscopy before and after sputtering, and the erosion rate is determined by measuring the crater depth with a surface profilometer and vertical scanning interferometry. The resulting roughness (20-30 nm), being an order of magnitude lower than the crater depth (0.2-0.5 microm), allows layer-by-layer profiling, although the ion-induced effects result in an uncertainty of the depth calibration of a factor of 2. The XPS spectrum deconvolution and data evaluation applying target factor analysis allows chemical speciation on a molecular level. The elemental distribution as a function of the sputtering time is obtained, and the formation of two layers is observed-one hydroxide (mainly iron-nickel based) on top and a second one deeper, mainly consisting of iron-chromium oxides.

Journal Article↗

Image Formation in Femtosecond Confocal Interference Microscopy

: Three-dimensional image formation in an interference confocal scanning microscope under ultrashort pulsed beam illumination is investigated in this study. The novelty of this new image system is that it keeps advantages in femtosecond interferometry but also provides a femtosecond-resolved three-dimensional image without necessarily using an ultrafast detector. For a 5-fs pulsed beam illumination, spatial resolution in the axial and transverse directions in this system is improved by approximately 45% and 15%, respectively, compared with that in the case of continuous wave illumination. However, strong chromatic aberration caused by an ultrashort pulsed beam can result in a degradation of spatial and temporal resolution, whereas weak chromatic aberration may lead to an improvement in transverse resolution.

Journal Article↗

Fourier transform spectroscopic imaging using an infrared focal-plane array detector.

A powerful new mid-infrared spectroscopic chemical imaging technique combining step-scan Fourier transform Michelson interferometry with indium antimonide focal-plane array (FPA) image detection is described. The coupling of an infrared focal-plane array detector to an interferometer provides an instrumental multiplex/multichannel advantage. Specifically, the multiple detector elements enable spectra at all pixels to be collected simultaneously, while the interferometer portion of the system allows all the spectral frequencies to be measured concurrently. With this method of mid-infrared spectroscopic imaging, the fidelity of the generated spectral images is limited only by the number of pixels on the FPA detector, and only several seconds of starting time is required for spectral image acquisition. This novel, high-definition technique represents the future of infrared chemical imaging analysis, a new discipline within the chemical and material sciences, which combines the capability of spectroscopy for molecular analysis with the power of visualization. In particular, chemical imaging is broadly applicable for noninvasive, molecular characterization of heterogeneous materials, since all solid-state materials exhibit chemical nonuniformity that exists either by design or by development during the course of material preparation or fabrication. Imaging, employing Raman and infrared spectroscopy, allows the precise characterization of the chemical composition, domain structure, and chemical architecture of a variety of substances. This information is often crucial to a wide range of activities, extending from the fabrication of new materials to a basic understanding of biological samples. In this study, step-scan imaging principles, instrument design details, and infrared chemical imaging results are presented. Since the prospect of performing high-resolution and high-definition mid-infrared chemical imaging very rapidly has been achieved with the step-scan approach, the implications for the chemical analysis of materials are many and varied.

Image Processing, Computer-Assisted↗

Precise relative ion abundances from Fourier transform ion cyclotron resonance magnitude-mode mass spectra.

The area under a correctly phased absorption-mode spectral peak is a direct measure of the number of oscillators (ions, spins, molecules) in Fourier transform spectrometry (ion cyclotron resonance, magnetic resonance, interferometry absorbance). However, phase correction can prove difficult when (as in broad-band Fourier transform ion cyclotron resonance (FT/ICR] detection is considerably time-delayed after excitation. In the absence of noise, Huang, Rempel, and Gross showed that a "complex area" method yields the correct absorption-mode peak area, for an unphased noiseless spectrum. In this paper, we show that the number of oscillators may also be obtained from a least-squares fit to a magnitude-mode (i.e., phase-independent) spectrum. In the presence of noise and in the absence of peak overlap, the magnitude-mode method offers precision superior to that based on magnitude-mode peak height, "complex area", or even direct digital integration of a correctly phased absorption-mode peak, as demonstrated by both theoretical derivation and experimental FT/ICR results. The present method thus appears to offer the best available determination of the relative abundances of ions of different mass-to-charge ratio in FT/ICR mass spectrometry.

Fourier Analysis↗

Porous SiO2 interferometric biosensor for quantitative determination of protein interactions: binding of protein A to immunoglobulins derived from different species.

