Spectral Extinction of Colloidal Gold and Its Biospecific Conjugates

We have prepared gold sols with mean particle diametersd_min the range 4 to 50 nm and measured their extinction spectra and size dependences of the extinction peak position λ_maxand valueE_max. The measured increasing function λ_max(d_m) displays a pronounced bend near the particle diameterd_m∼ 10 nm, where the value of λ_maxsharply decreases with reduction in the particle size. To explain these findings, the extinction spectra of sols with the particle size and axial ratio polydispersity are calculated using Mie's theory, the T-matrix method, and various experimental sets of the bulk gold optical constants modified with regard to size-limiting effects. It is shown that the measured λ_max(d_m) andE_max(d_m) dependences are inconsistent with calculations based on Mie's theory and the bulk gold optical constants. The most generalized model including the size dependence of the imaginary part of the dielectric permeability and the size and shape polydispersity gives good agreement with experimental extinction spectra for 5-, 10-, 24-, and 40-nm sols, as well as with the measured functions λ_max(d_m) andE_max(d_m). Based on electron-microscopic and spectral data, calibration curves are obtained for efficient spectrophotometric control over the particle size and for estimation of the amount of restorer essential for the preparation of particles of a given size. A simplest two-layer spherical model is employed to elucidate the basic changes in sol spectra after conjugation with specific biomacromolecules and to draw some conclusions about the conjugate shell structure.     

A Multilayer Model for Gold Nanoparticle Bioconjugates: Application to Study of Gelatin and Human IgG Adsorption Using Extinction and Light Scattering Spectra and the Dynamic Light Scattering Method

A new model of colloidal gold (CG) bioconjugates is proposed. The model consists of a gold core and a primary polymer shell formed during conjugate synthesis. Additionally, the conjugate includes a secondary shell formed during its interaction with target molecules. Each of the inhomogeneous shells is modeled by the arbitrary number of discrete layers. Using Mie theory for multilayered spheres, we calculated the extinction and static light scattering (SLS, at 90°) spectra, as well as differential spectra A(), I() describing the effects of primary and secondary shells. Our calculations are performed for the conjugates with gold particle diameters d = 10–160 nm and two 5-nm shells. The primary shell consists of two 2.5-nm layers with the refractive indices of 1.50 and 1.45; the secondary shell, of two 2- and 3-nm layers with the refractive indices of 1.45 and 1.40. The differential spectra are related to the adsorption of target molecules and possess a characteristic resonance that is shifted to the red region of spectra compared to the usual localized plasmon resonances of gold particles. The maximal values of differential resonances A _max and I _max are observed for gold particles with diameters about 40–60 nm (extinction spectra) or 70–90 nm (the SLS spectra). The adsorption of human gamma-globulin (hIgG) and gelatin onto 15- and 34-nm gold particles was studied using the SLS and extinction spectra in combination with the dynamic light scattering measurements. It is shown that the thickness of adsorbed layer is equal to 5–6 nm for hIgG and to 15–18 nm for gelatin. The experimental extinction and SLS spectra for CG + hIgG conjugates are well explained by a simple model with the gold core and homogeneous polymer coating. For the CG + gelatin conjugates, we used the new model with inhomogeneous polymer coating, which is modeled by 10 discrete layers with the total thickness of 16–18 nm and exponential spatial profile of shell refractive index.     

Anodic Dissolution of Gold in Cyanide Solutions Containing Lead Ions: Effect of the Solution pH

The effect of the electrode potential on the gold dissolution rate in alkali–cyanide solutions with and without 10^–5 M of hydroxy compounds of lead is studied. With the compounds, the process rate passes through a maximum, whose potential E _m shifts in the negative direction and whose height drops with increasing pH. The pH dependence of E _m is linear, with the slope dE _m/dpH = –71 ± 5 mV, and correlates with that of the potential at which lead adatoms start to undergo desorption from the gold surface in alkali solutions. Without the compounds, the gold dissolution rate in alkali–cyanide solutions is independent of the solution pH at E < 0. Thus, the effect of the solution pH in this potential range is connected not with a direct participation of hydroxide ions in the anodic process but is of a secondary nature caused by the dependence of the region of adsorption of catalytically active lead adatoms on the hydroxide ion content in solution.     

