Affinity capillary electrophoresis study of the linkage existing between proton and zinc ion binding to bacitracin A1

Measurements by capillary electrophoresis (CE) of bacitracin A(1) effective mobility at different pH values permitted to estimate the five acidic dissociation constants and the Stokes radii at different protonation stages of the macrocyclic dodecapeptide. The pK(a) values were 3.6 and 4.4 for the two carboxylic groups of the lateral chains of D-Asp-11 and D-Glu-4, respectively, 6.4 for the aza-atom of the imidazole ring of His-10, 7.6 for the amino group of N-terminal Ile-1 and 9.7 for the delta-amino group of D-Orn-7, very close to the values obtained by other researchers by titration experiments. In agreement with a rigid macrocyclic structure the Stokes radii of different protonated forms ranged only between 14.3 and 14.8 A. Best fitting procedures performed on experimental mobility measured at two different pH values (5.50 and 6.72) in the presence of increasing Zn(+2) concentration allowed confirming the model that assumes the binding of Zn(+2) to P(0) peptide form with a 1.5 x 10(3) M(-1) intrinsic association constant. Following to Zn(+2) binding, the pK(a) of the amino group of N-terminal Ile-1 is shifted from 7.6 to 5.9 and the Stokes radius is reduced of about 3 A. The mean charge of the bacitracin A(1)-Zn(+2) complex resulted +1.67 and +1.12 at pH 5.50 and 6.72, respectively. These results suggest that the amino group of N-terminal Ile-1 is not essential for Zn(+2) binding.     

Enhancement of the SHG efficiency in a doubly resonant 2D-photonic crystal microcavity

In this paper we discuss the conditions to obtain the enhancement of second harmonic generation in a two-dimensional circular photonic crystal AlGaAs cavity. The photonic crystal circular cavity offers the possibility of having high-Q resonance modes with respect to those obtained with other types of photonic crystal lattices. The crystallographic cut of the AlGaAs provides a strong nonlinear coupling between a transverse-magnetic (TM) polarized resonant mode at the fundamental wavelength and a transverse-electric (TE) polarized resonant mode at second harmonic wavelength. The double resonance condition leads to a strong improvement of the second harmonic generation process. A preliminary linear analysis has been performed by using the finite-difference time-domain method, which includes the dispersive response of the material, modeled using the well-known one-pole pair Lorentzian function.     

Design of Planar Optic Sensors for Hydrocarbon Detection

A realistic design of evanescent field optical sensors, constituted by three different kinds of planar waveguides covered by a sensing polymeric overlay, is performed. More precisely, the slab, the embedded strip and the ridge waveguides are considered. The sensor operation is simulated, in both the cases of lossy guided and leaky mode propagation, via a home made computer code. The optimal waveguide transverse section and length are identified, the advantages and drawbacks are shown. The ridge waveguide sensor exhibits appreciable characteristics: for a concentration C _w = 200 ppm of toluene in water, the absorbance pertaining to a device L = 2.6 cm long and for the guided quasi-TE₀₀ mode is A ≅ 5, while it is A ≅ 0.054 for a device long L ≅ 24.1 μm and the leaky quasi-TE₁₀ mode. The simulation results suggest that a selective excitation of the suitable propagation mode can enhance the sensor performance.     

Chloride-sulfate exchange on anion resins. Kinetic investigation. X. Use of autoradiography and scanning electron microscopy

Use of autoradiography and scanning electron microscopy, coupled with potentiometric and radionalytical investigation techniques, allows to confirm experimentally that the rate of Cl⁻→SO ₄ ²⁻ conversion of different anion resins at 0.006N solution concentration is not controlled) by ion interdiffusion and that sulfate penetration into the resin bead occurs according to a progressive conversion mechanism.     

Double Vivaldi antenna for wireless optical networks on chip

In this paper we present a double plasmonic Vivaldi antenna for on-chip optical wireless communication. The proposed antenna is a two-element broadside array fed by a silicon waveguide. The designs of the power splitter and of the hybrid Si-plasmonic coupler used for antenna excitation are described in detail. The array radiation characteristics are optimized through Finite Difference Time Domain simulations and the performance of a point-to-point link is evaluated. The proposed double Vivaldi array increases the gain of 3 dB with respect to a single antenna, improving the received power on a link of 6 dB when the double antenna is used for both transmitting and receiving sections.     