Determination of kinetic and thermodynamic protein binding constants using interferometry from a porous Si Fabry-Perot layer is presented. A protein A capture probe is adsorbed within the pores of an oxidized porous Si matrix, and binding of immunoglobulin G (IgG) antibodies derived from different species is investigated. The relative protein A/IgG binding affinity is human > rabbit > goat, in agreement with literature values. The equilibrium binding constant (Ka) for human IgG binding to surface-immobilized protein A is determined to be (3.0 +/- 0.5) x 107 M-1 using an equilibrium Langmuir model. Kinetic rate constants are calculated to be kd = (2.1 +/- 0.2) x 10-4 s-1 and ka = (1.2 +/- 0.4) x 104 M-1 s-1 using nonlinear least-squares analysis, yielding an equilibrium binding constant of Ka = (5.5 +/- 1.5) x 107 M-1. Both steady-state and time-dependent measurements yield equilibrium binding constants that are consistent with literature values. Kinetic rate constants determined through nonlinear least-squares analysis are also in agreement with protein A/IgG binding on a surface. Dosing with a high concentration of analyte leads to deviations from ideal binding behavior, interpreted in terms of restricted analyte diffusion within the porous SiO2 matrix. It is shown that the diffusion limitations can be minimized if the kinetic measurements are performed at low analyte concentrations or under conditions in which the protein A capture probe is not saturated with analyte. Potential limitations of the use of porous SiO2 interferometers for quantitative determination of protein binding constants are discussed.

Animals↗

Typical physicochemical behaviors of chitosan in aqueous solution.

Physicochemical properties of a homogeneous series of chitosans with different degrees of acetylation and almost the same degree of polymerization were investigated in an ammonium acetate buffer. Techniques such as interferometry, static light scattering (in batch or coupled on line with a chromatographic system), and viscometry were processed. All of the results agree with a unique law of behavior only depending on the degree of acetylation of the polymer. Indeed, values of the refractive index increment, radius of gyration, second viral coefficient, and intrinsic viscosity are decreasing in the same way as DA is increasing. Three distinct domains of DA were defined and correlated to the different behaviors of chitosans: (i) a polyeletrolyte domain for DA below 20%; (ii) a transition domain between DA = 20% and 50% where chitosan loses its hydrophilicity; (iii) a hydrophobic domain for DAs over 50% where polymer associations can arise. Conformations of chitosan chains were studied by the calculations of the persistence lengths (L(p)). The average value was found to be close to 5 nm, in agreement with the wormlike chain model, but no significant variation of L(p) with the degree of acetylation was noticed.

Chemical Phenomena↗

Light scattering studies of the solution properties of chitosans of varying degrees of acetylation.

The use of two techniques, differential interferometry and quasi-elastic light scattering (QELS), allowed us to study solutions of chitosan varying in degree of acetylation (DA), degree of dissociation (alpha), and concentration (C(p)). With the first technique, we demonstrated the modification of the electric polarizability of the polymer chains, through a law of behavior of the variation of the refractive index increment dn/dC with DA and alpha. This brought us information on the various kinds of interactions (H-bonds, electrostatic, and hydrophobic) involved in the evolution of the solution properties. QELS experiments performed in dilute regime showed the presence of supramolecular structures depending on DA and alpha. The topology and the nature of these objects are discussed. The typical presence of aggregates and their evolution with concentration was also demonstrated in semidilute regime.

Acetylation↗

Recycled wool-based nonwoven material as an oil sorbent.

The aim of this study was to highlight the possibility of using recycled wool-based nonwoven material as a sorbent in an oil spill cleanup. This material sorbed higher amounts of base oil SN 150 than diesel or crude oil from the surface of a demineralized or artificial seawater bath. Superficial modification of material with the biopolymer chitosan and low-temperature air plasma led to a slight decrease of sorption capacity. Loose fibers of the same origin as nonwoven material have significantly higher sorption capacities than investigated nonwoven material. White light scanning interferometry analysis of the fibers suggested that roughness of the wool fiber surface has an important role in oil sorption. The laboratory experiments demonstrated that this material is reusable. Recycled wool-based nonwoven material showed good sorption properties and adequate reusability, indicating that a material based on natural fibers could be a viable alternative to commercially available synthetic materials that have poor biodegradability.