Laser and radiofrequency spectroscopy of the 5d 4 6s 6 D multiplet in Ta I

The hyperfine structure (hfs) of¹⁸¹Ta has been investigated using laser radio-frequency double resonance and high resolution laser spectroscopy on collimated atomic beams. The magnetic dipole and electric quadrupole hyperfine structure coupling constants of the 5d ^{4 6} s 6D _{3/2, 5/2, 7/2, 9/2} metastable states have been determined using radio-frequency spectroscopy. In the 5d ⁴ 6s ⁶ D _1/2 metastable state and the excited 5d ³ 6s 6p ⁴ D _3/2,⁶ D _{5/2, 9/2} as well as the unidentified 28 182.6 cm^–1 and 30 021.2 cm^–1 states, hfs constants have been obtained from high resolution laser spectroscopy. A radio-frequency converter has been developed in order to reach the frequency region 2.7–10 GHz.     

Kinetics of limonene autooxidation

The kinetic parameters of the oxidizability of Iimonene,k _p/(2k _t)^0.5 = 6.0- 10^–3 L^{0 5} mol^–5 s^–0.5, and of the bimolecular radical decomposition of hydroperoxides 2ek _d = 6.0 · 10^–6 L mol^–1 s^–1 were determined at 60 °C The oxidation rate increases in the presence of micro additives of water. Average effective diameters of particles formed in the water-AOT-(n-decane + lirnonene) microemulsion were measured by the light scattering technique. The hydroperoxides were found to affect the size of the microemulsion particles.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 7, pp. 1682–1685, July. 1996.     

Radiative recombination rates with different statistical distributions

The isotope shift and hyperfine structure in a rhenium hollow cathode discharge was studied for transitions of the type 5d ⁵6s7s 5d ⁵6s6p and 5d ⁵6s6d 5d ⁵6s6p through Doppler-free saturation absorption laserspectroscopy and high resolution interferometry. Taking configuration mixing in the lower levels of 5d ⁵6s6p under consideration, we obtain average configuration isotope shift values for 5d ⁵6s7s of –1760(100) MHz and for 5d ⁵6s6d of –1970(200) MHz. These experimental values compare extremely well with the theoretically predicted configuration isotope shifts in rhenium, based on pseudo-relativistic Hartree-Fock calculations, of –1710 MHz and –1940 MHz, resp. In addition hyperfine structure constants for rhenium levels of 5d ⁵6s6d are reported here for the first time.Research scientist from the University of Istanbul, Turkey     

Electrophoresis of large colloidal particles with surface charge layers. Position of the slipping plane and surface layer thickness

A theory is proposed for the electrophoresis of a large colloidal particle with a surface charge layer. The slipping plane is assumed to be located within the surface layer but may not be located at the boundary between the surface layer and the particle core. In previous studies, the depth of the slipping plane is assumed to coincide with the surface layer thickness. The present theory makes it possible to examine the separate dependence of the electrophoretic mobility on the position of the slipping plane and on the surface layer thickness. It is shown that, at constant amount of particle-fixed charges in the surface layer, the mobility increases as the depth of the slipping plane (d _s ) increases, while it decreases as the surface layer thickness (d _c ) increases, causing a mobility maximum in some cases ifd _s =d _c . Several approximate analytic expressions for the mobility are presented.     

The well-tempered model core potentials for the main-group elements Li–Rn

The well-tempered model core potential (wtMCP) parameters and valence basis sets, based on the well-tempered basis set expansion, were developed for the main-group elements Li–Rn. For the s–block elements, the valence space comprises the ns valence shell and the outermost core (n–1)p shell. For the p-block elements, the ns and np shells together with the (n–1)d shell make up the valence space. Nonrelativistic wtMCPs were developed for all atoms. Scalar-relativistic wtMCPs were prepared for all atoms heavier than Ar by using the relativistic elimination of small components to obtain the reference and core orbitals. The new potentials were tested at the restricted Hartree–Fock, second-order Mø øller–Plesset perturbation theory and density functional theory with Beckes three-parameter hybrid functional combined with Perdews 1991 gradient-corrected correlation functional levels for several diatomic molecules and the results were compared with those obtained from all-electron calculations and experimental values. Excellent agreement between the results was obtained.     

