Detection of ferricyanide as a probe for the effect of hematocrit in whole blood biosensors.

Measurement of the concentration of an analyte in whole blood can be influenced by a range of factors; the red cell content or hematocrit (Hct) of the sample, the distribution and rate of movement of analyte between red cells and plasma, the amount of protein in solution, the viscosity of the sample and fouling of the sensor. The effect of the red cells is the major factor that must be taken into account. Using the analyte molality rather than the analyte molarity, the theoretical response for a range of analytes which are found in plasma and in the red cells can be calculated. For an analyte which is found in plasma alone, the effect of hematocrit is significant, with a bias of -1% per %Hct; if the analyte can freely and rapidly diffuse between the red cells and plasma, this bias is reduced to zero. Using ferrocyanide as a model analyte, the effects of fouling and reduced sample viscosity were measured to be -0.2% per %Hct, giving an overall bias of -1.2% per %Hct, a level of bias which is not clinically acceptable. This bias can be negated by measuring the hematocrit separately and incorporating it into the measurement algorithm. Such a correction is essential for the correct measurement of the concentration of an analyte in whole blood.     

Divergent Solid‐Phase Synthesis of Natural Product‐Inspired Bipartite Cyclodepsipeptides: Total Synthesis of Seragamide A

Macrocyclic natural products (NPs) and analogues thereof often show high affinity, selectivity, and metabolic stability, and methods for the synthesis of NP‐like macrocycle collections are of major current interest. We report an efficient solid‐phase/cyclorelease method for the synthesis of a collection of macrocyclic depsipeptides with bipartite peptide/polyketide structure inspired by the very potent F‐actin stabilizing depsipeptides of the jasplakinolide/geodiamolide class. The method includes the assembly of an acyclic precursor chain on a polymeric carrier, terminated by olefins that constitute complementary fragments of the polyketide section and cyclization by means of a relay‐ring‐closing metathesis (RRCM). The method was validated in the first total synthesis of the actin‐stabilizing cyclodepsipeptide seragamide A and the synthesis of a collection of structurally diverse bipartite depsipeptides.     

Eigenstate statistics and optical properties of one-dimensional disordered photonic crystals

Optical eigenstates in one-dimensional disordered photonic crystals were studied. The threshold disorder level was established below which the probability of appearance of an eigenstate at the photonic bandgap center is negligible. The threshold is reached when the relative fluctuation in the optical lengths of the structure periods becomes equal to the square root of one-third of the relative bandgap width. The dependence of the ensemble-averaged structure transmission coefficient on the fluctuation of the period optical length has a break corresponding to the threshold fluctuation.     

High intensity coherent transient in multiple quantum wells

In this paper we report Degenerate Four Wave Mixing (DFWM) experiments on the excitons of GaAs/AlGaAs Multiple Quantum Well (MQW) at high incident intensities. These experiments provide a clear manifestation of Many-Body Interactions (MBI) among the excitons, in the form of a multi-photon (intensity-dependant) resonance at the low energy side of the heavy-hole exciton of the first subband of the MQW. The temporal resolution of the DFWM response provides a demonstration of the multi-photon nature of this resonance and, hence, of its MBI origin.     

Fabrication and testing of off-axis parabolic mirrors

Methods have been devised to fabricate and test off-axis segments of parabolic mirrors manufactured from a parent parabolic mirror. Four off-axis parabolic mirrors were fabricated from Zerodur (special grade) by cutting up one large on-axis parabolic mirror. Interferometric measurements were made on the parent mirror and off-axis segments before and after cutting. The measurements show that the surface figure of the segments did not change as a result of the cutting. The surface figure of the final mirror segments was better than λ/13 peak-to-valley and λ/13rms (λ = 0.6328 μm).     

Semiclassical interpretation of the gross-shell structure in deformed nuclei

An analysis of the classical closed orbits in the infinitely deep elongated ellipsoidal well is given with respect to their relevance to the gross-shell structure of the single-particle spectra in deformed nuclei. It is shown that the deformed-shape gross-shells responsible for the ground state deformations, as well as those responsible for the fission intermediate states, find a reasonable explanation in terms of the semiclassical three-dimensional quantization involving the planar orbits in the axis-of-symmetry plane and the simplest three-dimensional orbits which appear at large distortions. The former are found important for the ground state shapes. The results are also compared with the harmonic oscillator model.     

