Synthesis of optically complex core-shell colloidal suspensions: Pathways to multiplexed biological screening

The ability to generate enormous random libraries of DNA probes via split-and-mix synthesis on solid supports is an important biotechnological application of colloids that has not been fully utilized to date. To discriminate between colloid-based DNA probes each colloidal particle must be 'encoded' so it is distinguishable from all other particles. To this end, we have used novel particle synthesis strategies to produce large numbers of optically encoded particle suitable for DNA library synthesis. Multifluorescent particles with unique and reproducible optical signatures (i.e., fluorescence and light-scattering attributes) suitable for high-throughput flow cytometry have been produced. In the spectroscopic study presented here, we investigated the optical characteristics of multi-fluorescent particles that were synthesized by coating silica 'core' particles with up to six different fluorescent dye shells alternated with non-fluorescent silica 'spacer' shells. It was observed that the diameter of the particles increased by up to 20% as a result of the addition of twelve concentric shells and that there was a significant reduction in fluorescence emission intensities from inner shells as an increasing number of shells were deposited.

Synthesis of gadolinium-labeled shell-crosslinked nanoparticles for magnetic resonance imaging applications

Shell-crosslinked knedel-like nanoparticles (SCKs; knedel is a Polish term for dumplings) were derivatized with gadolinium Shell chelates and studied as robust magnetic-resonance-imaging-active structures with hydrodynamic diameters of 40 +/- 3 nm. SCKs possessing an amphiphilic core-shell morphology were produced from the aqueous assembly of diblock copolymers of poly(acrylic acid) (PAA) and poly(methyl acrylate) (PMA), PAA(52)-b-PMA(128), and subsequent covalent crosslinking by amidation upon reaction with 2,2'-(ethylenedioxy)bis(ethylamine) throughout the shell layer. The properties of these materials, including non-toxicity towards mammalian cells, non-immunogenicity within mice, and capability for polyvalent targeting, make them ideal candidates for utilization within biological systems. The synthesis of SCKs derivatized with Gd-III and designed for potential use as a unique nanometer-scale contrast agent for MRI applications is described herein. Utilization of an amino-functionalized diethylenetriaminepentaacetic acid-Gd analogue allowed for direct covalent conjugation throughout the hydrophilic shell layer of the SCKs and served to increase the rotational correlation lifetime of the Gd. In addition, the highly hydrated nature of the shell layer in which the Gd was located allowed for rapid water exchange; thus, the resulting material demonstrated large ionic relaxivities (39 s(-1) mM(-1)) in an applied magnetic field of 0.47 T at 40 degrees C and, as a result of the large loading capacity of the material, also demonstrated high molecular relaxivities (20 000 s(-1) mM(-1)).

Inorganic surface passivation of PbS nanocrystals resulting in strong photoluminescent emission

Strong photoluminescent emission has been obtained from 3 nm PbS nanocrystals in aqueous colloidal solution, following treatment with CdS precursors. The observed emission can extend across the entire visible spectrum and usually includes a peak near 1.95 eV. We show that much of the visible emission results from absorption by higher-lying excited states above 3.0 eV with subsequent relaxation to and emission from states lying above the observed band-edge of the PbS nanocrystals. The fluorescent lifetimes for this emission are in the nanosecond regime, characteristic of exciton recombination.

Polarized photoluminescence from surface-passivated lead sulfide nanocrystals

Effective surface passivation of lead sulfide (PbS) nanocrystals (NCs) in an aqueous colloidal solution has been achieved following treatment with CdS precursors. The resultant photoluminescent emission displays two distinct components, one originating from the absorption band edge and the other from above the absorption band edge. We show that both of these components are strongly polarized but display distinctly different behaviours. The polarization arising from the band edge shows little dependence on the excitation energy while the polarization of the above-band-edge component is strongly dependent on the excitation energy. In addition, time-resolved polarization spectroscopy reveals that the above-band-edge polarization is restricted to the first couple of nanoseconds, while the band edge polarization is nearly constant over hundreds of nanoseconds. We recognize an incompatibility between the two different polarization behaviours, which enables us to identify two distinct types of surface-passivated PbS NC.

Investigation of the role of cadmium sulfide in the surface passivation of lead sulfide quantum dots

Surface passivation of PbS nanocrystals (NC), resulting in strong photoluminescence, can be achieved by the introduction of CdS precursors. The role of CdS in the surface passivation of PbS NCs is uncertain, as the crystalline structure of CdS and PbS are different, which should impede effective epitaxial overgrowth. Absorption spectroscopy is used to show that the CdS precursors strongly interact with the PbS NC surface. Electron microscopy reveals that the introduction of CdS precursors results in an increased particle size, consistent with overcoating. However, we also find the process to be highly non-uniform. Nevertheless, evidence for epitaxial growth is found, suggesting that effective surface passivation may be possible.

