Linear dichroism study of retinoids

Linear dichroism spectra of several retinoids and related polyenes incorporated in stretched polyethylene films were determined. It is suggested that the retinoids are oriented with the plane of the ring parallel to the stretching direction of the film, the long polyene chain being displaced from that direction.     

Metal island coated polymer sensor for direct determination of the volume effect of chaotropic agents

A new optical sensor is presented, based on the analyte reaction resulting in swelling and shrinking of a thin polymer layer. Changing the concentration of ions in a new bisazide photo-cross-linked poly(vinylpyrrolidone) polymer results in a concentration-dependent volume change of the hydrated gel. The volume response of the sensor induced by different ions is fully reversible over more than 250 cycles. The response of the device depends on the type, the charge and the concentration of the ions. The sensor material is part of an optical thin film system which transforms the variations in volume of the polymer into spectral information. The steady state of the sensor response is obtained within 60 s. The response time is mainly limited by the pump rate, the back pressure and the total volume of the system but not by the swelling of the sensor polymer. A comparative study of ion effects has demonstrated a fundamental correlation of the polymer swelling properties with the Hofmeister series of chaotropic agents. Thus it is concluded that the photopolymer, which is solubilized in aqueous solutions by the interaction of its amide structure with the solvent, behaves like the backbone amide structure of proteins.     

Gold particle interaction in regular arrays probed by surface enhanced Raman scattering

Lithographically designed two-dimensional arrays consisting of gold nanoparticles deposited on a smooth gold film are used as substrate to examine the SERS effect of the trans-1,2-bis (4-pyridyl) ethylene molecule. These arrays display two plasmon bands instead of the single one observed for the same arrays of particles but deposited on indium tin oxide coated glass. Laser excitation within the short wavelength band does not bring about any SERS spectrum, while excitation within the long wavelength band yields SERS spectra with a gain per molecule rising up to 10(8). The simultaneous investigation of extinction and Raman spectra of arrays exhibiting various topography parameters enables us to suggest an interpretation for both the occurrence of the two plasmon resonances and for the high Raman enhancement. We suggest to assign the short wavelength band to a plasmon wave propagating at the gold glass interface and the long wavelength one to an air/gold surface plasmon mode modified by particle-particle interaction.     

Encapsulation of Mithramycin in Liposomes in Response to a Transmembrane Gradient of Calcium Ions

The recent discovery that mithramycin(MTR) in aqueous solution forms a high affinity[Ca(MTR)4]2- complex led us to the idea thatCa2+-loaded liposomes might be able to accumulateMTR in their aqueous internal compartment. Wetherefore investigated the uptake of MTR into largeunilamellar vesicles (LUV) containing NaCl orCaCl2. Our data show that MTR was efficientlyaccumulated within LUV made fromdipalmitoylphosphatidylcholine and cholesterol, onlywhen the liposomes contained Ca2+ and wereresuspended in a Ca2+-free medium. A drugencapsulation efficiency as high as 60% was achieved,at a drug to lipid molar ratio of 1/18. The circulardichroism and fluorescence excitation spectra ofliposome-encapsulated MTR (LMTR) displayed strongsimilarities with those of the [Ca(MTR)4]2-complex. LMTR was found to be stable, when submittedto conditions that destabilized the[Ca(MTR)4]2- complex. Upon dilution andincubation for 24 h at 37 °C, MTR-containingliposomes did not release a significant amount of MTR.These properties were attributed to the formation ofa high affinity complex between MTR and Ca2+inthe aqueous compartment of liposomes.     

Femtosecond decay-time measurement of electron-plasma oscillation in nanolithographically designed silver particles

The decay time of the electron-plasma oscillation in silver nanoparticles is measured at a nanoparticle film consisting of regularly arranged, identically shaped and identically oriented particles. By design of a noncentrosymmetric particle shape, SHG in transmission at normal incidence of the fundamental beam is obtained. Therefore the autocorrelation function of the optical near field oscillation of the particle, excited by two emporally overlapping fs laser pulses separated by a defined delay time, could be measured. A decay time of 10¹ fs was extracted. This result shows that the damping of the electron-plasma oscillation in nanometric particles is approximately a factor of 2 larger than expected from the value of the imaginary part of the bulk metal dielectric funtion when consideration of the radiation damping in the particles is included. Received: 28 October 1996/Revised version: 2 December 1996     

Influence of thermal treatment on second-harmonic generation in silver islands films

A reduction in second-harmonic generation (SHG) efficiency at silver islands films is observed when such submicroscopic structures are tempered at approx. 410K. This behavior can be attributed to two facts: an increase in symmetry in film morphology and changes in the particles' electron plasma resonances causing field enhancements inside the particles. The observed correspondence between submicroscopic surface morphology and obtained second-harmonic signal suggests a SHG microscope for the maplike distinguishing between differently structured surface areas.Dedicated to Prof. Dr. Herbert Welling on the occasion of his 60th birthday     

Sliding plastics on ice: fluorescence spectroscopic studies on interfacial water layers in the μm thickness regime

Received: 28 July 1997/Revised version: 20 October 1997     

Investigation of localized surface plasmons with the photon scanning tunneling microscope

A Photon Scanning Tunneling Microscope (PSTM) with probe-sample distance control by electron tunneling is used to probe the localized surface-plasmon fields of individual nanometric silver particles. As samples, conventional island films produced by thermal evaporation and regular particle arrays produced by an electron-beam-lithography-based technique, respectively, are used. In either case the strength and spatial localization of the surface-plasmon fields strongly depend on the excitation wavelength. The results are interpreted as different resonance frequencies of individual particles or of different sample areas. On regular arrays consisting of particles with a smallest diameter of 40 nm, the PSTM maps represent the plasmon field strength spatially resolved for individual particles.