Aquation of α-cis-chloroaquoethylenediamine-N,N'-diacetatocobalt(III) in aqueous and in mixed solvents: A mechanistic study

Summary The displacement of chloride ligands from -cis-chloro-aquoethylenediamine-N,N-diacetatocobalt(III) in nonacidic aqueous solutions was followed conductimetrically at 30–45° and the products of aquation were characterised by conductance, spectral and ion-exchange techniques. The rate constants for aquation in aqueous media and in 1 : 4 v : v mixed solvents at 25° are: 4.0 × 10^–5 s^–1 in H₂O, 2.71 × 10^–5 s^–1 in MeOH : H₂O, 2.74 × 10^–5 s^–1 in EtOH: H₂,O and 2.58 × 10^–5 s^–1 n in Me₂CO : H₂O. The corresponding H&#x002A; and S&#x002A; values have also been evaluated. Solvent polarity has a marked influence on the rate of chloride ion release. The aquation rate constants and the activation parameters have been correlated with solvent parameters,e.g. D, Y-values, Dimroth's E_T and Kosower's Z-values and, based on these correlations, a dissociative interchange (I_d) mechanism is proposed rather than dissociative as observed for some other cobalt(III) complexes.Senior author.     

Constrained anisotropic dipole oscillator strength distribution techniques,and reliable results for anisotropic and isotropic dipole molecular properties,with applications to H2 and N2

Summary Constrained anisotropic dipole oscillator strength distribution techniques are discussed and applied to obtain reliable results for a wide variety of the anisotropic and isotropic dipole properties of H₂ and N₂. These include the dipole oscillator strength sumsS _k, k=2, 1, –1/2(–1/2) –2, –3, –4, ..., the logarithmic dipole sumsL _k and mean excitation energiesI _k, k=2(–1) – 2, and, as a function of wavelength, the dynamic polarizability and the associated anisotropy, the total depolarization ratio, the Rayleigh scattering cross section, and the Verdet constant. The anisotropic components of the DOSD for a molecule are obtained from a given recommended isotropic DOSD by using a constrained least squares procedure and a series of known anisotropic constraints. Assuming that sufficient input is available, the constrained DOSD approach used in this paper is the only available method for the reliable evaluation ofall the relevant anisotropic and isotropic dipole properties for a wide variety of atoms and molecules.This research was supported by a grant from the Natural Sciences and Engineering Research Council of CanadaOn leave from Department of Physics, Meerut University, Meerut, India     

Vibronic coupling effects in trimeric mixed-valence clusters

The spectrum of a trimeric mired-valence cluster d₁–d₁–d₂ is calculated in the Piepha-Krausz-Schatz vibronic model. Based on the vibronic spectra obtained magnetic properties of the d₁–d₁–d₂ cluster are investigated It is shown that spin of the system's ground state may change not only as a result of double exchange reduction by vibronic coupling, but also due to a diflerence in the eneqy dependence of the lowest vibronic states on the vibronic coupling constant for diflerent total spin values. Unlike previous studies of vibronic interactions in the d₁–d₁–d₂ cluster, in this study the diagonalizations of the vibronic-coupling and double-exchange matrices are fuljilled simultaneously, using Lanczos' method. Due to this, all types 4 vibronic state mixing by double exchange could be taken into account properly.Moldova State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 5, pp. 20–32, September–October, 1993.Translated by L. Smolina     

Simultaneous determination of NH3, SO2, NO and NO2 by direct UV-absorption in ambient air

Summary Direct spectroscopic methods are not hampered by wall losses, are highly specific, have a potential for real time detection and offer the possibility to measure several species simultaneously in one experiment. This is demonstrated for the determination of NH₃, NO and SO₂ in ambient air by a differential optical a2bs orption spectroscopy (DOAS) technique in the spectral region 207–221 nm. Detection limits were 1 ng/g or better.     