Vertical link solutions for multilayer optical-networks-on-chip topologies

This paper presents two different approaches that may allow the optical interconnection between superposed levels of multilayer photonic circuits as, for example, in optical-networks-on-chip. The first configuration is based on multi-mode interference devices, while the second one exploits multiple stacked directional couplers. The issues concerning the analytical and numerical design of such devices are discussed, together with a performance analysis in terms of efficiency and footprint.     

All-optical amplification via the interaction among guided and leaky propagation modes in lithium niobate waveguides exploiting the cascaded second-order nonlinearity

The aim of this paper consists of performing a theoretical investigation of an all-optical amplifier and discussing the problems for a realistic implementation. An original periodically poled lithium niobate channel waveguide, having the optical c-axis opportunely oriented on the xz plane was considered. The waveguiding structure, designed to operate in the second communication window of optical fibers, shows versatile properties as was theoretically demonstrated. In fact, it enables both the selection and the coupling strength of four different propagation modes, two guided and two leaky, interacting via the cascaded second-order nonlinearity. The coupling among guided and leaky modes is obtained by means of two different techniques: (i) birefringence phase-matching (BPM) via a suitable orientation of the optical c-axis crystal on the xz plane and (ii) quasi-phase-matching by periodical inversion of the lithium niobate ferroelectric domains. A strong diffusion of magnesium in the region external to the periodically poled waveguiding channel is needed in order to achieve the suitable BPM and to maximize the bounding of the electromagnetic field and, thus, the overlapping integrals. Finally, a powerful refinement of device operation via the use of the seeded second harmonic waves is proposed. Gains of the order of 20 dB are achieved with reduced bias powers. The order of magnitude of the bias power decreases, with respect to the unseeded second harmonic operation, from 145 to 32 W.     

Enhancement and inhibition of second-harmonic generation and absorption in a negative index cavity

We study second-harmonic generation in a negative-index material cavity. The transmission spectrum shows a bandgap between the electric and magnetic plasma frequencies. The nonlinear process is made efficient by local phase-matching conditions between a forward-propagating pump and a backward-propagating second-harmonic signal. By simultaneously exciting the cavity with counterpropagating pulses, and by varying their relative phase difference, one is able to enhance or inhibit linear absorption and the second-harmonic conversion efficiency.     

Different binding thermodynamics of Ni2+, Cu2+, and Zn2+ to bacitracin A1 determined by capillary electrophoresis

Thermodynamics of the binding of Ni(2+), Cu(2+) and Zn(2+) to bacitracin A(1) was studied by capillary electrophoresis measuring the peptide effective mobility at different pH in the presence of increasing concentration of the three ligands. The affinity follows the order Ni(2+) > Cu(2+) > Zn(2+), with association constant values of (2.3 +/- 0.1)x10(4), (4.9 +/- 0.2)x10(3), and (1.5 +/- 0.1)x10(3) M(-1), respectively. The only model able to rationalize mobility data implies that metal ion binds to the P(0) peptide form. Moreover, mobility values indicated a change of bacitracin A(1) acidic properties on Ni(2+) and Cu(2+) binding, with a shift of the pK(a) of N-terminal Ile-1 from 7.6 to about 5 and of the pK(a) of the delta-amino group of D-Orn-7 from 9.7 to about 7. Even though on Zn(2+) binding a shift of the N-terminal Ile-1 pK(a) was observed, restrictions in the pH range suitable for investigation, due to precipitation phenomena, did not allow establish if the shift of D-Orn-7 lateral chain pK(a) also occurred. Nonetheless, if present, the shift should be limited to the 7.8-9.7 range. Mobility data indicated that the Stokes radius of the complexes is ca. 3 A lower than that of the free peptide. The present results indicate that metal-ion binding to bacitracin A(1) is more complex than previously assumed.     

Design of an optical sensor array for hydrocarbon monitoring

Evanescent field optical sensors are accurately designed for hydrocarbon monitoring in water. Various kinds of waveguide sensors are optimized by considering a polydimethylsiloxane polymeric overlay as sensor region. The simulation results suggest that the selection of a suitable waveguide cross section can enhance the sensor performance. In particular, the hollow waveguide sensor exhibits very intriguing performance, the absorbance being quite linear with respect to the contaminant concentration. For the toluene pollution the absorbance exhibits a slope S_TE^A = 2.52 ×10^-2 ppm^-1{S_{\rm TE}^{A} =2.52 \times 10^{-2}\,{\rm ppm}^{-1}} for a waveguide reference length L = 1.18 mm. In order to simultaneously detect different pollutants in water such as toluene, benzene, chlorobenzene and ethilbenzene, an array of four miniaturized hollow waveguide sensors is designed.