Synthesis and aggregation behavior of four-arm star amphiphilic block copolymers in water

We report the first synthesis of amphiphilic four-arm star diblock copolymers consisting of styrene (STY) and acrylic acid (AA) made using reversible addition-fragmentation chain transfer (RAFT; Z group approach with no star-star coupling). The polymerization proceeded in an ideal living manner. The size of the poly(AA(132)-STYm)(4) stars in DMF were small and close to 7 nm, suggesting no star aggregation. Slow addition of water (pH = 6.8) to this mixture resulted in aggregates of 15 stars per micelle with core-shell morphology. Calculations showed that the polyAA blocks were slightly extended with a shell thickness of 15 nm. Treatment of these micelles with piperidine to cleave the block arms from the core resulted in little or no change on micelle size or morphology, but the polyAA shell thickness was close to 29 nm (33 nm is the maximum at full extension) suggesting a release of entropy when the arms are detached from the core molecule. In this work we showed through the use of star amphiphilic polymers that the micelle size, aggregation number, and morphology could be controlled.

On the validity of the shrinking core model in noncatalytic gas solid reaction

By using a matched asymptotic expansion technique, the shrinking core model (SCM) used in non-catalytic gas solid reactions with general kinetic expression is rigorously justified in this paper as a special case of the homogeneous model when the reaction rate is much faster than that of diffusion. The time-pendent velocity of the moving reacted-unreacted interface is found to be proportional to the gas flux at that interface for all geometries of solid particles, and the thickness order of the reaction zone and also the degree of chemical reaction at the interface is discussed in this paper.

Matrix elements of U(2n) generators in a multishell spin-orbit basis. I. The del-operator MEs in a two-shell composite Gelfand-Paldus basis

This is the first in a series of three articles which aimed to derive the matrix elements of the U(2n) generators in a multishell spin-orbit basis. This is a basis appropriate to many-electron systems which have a natural partitioning of the orbital space and where also spin-dependent terms are included in the Hamiltonian. The method is based on a new spin-dependent unitary group approach to the many-electron correlation problem due to Gould and Paldus [M. D. Gould and J. Paldus, J. Chem. Phys. 92, 7394, (1990)]. In this approach, the matrix elements of the U(2n) generators in the U(n) x U(2)-adapted electronic Gelfand basis are determined by the matrix elements of a single Ll(n) adjoint tensor operator called the del-operator, denoted by Delta(j)(i) (1 less than or equal to i, j less than or equal to n). Delta or del is a polynomial of degree two in the U(n) matrix E = [E-j(i)]. The approach of Gould and Paldus is based on the transformation properties of the U(2n) generators as an adjoint tensor operator of U(n) x U(2) and application of the Wigner-Eckart theorem. Hence, to generalize this approach, we need to obtain formulas for the complete set of adjoint coupling coefficients for the two-shell composite Gelfand-Paldus basis. The nonzero shift coefficients are uniquely determined and may he evaluated by the methods of Gould et al. [see the above reference]. In this article, we define zero-shift adjoint coupling coefficients for the two-shell composite Gelfand-Paldus basis which are appropriate to the many-electron problem. By definition, these are proportional to the corresponding two-shell del-operator matrix elements, and it is shown that the Racah factorization lemma applies. Formulas for these coefficients are then obtained by application of the Racah factorization lemma. The zero-shift adjoint reduced Wigner coefficients required for this procedure are evaluated first. All these coefficients are needed later for the multishell case, which leads directly to the two-shell del-operator matrix elements. Finally, we discuss an application to charge and spin densities in a two-shell molecular system. (C) 1998 John Wiley & Sons.

Matrix elements of U(2n) generators in a multishell spin-orbit basis. II. The two-shell nonzero shift ACCs and U(2n) generator MEs

This is the second in a series of articles whose ultimate goal is the evaluation of the matrix elements (MEs) of the U(2n) generators in a multishell spin-orbit basis. This extends the existing unitary group approach to spin-dependent configuration interaction (CI) and many-body perturbation theory calculations on molecules to systems where there is a natural partitioning of the electronic orbital space. As a necessary preliminary to obtaining the U(2n) generator MEs in a multishell spin-orbit basis, we must obtain a complete set of adjoint coupling coefficients for the two-shell composite Gelfand-Paldus basis. The zero-shift coefficients were obtained in the first article of the series. in this article, we evaluate the nonzero shift adjoint coupling coefficients for the two-shell composite Gelfand-Paldus basis. We then demonstrate that the one-shell versions of these coefficients may be obtained by taking the Gelfand-Tsetlin limit of the two-shell formulas. These coefficients,together with the zero-shift types, then enable us to write down formulas for the U(2n) generator matrix elements in a two-shell spin-orbit basis. Ultimately, the results of the series may be used to determine the many-electron density matrices for a partitioned system. (C) 1998 John Wiley & Sons, Inc.

