In this paper, the electromagnetic interactions between noble metal nanoparticles are studied by measuring the extinction spectra of two-dimensional arrays of Au and Ag cylinders and trigonal prisms that have been fabricated with electron beam lithography. The nanoparticles are typically 200 nm in diameter and 35 nm in height; both hexagonal and square array patterns have been considered with lattice spacings that vary from 230 to 500 nm. The extinction spectra typically have a maximum in the 700-800 nm region of the spectrum, and this maximum blue shifts as lattice spacing is reduced, having typically a 40 nm decrease in λ max for a 100 nm decrease in lattice spacing. The results are similar for the different noble metals, array patterns, and nanoparticle shapes. The extinction spectra have been modeled using coupled dipole calculations, and the observed spectral variations are in good qualitative agreement with experimental data. Moreover, the computational analysis indicates that the blue shifts are due to radiative dipolar coupling between the nanoparticles and retardation effects. These effects result in a net depolarization of the dipole couplings for lattice spacings of 200-500 nm.

We use high-quality electrodynamics methods to study the extinction spectra of one-dimensional linear chains and two-dimensional planar arrays of spherical silver nanoparticles, placing emphasis on the variation of the plasmon resonance wavelength and width with array structure (spacing, symmetry), particle size, and polarization direction. Two levels of theory have been considered, coupled dipoles with fully retarded interactions and T-matrix theory that includes a converged multipole expansion on each particle. We find that the most important array effects for particles having a radius of 30 nm or smaller are captured by the couple dipole approach. Our calculations demonstrate several surprising effects that run counter to conventional wisdom in which the particle interactions are assumed to be governed by electrostatic dipolar interactions. In particular, we find that for planar arrays of particles with polarization parallel to the plane the plasmon resonance blue shifts as array spacing D decreases for D larger than about 75 nm and then it red shifts for smaller spacings. In addition, we find that the plasmon narrows for D > 180 nm but broadens for smaller spacings. The results can be rationalized using a simple analytical model, which demonstrates that the plasmon wavelength shift is determined by the real part of the retarded dipole sum while the width is determined by the imaginary part of this sum. The optimal blue shifts and narrowing are found when the particle spacing is slightly smaller than the plasmon wavelength, while red shifts and broadening can be found for spacings much smaller than the plasmon wavelength at which electrostatic interactions are dominant. We also find that the array spectrum does not change significantly with array symmetry (square or hexagonal) or irradiated spot size (i.e., constant array size or constant particle number).

We present a time-dependent density functional theory (TDDFT) study of the size-dependence of the absorption and Raman scattering properties of pyridine interacting with small silver nanoclusters Ag n (n ) 2-8, 20). By employing a recently developed short-time approximation for the Raman scattering cross section we simulate both the normal and the "surface"-enhanced Raman spectra. The absorption spectra of the small silver clusters are studied both in the gas phase and embedded in rare gas matrices. We find that both the absorption and Raman properties depend strongly on cluster size and adsorption site. The normal Raman spectra of Ag npyridine complexes resemble that of isolated pyridine, with enhancements which increase as cluster size increases. In contrast to this, both the enhancement and the appearance of the "surface"-enhanced Raman spectrum show a very strong dependence on cluster size. The total enhancements for the complexes are between 10 3 and 10 4 and quite surprisingly the strongest enhancement is found for the Ag 2 -Py complex. However, the enhancement trends can be correlated with the distance of the molecule to the center of the metal cluster and with the resonance polarizability in a way that is suggestive of electromagnetic enhancements, so the enhancement mechanism for these small clusters is similar to what is found for larger particles.

Naturally occurring CD4+CD25+ regulatory T cells (Treg) exert an important role in mediating maternal tolerance to the fetus during pregnancy, and this effect might be regulated via maternal estrogen secretion. Although estrogen concentration in the pharmaceutical range has been shown to drive expansion of CD4+CD25+ Treg cells, little is known about how and through what mechanisms E2 within the physiological concentration range of pregnancy affects this expansion. Using in vivo and in vitro mouse models in these experiments, we observed that E2 at physiological doses not only expanded Treg cell in different tissues but also increased expression of the Foxp3 gene, a hallmark for CD4+CD25+ Treg cell function, and the IL-10 gene as well. Importantly, our results demonstrate that E2, at physiological doses, stimulated the conversion of CD4+CD25- T cells into CD4+CD25+ T cells which exhibited enhanced Foxp3 and IL-10 expression in vitro. Such converted CD4+CD25+ T cells had similar regulatory function as naturally occurring Treg cells, as demonstrated by their ability to suppress naïve T cell proliferation in a mixed lymphocyte reaction. We also found that the estrogen receptor (ER) exist in the CD4+CD25- T cells and the conversion of CD4+CD25- T cells into CD4+CD25+ T cells stimulated by E2 could be inhibited by ICI182,780, a specific inhibitor of ER(s). This supports that E2 may directly act on CD4+CD25- T cells via ER(s). We conclude that E2 is a potential physiological regulatory factor for the peripheral development of CD4+CD25+ Treg cells during the implantation period in mice.

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