Macroscopic resonances in planar geometry

Resonating response is a characteristic feature of free-particle system contained between two vibrating planar surfaces. Resonance frequencies and widths are determined by a mean period of motion of particles reflected from the walls. Resonances due to quasiperiodic macroscopic motion appear when the interaction among quasi-particles by means of perturbations of the common self-consistent field is included. They have finite widths corresponding to collisionless Landau dissipation. Possible relationship of this phenomenon to nuclear giant resonances is discussed.     

Rhenium complexes with triazine derivatives formed from semicarbazones and thiosemicarbazones

Benzil bis(semicarbazone), H2L(1), reacts with common rhenium(V) nitrido complexes such as [ReNCl2(PPh3)2] or [ReNCl2(PR2Ph)3] (R = Me, Et) under the release of one semicarbazone unit, cyclization, and formation of stable triazine-3-onato complexes of rhenium(V). The resulting 5,6-diphenyltriazine-3-one, HL (2), acts as monodentate or chelating, monoanionic ligand depending on the reaction conditions applied. Complexes of the compositions [ReNCl(L(2)-kappaN(2),kappaO)(PR2Ph)2] (R = Me, Et) or [ReN(L(2)-kappa N(2),O)(L(2)-kappaN(2))(PPh3)2] were isolated. The N(2) nitrogen atom is the preferred binding site of the monodentate form of the ligand. This contrasts the behavior of the analogous thione HL(3), which preferably coordinates to nitridorhenium(V) centers via the sulfur atom. HL(3) is readily formed by the abstraction of methanol from 5-methoxy-5,6-diphenyl-4,5-dihydro-2H-[1,2,4]triazine-3-thione, H2L(3)OCH 3. In the presence of [ReNCl2(PPh3)2] or [ReNCl2(PR2Ph)3] complexes (R = Me, Et), this reaction yields stable complexes of the composition [ReN(L(3)-kappaN(2),kappaS)(L(3)-kappaS)(PR2Ph)2] (R = Me, Et, Ph) in good yields. Reduction of the metal atom and formation of the seven-coordinate [Re(PPh3)(L(3)-kappaN(2),kappaS)3] was observed during reactions of H2L(3)OCH3 with [ReOCl3(PPh3)2] or [ReO2I(PPh3)2], while no rhenium complexes could be isolated during similar reactions with H2L(1), although cyclization of the bis(semicarbazone) and the formation of H 2L(2)OEt were observed.     

Rhenium and technetium complexes with tridentate N-[(N',N'-dialkylamino)(thiocarbonyl)]-N'-substituted benzamidine ligands

N-[(Dialkylamino)(thiocarbonyl)]benzimidoyl chlorides react with functionalized amines such as 2-aminophenol, 2-methylaminopyridine, and 2-aminobenzoic acid in clean and high-yield procedures with the formation of the novel tridentate N-[(N', N'-dialkylamino)(thiocarbonyl)]- N'-substituted benzamidine ligands H2L1, HL2, and H2L3. By starting from (NBu4)[MOCl4] (M = Re, Tc) or [ReOCl3(PPh3)2] and H2L1, a series of oxorhenium(V) and oxotechnetium(V) complexes of the composition [MOCl(L1)] were synthesized and characterized by spectroscopic methods and X-ray crystallography. The monomeric, five-coordinate compounds are air-stable and bind (L1)(2-) tridentate in the equatorial coordination sphere. Dimeric products of the compositions [(ReOCl(L2))2O] and [ReOCl(L3)]2 were isolated during reactions with HL2 and H2L3. While dimerization in [(ReOCl(L2))2O] is established via an oxo bridge, the metal atoms in [ReOCl(L3)]2 are connected by the carboxylic group of the ligand, and the product represents the first example of a high-oxidation state rhenium complex displaying such a bonding feature.