Adsorption↗

Tetrahedral onsager crosses for solubility improvement and crystallization bypass.

Pure organic molecules exhibiting a suitable concave rigid shape are expected to give porous glasses in the solid state. Such a feature opens new opportunities to avoid crystallization and to improve molecular solubility in relation to the high internal energy of these solid phases. To quantitatively explore the latter strategy, a series of rigid tetrahedral conjugated molecules nC and the corresponding models nR have been synthesized. Related to the present purpose, several properties have been investigated using UV absorption, steady-state fluorescence emission, differential scanning calorimetry, (1)H NMR translational self-diffusion, magic angle spinning (13)C NMR, and multiple-beam interferometry experiments. The present tetrahedral crosses are up to 8 orders of magnitude more soluble than the corresponding model compounds after normalization to the same molecular length. In addition, they give concentrated monomeric solutions that can be used to cover surfaces with homogeneous films whose thickness goes down to the nanometer range. Such attractive features make cross-like molecular architectures promising for many applications.

Journal Article↗

Properties of confined and sheared rhodamine B films studied by SFA-FECO spectroscopy.

We have used a surface forces apparatus and multiple beam interferometry to measure the absorbance of thin films of rhodamine B in water/ethylene glycol solutions while applying and measuring normal and lateral (shear) forces. Both normal and shear forces induced changes in the absorption spectra indicating a change in molecular alignment, and rhodamine-rhodamine and rhodamine-surface interactions. We also measured differences in the absorbance spectra in different regions of the contact indicating, as expected, that the stresses are not uniform throughout the contact area. We also observed crystallization (solidification) parallel to the shearing direction.

Journal Article↗

Scattered light interference from a single metal nanoparticle and its mirror image.

The spatial distribution of surface plasmon scattering from a single nanoparticle changes dramatically near a metal surface as a result of interference from the direct scattered light and indirect scattered light from the mirror reflection. The unique interference patterns have been reproduced by simulations based on Huygens-Fresnel wave propagation theory. The large spectral width of the surface plasmon scattering enables a vertical distance measurement with 10 nm resolution through this nonintrusive far field interferometry.

Letter↗

Two-dimensional infrared spectra of the 13C=18O isotopomers of alanine residues in an alpha-helix.

The parameters needed to describe the two-dimensional infrared (2D IR) spectra of the isotopically labeled alpha-helix are presented. The 2D IR spectra in the amide-I' spectral region of a series of singly 13C=18O-labeled 25-residue alpha-helices were measured by three-pulse heterodyned spectral interferometry. The dependence of the spectra on the population time was measured. Individual isotopomer levels (residues 11-14) were clearly identified in 2D IR, downshifted by approximately 61 cm(-1) from the main helical band. By analyzing the line shapes of the 13C=18O diagonal peaks that appeared at approximately 1571.3 +/- 0.8 cm(-1) for all four labeled samples, we observed wider structural distributions for residues 14 and 11 than those for 12 and 13. A small fast component in the correlation function was used to estimate the dynamics of these distributions. In all cases, the v = 1 --> 2 transition showed a more Lorentzian-like line shape and also decayed faster than the v = 0 --> 1 transition, indicating that the population relaxation time of the v = 2 state was significantly faster than the v = 1 state. The amide transitions with naturally abundant 13C=16O appeared at approximately 1594 cm(-1), forming very weak and blurred cross-peaks with 13C=18O isotopomer modes. The effects of spectral interferences on the coherence time dependence of the detection frequency spectrum were also investigated. The methods of first moments and Wigner analysis were developed to circumvent the interference effects on the weak isotopomer transitions. The structural origin of the distributions for individual isotopomers was proposed to be an effect of nearby lysine residues on the intrahelical hydrogen-bond network.

Alanine↗

Theory of diatomic molecules in an external electromagnetic field from first quantum mechanical principles.

We study a general problem of the translational/rotational/vibrational/electronic dynamics of a diatomic molecule exposed to an interaction with an arbitrary external electromagnetic field. The theory developed in this paper is relevant to a variety of specific applications, such as alignment or orientation of molecules by lasers, trapping of ultracold molecules in optical traps, molecular optics and interferometry, rovibrational spectroscopy of molecules in the presence of intense laser light, or generation of high order harmonics from molecules. Starting from the first quantum mechanical principles, we derive an appropriate molecular Hamiltonian suitable for description of the center of mass, rotational, vibrational, and electronic molecular motions driven by the field within the electric dipole approximation. Consequently, the concept of the Born-Oppenheimer separation between the electronic and the nuclear degrees of freedom in the presence of an electromagnetic field is introduced. Special cases of the dc/ac-field limits are then discussed separately. Finally, we consider a perturbative regime of a weak dc/ac field, and obtain simple analytic formulas for the associated Born-Oppenheimer translational/rotational/vibrational molecular Hamiltonian.

