Ueber Zuckerbestimmungen

Analytical and Bioanalytical Chemistry -     

Hot bands in jet-cooled and ambient temperature spectra of chloromethylene

Rotationally resolved spectra of several bands lying to the red of the origin of the A(1)A" - X (1)A' band system of chloromethylene (HCCl), were recorded by laser absorption spectroscopy in ambient temperature and jet-cooled samples. The radical was made by excimer laser photolysis of dibromochloromethane, diluted in inert gas, at 193 nm. The jet-cooled sample showed efficient rotational but less vibrational cooling. Analysis showed that the observed bands originate in the (upsilon(1),upsilon(2),upsilon(3)) = (010), (001), and (011) vibrational levels of the ground electronic state of the radical, while the upper-state levels involved were (000), (010), (001), and (011). Vibrational energies and rotational constants describing the rotational levels in the lower-state vibrational levels were determined by fitting to combination differences. The analysis also resulted in a reevaluation of the C-Cl stretching frequency in the excited state and we find E(001)' = 13 206.57 or 926.17 cm(-1) above the A(1)A" (000) rotationless level for HC(35)Cl. Scaled ab initio potential energy surfaces for the A and X states were used to compute the transition moment surface and thereby the relative intensities of different vibronic transitions, providing additional support for the assignments and permitting the prediction of the shorter wavelength spectrum. All the observed upper state levels showed some degree of perturbation in their rotational energy levels, particularly in K(a) = 1, presumably due to coupling with near-resonant vibrationally excited levels of the ground electronic state. Transitions originating in the low-lying a(3)A" were also predicted to occur in the same wavelength region, but could not be identified in the spectra.     

Protein concentration and adsorption time effects on fibrinogen adsorption at heparinized silica interfaces

Heparin was modified with adipic dihydrazide and covalently linked to surface-activated silica wafers. X-ray photoelectron spectroscopy was used at each stage of derivatization and showed that successful immobilization had taken place. Surfaces were imaged with atomic force microscopy to determine the uniformity of the heparin layer as well as its thickness. In situ ellipsometry was used to estimate layer thickness as well, and to study protein concentration and adsorption time effects on the adsorption and elution kinetics exhibited by human plasma fibrinogen. The adsorbed amount of fibrinogen increased with time and concentration on each type of surface. Under all experimental conditions, fibrinogen adsorbed at a lower rate and to a lower extent on heparinized as compared to unheparinized silica. In addition, buffer elution experiments showed that fibrinogen was less tightly bound to heparinized silica. In order to examine behavior relative to fibrinogen mobility at these interfaces, the sequential adsorption of fibrinogen was recorded. The difference in adsorption rates between the first and second adsorption cycles, evaluated at identical mass density, indicated that post-adsorptive molecular rearrangements had taken place. In general, higher solution concentration and longer adsorption time in the first adsorption step led to more rearrangement, and these history dependent effects were more pronounced on the heparinized silica. These rearrangements are suggested to involve clustering of adsorbed fibrinogen, in this way increasing the amount of unoccupied area at the interface. These rearrangements were presumably facilitated on the heparinized silica by enhanced lateral mobility of fibrinogen at this negatively charged, highly hydrophilic interface.     

Effective Kerr nonlinearity and two-color solitons in photonic band-gap fibers filled with a Raman active gas

We predict a strong effective Kerr nonlinearity in hollow-core photonic crystal fibers filled with a Raman active gas which exceeds the intrinsic Kerr nonlinearity by 2 orders of magnitude. Two-color bright-bright and dark-bright solitons supported by this nonlinearity are found and the feasibility of their experimental observation is demonstrated.     

A study of the decay KL0 → π±e∓νe

In a study of charged K_L⁰ three-body decays a sample of 6668 K_L⁰ → π^±e^?ν candidates has been obtained. The Dalitz plot distribution is in agreement with V ? A theory, and limits are presented for scalar and tensot contributions to the weak current. Using a conventional expansion for the form factor f₊ we find λ₊ = 0.055 ± 0.010 with systematic effects estimated at ± 0.01.     

A one-step procedure for the monoacylation of symmetrical 1,2-diols

A series of lanthanide (III) salts have been shown to catalyze the monoacylation of symmetrical 1,2-diols by carboxylic acid anhydrides with surprisingly high selectivity.     

Tunneling and nonhyperbolicity in quantum dots

We argue that many major features in electronic transport in realistic quantum dots are not explainable by the usual semiclassical approach, due to the contributions of the quantum-mechanical tunneling of the electrons through the Kolmogorov-Arnol'd-Moser islands. We show that dynamical tunneling gives rise to a set of resonances characterized by two quantum numbers, which leads to conductance oscillations and concentration of wave functions near stable and unstable periodic orbits. Experimental results agree very well with our theoretical predictions, indicating that tunneling has to be taken into account to understand the physics of transport in generic nanostructures.