Enhanced surface-plasmon resonance absorption in metal-dielectric-metal layered microspheres

We present a theoretical study of the dispersion relation of surface-plasmon resonances of mesoscopic metal-dielectric-metal microspheres. By analyzing the solutions to Maxwell's equations, we obtain a simple geometric condition for which the system exhibits a band of surface-plasmon modes whose resonant frequencies are weakly dependent on the multipole number. Using a modified Mie calculation, we find that a large number of modes belonging to this flat-dispersion band can be excited simultaneously by a plane wave, thus enhancing the absorption cross section. We demonstrate that the enhanced absorption peak of the sphere is geometrically tunable over the entire visible range.     

Synthesis, crystal structures and magnetic behaviour of dimeric and tetrameric gadolinium carboxylates with trichloroacetic acid

The novel gadolinium(III) containing compounds (CH3NH3)2[Gd2(CCl3COO)6(H2O)6](CCl3COO)2.2CCl3COOH (1) and (NH3CH3)2[Gd4(OH)4(CCl3COO)10(H2O)6].2H2O (2) were synthesized and structurally characterized by X-ray crystallography. In the crystal structure of 1 the gadolinium ions are bridged by carboxylate groups to dimers with a Gd3+ -Gd3+ distance of 420.2(3) pm. The compound crystallizes in the triclinic space group P1. In the crystal structure of the Gd3+ ions are bridged by hydroxide ions and carboxylate groups to tetramers with Gd3+ -Gd3+ distances between 380.3(1) and 388.0(1) pm. The compound crystallizes in the triclinic space group P1. The magnetic behaviour of these two compounds as well as of Gd2(CCl3COO)6(bipy)2(H2O)2.4bipy (3) (bipy = 2,2'-bipyridyl) was investigated in the temperature range 1.77-300 K. The magnetic data for these compounds indicate weak antiferromagnetic interactions.     

Conformal Metrics on the Unit Ball in Euclidean Space

We study densities on the unit ball in euclidean space whichsatisfy a Harnack type inequality and a volume growth conditionfor the measure associated with . For these densities a geometrictheory can be developed which captures many features of thetheory of quasiconformal mappings. For example, we prove generalizationsof the Gehring-Hayman theorem, the radial limit theorem andfind analogues of compression and expansion phenomena on theboundary. 1991 Mathematics Subject Classification: 30C65.     

Synthesis of the potent immunostimulatory adjuvant QS-21A

QS-21A is one of the most promising new adjuvants for immune response potentiation and dose-sparing in vaccine therapy, given its exceedingly high level of potency and its favorable toxicity profile. Melanoma, breast cancer, small cell lung cancer, prostate cancer, HIV-1, and malaria are among the numerous maladies targeted in more than 80 recent and ongoing clinical trials involving QS-21A as a critical component for immune response augmentation in microgram doses. Herein is reported the first synthesis and structure verification of QS-21Aapi, applying novel glycosylation methodologies in the convergent modular construction of this rare and potent natural product immunostimulant.     

XAS characterization of end-on and side-on peroxoiron(III) complexes of the neutral pentadentate N-donor ligand N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine

Peroxo intermediates are implicated in the catalytic cycles of iron enzymes involved in dioxygen metabolism. X-ray absorption spectroscopy has been used to gain insight into the iron coordination environments of the low-spin complex [Fe(III)(Me-TPEN)(eta(1)-OOH)](2+)(1) and the high-spin complex [Fe(III)(Me-TPEN)(eta(2)-O(2))](+)(2)(the neutral pentadentate N-donor ligand Me-TPEN =N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine) and obtain metrical parameters unavailable from X-ray crystallography. The complexes exhibit relatively large pre-edge peak areas of approximately 15 units, indicative of iron centers with significant distortions from centrosymmetry. These distortions result from the binding of peroxide, either end-on hydroperoxo for 1 (r(Fe-O)= 1.81A) or side-on peroxo for 2 (r(Fe-O)= 1.99 A). The XAS analyses of 1 strongly support a six-coordinate low-spin iron(III) center coordinated to five nitrogen atoms from Me-TPEN and one oxygen atom from an end-on hydroperoxide ligand. However, the XAS analyses of 2 are not conclusive: Me-TPEN can act either as a pentadentate ligand to form a seven-coordinate peroxo complex, which has precedence in the DFT geometry optimization of [Fe(III)(N4Py)(eta(2)-O(2))](+)(the neutral pentadentate N-donor ligand N4Py =N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), or as a tetradentate ligand with a dangling pyridylmethyl arm to form a six-coordinate peroxo complex, which is precedented by the crystal structure of [Fe(2)(III)(Me-TPEN)(2)(Cl)(2)(mu-O)](2+).     

Development and evaluation of on-line nanoliter flow analysis of protein digests by pneumatic-splitter electrospray liquid chromatography mass spectrometry

We have developed a novel approach to characterize protein digests by pneumatic-splitter electrospray ionization liquid chromatography mass spectrometry (PSESI-LCMS). This technique involves an interfacing of a pneumatic splitter that can dynamically generate and control a steady split flow rate of nanoliters per minute. An average PSESI-LCMS analysis, depending on the desired split ratio, consumes less than 200 femtomoles of sample. A tryptic digest map of a glycoprotein, fetuin, and a Lys-C digest map of a recombinant neurotrophin protein, neurotrophin-3, are reported here for this investigation.     

Polyarylenes on the Basis of Alkylpyrrole and Alkylcarbazole Derivatives and their Oligomeric Model Systems

The redox and spectroscopic properties of soluble poly- (9-decylcarbazole) derivatives and poly(1-decylpyrrole) were studied. The polymers were synthesized via the Yamamoto polycondensation method. Analyzing the electrochemical and optical properties of 3,6-linked poly(alkylcarbazole)s it is evident that the conjugation segment is the benzidine system and the overall properties of these polymers can be compared with meta linked poly(phenylene)s. In opposite, 2,7-linked poly(alkylcarbazole)s reveal an even longer conjugation segment comparable with para linked poly(phenylene)s. First observations in the case of poly(1-decylpyrrole) suggest a higher steric hinderance compared to poly- (1-methylpyrrole). Molecular modeling studies confirm this. © 1997 John Wiley & Sons, Ltd.