Dynamic Contact Angles of Water in Ultrathin Capillaries

Velocities of motion V of advancing meniscus of water in quartz capillaries with radii from 45 to 270 nm was directly measured using an optical microscope. In the case, when the meniscus advanced over the wetting film that is remained after the previous meniscus receding, hysteresis was not observed, and the wetting was complete. When the meniscus advanced over the yet unwetted surface, the dynamic contact angle _d greatly depended on V, this dependence was the more pronounced, the smaller the r value. As the velocity V increases to 10^–3 cm s^–1, the value of _d rises to 60°–70° reaching the plateau. Preliminary adsorption of water vapors on the capillary surface markedly decreases the values of _d. The results obtained cannot be explained in terms of hydrodynamic and barrier theories of the contact angle. It was assumed that the controlling factor is the kinetics of vapor adsorption on the capillary surface in front of advancing meniscus.     

Static electric properties of LiH: explicitly correlated coupled cluster calculations

Explicitly correlated MBPT-R12 and coupled cluster [up to CCSD(T)-R12] methods have been used in calculations of various (vibrationless) electrical properties for the LiH molecule, including the dipole and quadrupole moments, dipole and quadrupole polarizability tensors, dipole hyperpolarizability tensors, and the second dipole hyperpolarizability tensors. Generally, with extension of the basis set the R12 method did not lead to faster convergence for the calculated properties towards the basis limit. Nevertheless, R12 calculations serve as useful indicators to judge the reliability of the results, and substantially help in determining the accuracy. Results obtained with the 11s8p6d5f/9s8p6d5f basis and CCSD(T)-R12 calculated within this work should be close to the basis set limit. Received: 8 June 1998 / Accepted: 23 July 1998 / Published online: 7 October 1998     

Development of a PLS based method for determination of the quality of beers by use of NIR: spectral ranges and sample-introduction considerations

Near infrared spectroscopy (NIR) has been used to determine important indicators of the quality of beers, for example original and real extract and alcohol content, using a partial least squares (PLS) calibration approach. A population of 43 samples, obtained commercially in Spain and including different types of beer, was used. Cluster hierarchical analysis was used to select calibration and validation data sets. Absorbance sample spectra, in transmission mode, were obtained in triplicate by using a 1-mm pathlength quartz flow cell and glass chromatography vials of 6.5 mm internal diameter. The two methods of sample introduction were compared critically, on the basis of spectral reproducibility for triplicate measurements and after careful selection of the best spectral pre-processing and the spectral range for building the PLS model, to obtain the best predictive capability. For each mode of sample introduction two calibration sets were assayed, one based on the use of 15 samples and a second extended based on use of 30 samples, thus leaving 28 and 13 samples, respectively, for validation. The best results were obtained for 1 mm flow cell measurements. For this method original zero-order spectra data in the ranges 2220–2221 and 2250–2350 nm were chosen. For the real extract, original extract, and alcohol d_x-y and s_x-y values of –0.04 and 0.07% w/w, –0.01 and 0.13% w/w, and –0.01 and 0.1% v/v, respectively, were obtained. The maximum errors in the prediction of any of these three indicators for a new sample were 2.2, 1.2, and 1.9%, respectively. This method compares favorably with the automatic reference method in terms of speed, reagent consumed, and waste generated.     

Application of an ion-fitted pseudopotential to HF,H2O,NH3, BeO,and HCl in a Gaussian lobe basis

The core potentials for atoms of atomic numer 1–18 fitted to ion spectra by Chang, Habitz, Pittel, and Schwarz have been extended to the molecular case in a Gaussian lobe basis by using a six-Gaussian (6G-POT ) representation for the exponential factors of the atomic core potentials. In a (9s/5p/1d) basis the 6G-POT one-electron energies, dipole moments, and Mulliken charges are improved over a one-Gaussian potential form for HF, NH₃, and H₂O; BeO also yields good agreement within 2.6% of the experimental bond length. For HCl, the core potential shows larger errors in the dipole moment (7%) and one-electron eigenvalues (2%), but a 75% saving in computer time is realized for HCl compared with only about 35% for first-row systems using the 6G-POT core potentials. Analytical expressions are given to extend the 6G-POT method up to s, p, d, f, and g valence shells.     