Journal Article↗

Direct measurement of ion accumulation at the electrode electrolyte interface under an oscillatory electric field.

The ionic charge accumulation at the metal-electrolyte interface is directly measured by using differential interferometry as a function of magnitude and frequency (2-50 kHz) of external electric field. The technique developed probes the ion dynamics confined to the electrical double layer. The amplitude of modulation of the ions is linearly proportional to the amplitude of applied potential. The linearity is observed up to high electrode potentials and salt concentrations. The frequency response of the ion dynamics at the interface is interpreted in terms of the classical RC model.

Electrodes↗

Fabrication of ordered mesoporous thin films for optical waveguiding and interferometric chemical sensing.

Planar optical waveguides with a propagation loss of 2.9 dB/cm at 633 nm were fabricated using ordered mesoporous thin films of TiO2-P2O5 nanocomposite deposited on the tin-rich surfaces of float glass slides. The resulting waveguides show substantial sensitivity to parts-per-million-level ammonia gas at room temperature on the basis of single-beam polarimetric interferometry.

Microscopy, Electron, Transmission↗

Coherent electronic and nuclear dynamics for charge transfer in 1-ethyl-4-(carbomethoxy)pyridinium iodide.

Although polaronic interactions and states abound in charge transfer processes and reactions, quantitative and separable determination of electronic and nuclear relaxation is still challenging. The present paper employs the amplitudes, polarizations, and phases of four-wave mixing signals to obtain unique dynamical information on relaxation processes following photoinduced charge transfer between iodide and 1-ethyl-4-(carbomethoxy)pyridinium ions. Pump-probe signal amplitudes reveal the coherent coupling of an underdamped 115 cm(-1) nuclear mode to the charge transfer excitation. Assignments of this recurrence to intramolecular vibrational modes of the acceptor and to modulation of the intermolecular donor-acceptor distance are discussed on the basis of a high-level density functional theory normal-mode analysis and previously observed wave packet dynamics of solvated molecular iodine. Nuclear relaxation of the acceptor induces sub-picosecond decay of the pump-probe polarization anisotropy from an initial value of 0.4 to an asymptotic value of -0.05. Electronic structure calculations suggest that relaxation along the torsional coordinate of the ethyl group is the origin of the anisotropy decay. Electric-field-resolved transient grating (EFR-TG) signal fields are obtained by spectral interferometry with a diffractive optic based interferometer. These measurements show that the signal phase and amplitude possess similar dynamics. Model calculations are used to demonstrate how the EFR-TG signal phase yields unique information on transient material resonances located outside the laser pulse spectrum. This effect can be rationalized in that the real and imaginary parts of the nonlinear polarization are related by the Kramers-Kronig transformation, which allows the dispersive component of the polarization response to exhibit spectral sensitivity over a larger frequency range than that defined by the absorption bandwidth.

Algorithms↗

Interfacial slip in entrained soap films containing associating hydrosoluble polymer.

Frankel's law predicts that the thickness of a Newtonian soap film entrained at small capillary number scales as Ca2/3 provided the bounding surfaces are rigid. Previous studies have shown that soap films containing low concentrations of high molecular weight (Mw) polymer can exhibit strong deviations from this scaling at low Ca, especially for associating surfactant-polymer solutions. We report results of extensive measurements by laser interferometry of the entrained film thickness versus Ca for the associating pair SDS/PEO over a large range in polymer molecular weight. Comparison of our experimental results to predictions of hydrodynamic models based on viscoelastic behavior shows poor agreement. Modification of the Frankel derivation by an interfacial slip condition yields much improved agreement. These experiments also show that the slip length increases as where zeta = 0.58 +/- 0.07. This correlation is suggestive of the Tolstoi-Larsen prediction that the slip length increases in proportion to the characteristic size of the fluid constituent despite its original derivation for liquid-solid interfaces.

Journal Article↗