Mode manipulation in system of coupled microcavities with whispering gallery modes

In recent years the studies of electromagnetic modes in solid spherical microcavities have been of great interest both for their potential applications and fundamental optical properties. A system of coherently coupled microcavities may be called a “photonic molecule” and can be employed in the tight-binding device in order to manipulate photons in micrometer length scale. In this work we demonstrate the possibility of mode manipulation in systems of symmetric photonic molecules formed by placing several high-Q micro-spheres in contact. We observe photonic nanojets that reflect the symmetry of the photonic molecule, with 3 jets located at 120 degrees with respect to each other for the triangular photonic molecule. A benzene molecule-like structure consisting of a 7-microspheres cyclic photonic molecule shows a field emission pattern similar to the spatial distribution of the orbitals of the benzene molecule. We also present some results showing the coexistence of whispering gallery modes and photonic nanojets in the same structure.     

Self-Sorting Supramolecular Polymerization: Helical and Lamellar Aggregates of Tetra-Bay-Acyloxy Perylene Bisimide

A new perylene bisimide (PBI), with a fluorescence quantum yield up to unity, self-assembles into two polymorphic supramolecular polymers. This PBI bears four solubilizing acyloxy substituents at the bay positions and is unsubstituted at the imide position, thereby allowing hydrogen-bond-directed self-assembly in nonpolar solvents. The formation of the polymorphs is controlled by the cooling rate of hot monomer solutions. They show distinctive absorption profiles and morphologies and can be isolated in different polymorphic liquid-crystalline states. The interchromophoric arrangement causing the spectral features was elucidated, revealing the formation of columnar and lamellar phases, which are formed by either homo- or heterochiral self-assembly, respectively, of the atropoenantiomeric PBIs. Kinetic studies reveal a narcissistic self-sorting process upon fast cooling, and that the transformation into the heterochiral (racemic) sheetlike self-assemblies proceeds by dissociation via the monomeric state.     

An immobilized homogeneous catalyst for efficient and selective hydrogenation of functionalized aldehydes, alkenes, and alkynes

An immobilized cationic rhodium(I) catalyst bearing the diphosphine 1,1'-bis(diisopropylphosphino)ferrocene (DiPFc, 1) allows efficient and chemoselective hydrogenation of a range of functionalized aldehydes, as well as alkenes and alkynes, under mild conditions. This heterogenized catalyst system is convenient to prepare, is stable to air and moisture over extended periods, and is readily recycled.     

Difference frequency generation in LiIO3 using two tunable dye lasers

A report is given on difference frequency generation in LiIo₃ within a spectral range from 1.5 μ through 4.8 μ using two flashlamp-pumped tunable dye lasers. A novel phase matching geometry having parallel Poynting vectors inside the crystal was experimentally tested.     

Low-temperature PECVD of silicon dioxide on polymeric hydrogels

In this work, a complex investigation of the film surface composition and nanoscale mechanical properties, i.e. hardness and elastic modulus, of plasma-modified and silica-coated hydrogel thin films was carried out. Plasma treatment was performed in a reactive ion etching chamber (SF₆, CHF₃) at radio frequency (rf, 13.56 MHz) and in a plasma-enhanced chemical vapor deposition chamber (SiH₄/N₂, NH₃, N₂O) at radio frequency and dual frequency (13.56 MHz/100 kHz), respectively. The use of the dual-frequency configuration comprising two power supplies and operated in a switched mode enabled the investigation of the ion-bombardment influence on the polymer properties. For the application in silicon micromachined sensors best results were obtained by using a NH₃ or SiH₄/N₂ low-pressure plasma modification and a silica coating of the sensitive hydrogel film. PACS 81.05.Lg; 81.15.Gh; 81.65.Cf; 81.70.Bt     

Use of 19F NMR spectroscopy to screen chemical libraries for ligands that bind to proteins

Identification of compounds from chemical libraries that bind to macromolecules by use of NMR spectroscopy has gained increasing importance during recent years. A simple methodology based on (19)F NMR spectroscopy for the screening of ligands that bind to proteins, which also provides qualitative information about relative binding strengths and the presence of multiple binding sites, is presented here. A library of fluorinated compounds was assembled and investigated for binding to the two bacterial chaperones PapD and FimC, and also to human serum albumin (HSA). It was found that library members which are bound to a target protein could be identified directly from line broadening and/or induced chemical shifts in a single, one-dimensional (19)F NMR spectrum. The results obtained for binding to PapD using (19)F NMR spectroscopy agreed well with independent studies based on surface plasmon resonance, providing support for the versatility and accuracy of the technique. When the library was titrated to a solution of PapD chemical shift and linewidth changes were observed with increasing ligand concentration, which indicated the presence of several binding sites on PapD and enabled the assessment of relative binding strengths for the different ligands. Screening by (19)F NMR spectroscopy should thus be a valuable addition to existing NMR techniques for evaluation of chemical libraries in bioorganic and medicinal chemistry.     