Laser induced stepwise and two-photon ionization studies of strontium in the air acetylene flame

Using strontium atoms present as a trace constituent in an air-acetylene flame as an example, a rich laser enhanced ionization spectrum was obtained. One pulsed tunable dye laser was tuned to a transition originating from the ground state (460.73 nm) and another scanned over different spectral regions. The lines obtained were spectroscopically characterized as to the type of absorption process, which included non-resonant processes as well as single wavelength, two-wavelength, and two-photon resonant processes.With a maximum irradiance of 100 MW cm⁻², two-photon transitions resulting in collisionally assisted ionization included the 5sns and 5dnd Rydberg series (up to 37s and 15d) together with a strong auto-ionizing transition at 431.10 nm. The complexity of the observed ionization spectrum when the irradiance is high indicates that spectral interferences need to be carefully considered in analytical applications.     

Cationic polymerization of hydrocarbon monomers under the action of acyl halide complexes with Lewis acids

Polymerization of isobutylene in hexane at –78 °C under the action of the complex AcBr · 2AlBr₃ (Ac-2) affords polyisobutylene having C=O groups at the head and C-Br or C=C groups at the tail of all the molecules. The presence of the latter indicates that there occurs proton elimination from the growing carbocation with the formation of a superacid HBr · 2AlBr₃ which is unable to initiate the polymerization repeatedly under given contitions. This makes it possible to consider proton elimination as the reaction of the decay of active centers with the rate constantk _d. This value has been calculated from the rate of accumulation of the polymeric molecules having terminal C=C bonds:k _d=3.5 · 10^–4 s^–1. The rate constant of chain growthk _g has been determined from polymerization kinetics and from the content of active centers:k _g=6.2 L mol^–1 s^–1.For part 3, see ref. 4.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 883–886, May, 1993.     

Electrooptics of β-FeOOH Particles in Aqueous Media: 1. Reversing-Pulse Electric Birefringence in the Low Field Region

Reversing-pulse electric birefringence (RPEB) of a nearly monodisperse iron(III) hydroxide oxide sample in the β-form (β-FeOOH) was measured at 25°C and at a wavelength of 633 nm in aqueous media in the presence of NaCl. The concentrations of β-FeOOH and added NaCl varied between 0.00111 and 0.0555 g/L and 0.03 and 2.0 mM, respectively. Except for the suspensions with high salt concentrations, each RPEB signal showed a dip or minimum in the reverse process upon electric field reversal, together with a smooth rise in the buildup and a fall in the decay process. The observed signals were analyzed with a new RPEB theory, which takes into account not only the permanent electric dipole moment (μ) but also the root-mean-square ionic dipole moment (m^21/2) due to the ion fluctuation in ion atmosphere, in addition to the field-induced electronic (covalent) dipole moment Δα′ E. The results showed that the slowly fluctuating moment of m^21/2 is by far the most predominant one for the field orientation of the β-FeOOH particle, though the permanent dipole moment μ may not be completely excluded. The rotational relaxation time of the whole particle was evaluated from the decay signal, while the relaxation time for fluctuating ions was estimated from RPEB signal fitting. The sign of the steady-state birefringence for β-FeOOH suspensions was positive without exception under the present conditions. The birefringence signals in the steady state (δ/d) were proportional to the second power of the applied field strength (E) in the low field region; thus, the Kerr law was verified to hold for β-FeOOH suspensions. The specific Kerr constant was evaluated for each suspension by extrapolating the values of δ/d to zero field (E→0).     

Effects of strong inter-hydrogen bond dynamical couplings in the polarized IR spectra of adipic acid crystals

This paper presents the results of the re-investigation of polarized IR spectra of adipic acid and of its d₂, d₈ and d₁₀ deuterium derivative crystals. The spectra were measured at 77 K by a transmission method using polarized light for two different crystalline faces. Theoretical analysis concerned linear dichroic effects and H/D isotopic effects observed in the spectra of the hydrogen and deuterium bonds in adipic acid crystals at the frequency ranges of the ν_O–H and the ν_O–D bands. The two-branch fine structure pattern of the ν_O–H and ν_O–D bands and the basic linear dichroic effects characterizing them were ascribed to the vibronic mechanism of vibrational dipole selection rule breaking for IR transitions in centrosymmetric hydrogen bond dimers. It was proved that for isotopically diluted crystalline samples of adipic acid, a non-random distribution of protons and deuterons occurs in the dimers (H/D isotopic “self-organization” effect). This effect results from the dynamical co-operative interactions involving the dimeric hydrogen bonds.