Foraging and vein-cutting behaviour of Euploea core corinna (W.S. Macleay) (Lepidoptera : Nymphalidae) caterpillars feeding on latex-bearing leaves

Caterpillars of Euploea core corinna (W. S. Macleay) sever leaf veins prior to feeding on their latex-bearing host plants, which restricts the flow of latex at feeding sites. The severing of leaf veins by insects feeding on latex-bearing plants is commonly referred to as 'sabotaging' and is thought to be an evolved response by the insect to counter the negative effects of feeding on latex-rich leaves. Sabotaging behaviour is described for all instars of E. core corinna, with particular attention given to neonates. Vein cutting by neonate E. core corinna caterpillars can occur within 2 h of hatching, with most caterpillars establishing feeding sites within 10 h. Commonly, first instars cut an are-shaped row of leaf side-veins parallel to the leaf margin, but they may also cut the leaf mid-rib in a fashion similar to older instar larvae. From a sample of 50 E. core corinna larvae, representing all instars, we found that the diameters of the veins cut by caterpillars are closely correlated to larval head width (r=0.90). Through manipulative experiments, we demonstrate for the first time that sabotaging behaviour in neonate caterpillars imposes no detectable short-term physiological costs on those caterpillars.

Change in the rate of shell deposition and shell microstructure in response to shell borers in the abalone Haliotis rubra

Gastropod shells consist of two crystal types of calcium carbonate, an outer, prismatic calcite layer and an inner nacreous layer made of aragonite. In cross-section, the nacre of the nacreous layer appears to have a regular brick-like microstructure composed of thin laminae of aragonite crystals, separated by very thin sheets of protein (Lutz and Rhoads, 1980; Nakahara, 1983). In abalone (Genus, Haliotis) and other gastropods, thin layers of non-lamellar pigmented material occur within the nacre and have been termed alternatively, fine lines, growth rings or growth lines (Shepherd et al., 1995). It has been suggested that these pigmented layers are small, prismatic, calcite layers (Shepherd and Avalos-Borja, 1997; Zaremba et al., 1996) but investigations using a Raman laser in Haliotis rubra show that they contain aragonite rather than calcite (Hawkes et al, 1996). Day and Fleming (1992) suggest that the occurrence of pigmented layers is correlated with regular exogenous cues such as reproduction or temperature changes and indeed in some species, pigmented layers in the shell can be used to age abalone (review: Shepherd and Triantafillos, 1997). However, McShane and Smith (1992) suggest that pigmented layers can occur irregularly and therefore may be unreliable indicators of age.

Continental extension: From core complexes to rigid block faulting

Extension of overthickened continental crust is commonly characterized by an early core complex stage of extension followed by a later stage of crustal-scale rigid block faulting. These two stages are clearly recognized during the extensional destruction of the Alpine orogen in northeast Corsica, where rigid block faulting overprinting core complex formation eventually led to crustal separation and the formation of a new oceanic backarc basin (the Ligurian Sea). Here we investigate the geodynamic evolution of continental extension by using a novel, fully coupled thermomechanical numerical model of the continental crust. We consider that the dynamic evolution is governed by fault weakening, which is generated by the evolution of the natural-state variables (i.e., pressure, deviatoric stress, temperature, and strain rate) and their associated energy fluxes. Our results show the appearance of a detachment layer that controls the initial separation of the brittle crust on characteristic listric faults, and a core complex formation that is exhuming strongly deformed rocks of the detachment zone and relatively undeformed crustal cores. This process is followed by a transitional period, characterized by an apparent tectonic quiescence, in which deformation is not localized and energy stored in the upper crust is transferred downward and causes self-organized mobilization of the lower crust. Eventually, the entire crust ruptures on major crosscutting faults, shifting the tectonic regime from core complex formation to wholesale rigid block faulting.

Structure optimization combining soft-core interaction functions, the diffusion equation method, and molecular dynamics

Smoothing the potential energy surface for structure optimization is a general and commonly applied strategy. We propose a combination of soft-core potential energy functions and a variation of the diffusion equation method to smooth potential energy surfaces, which is applicable to complex systems such as protein structures; The performance of the method was demonstrated by comparison with simulated annealing using the refinement of the undecapeptide Cyclosporin A as a test case. Simulations were repeated many times using different initial conditions and structures since the methods are heuristic and results are only meaningful in a statistical sense.