Protein adsorption onto silica nanoparticles: conformational changes depend on the particles' curvature and the protein stability

We have analyzed the adsorption of protein to the surfaces of silica nanoparticles with diameters of 6, 9, and 15 nm. The effects upon adsorption on variants of human carbonic anhydrase with differing conformational stabilities have been monitored using methods that give complementary information, i.e., circular dichroism (CD), nuclear magnetic resonance (NMR), analytical ultracentrifugation (AUC), and gel permeation chromatography. Human carbonic anhydrase I (HCAI), which is the most stable of the protein variants, establishes a dynamic equilibrium between bound and unbound protein following mixture with silica particles. Gel permeation and AUC experiments indicate that the residence time of HCAI is on the order of approximately 10 min and slowly increases with time, which allows us to study the effects of the interaction with the solid surface on the protein structure in more detail than would be possible for a process with faster kinetics. The effects on the protein conformation from the interaction have been characterized using CD and NMR measurements. This study shows that differences in particle curvature strongly influence the amount of the protein's secondary structure that is perturbed. Particles with a longer diameter allow formation of larger particle-protein interaction surfaces and cause larger perturbations of the protein's secondary structure upon interaction. In contrast, the effects on the tertiary structure seem to be independent of the particles' curvature.     

Structure and bonding in solution of dioxouranium(VI) oxalate complexes: isomers and intramolecular ligand exchange

Structural isomers of [UO(2)(oxalate)(3)](4-), [UO(2)(oxalate)F(3)](3-), [UO(2)(oxalate)(2)F](3-), and [UO(2)(oxalate)(2)(H(2)O)](2-) have been studied by using EXAFS and quantum chemical ab initio methods. Theoretical structures and their relative energies were determined in the gas phase and in water using the CPCM model. The most stable isomers according to the quantum chemical calculations have geometries consistent with the EXAFS data, and the difference between measured and calculated bond distances is generally less than 0.05 A. The complex [UO(2)(oxalate)(3)](4-) contains two oxalate ligands forming five-membered chelate rings, while the third is bonded end-on to a single carboxylate oxygen. The most stable isomer of the other two complexes also contains the same type of chelate-bonded oxalate ligands. The activation energy for ring opening in [UO(2)(oxalate)F(3)](3-), deltaU++ = 63 kJ/mol, is in fair agreement with the experimental activation enthalpy, deltaH++ = 45 +/- 5 kJ/mol, for different [UO(2)(picolinate)F(3)](2-) complexes, indicating similar ring-opening mechanisms. No direct experimental information is available on intramolecular exchange in [UO(3)(oxalate)(3)](4-). The theoretical results indicate that it takes place via the tris-chelated intermediate with an activation energy of deltaU++ = 38 kJ/mol; the other pathways involve multiple steps and have much higher activation energies. The geometries and energies of dioxouranium(VI) complexes in the gas phase and solvent models differ slightly, with differences in bond distance and energy of typically less than 0.06 A and 10 kJ/mol, respectively. However, there might be a significant difference in the distance between uranium and the leaving/entering group in the transition state, resulting in a systematic error when the gas-phase geometry is used to estimate the activation energy in solution. This systematic error is about 10 kJ/mol and tends to cancel when comparing different pathways.     

Magneto-optical trapping of Stark-slowed metastable He atoms

We report on the first successful loading of a magneto-optical trap (MOT) with metastable He atoms from a Stark-slower. Thereby, deceleration of the atoms relies on laser-atom interaction in an inhomogeneous electric field. We show that the results obtained are comparable with early results from other groups achieved with a Zeeman slower. The Stark slower, which is able to fully control the final velocity of the atomic He beam, is the first step in achieving complete spin independent kinematic control based solely on electric fields. Received 2 October 2002 / Received in final form 20 January 2003 Published online 29 April 2003 RID="a" ID="a"e-mail: eichmann@mbi-berlin.de