The excitation wavelength (λ) dependence of the photoluminescence (PL) quantum yield (Φ) and decay behavior (τ) of a series of CdSe/CdS quantum dot/quantum rods (QDQRs), consisting of the same spherical CdSe core and rod-shaped CdS shells, with aspect ratios ranging from 2 to 20 was characterized. λ between 400-565 nm were chosen to cover the first excitonic absorption band of the CdSe core material, the onset of absorption of the CdS shell, and the region of predominant shell absorption. A strong λ dependence of relative and absolutely measured Φ and τ was found particularly for the longer QDQRs with higher aspect ratios. This is attributed to combined contributions from a length-dependent shell-to-core exciton localization efficiency, an increasing number of defect states within the shell for the longest QDQRs, and probably also the presence of absorbing, yet non-emitting shell material. Although the Φ values of the QDQRs decrease at shorter wavelength, the extremely high extinction coefficients introduced by the shell outweigh this effect, leading to significantly higher brightness values at wavelengths below the absorption onset of the CdS shell compared with direct excitation of the CdSe cores. Moreover, our results present also an interesting example for the comparability of absolutely measured Φ using an integrating sphere setup and Φ values measured relative to common Φ standards, and underline the need for a correction for particle scattering for QDQRs with high aspect ratios.

The phase transfer of fluorescent CdSe based quantum dots (QDs) while retaining their properties and offering some advantages concerning the stability and functionalization characteristics is an important and intensively investigated field of research. Here we report how to tune and control the properties of CdSe/CdS/ZnS core-shell-shell QDs in water, using poly(isoprene-block-ethylene oxide) (PI-b-PEO) as a versatile system of amphiphilic diblock copolymers for the micellular encapsulation of nanoparticles (NPs). We show the synthesis of a novel PI-b-(PEO)2 miktoarm star polymer and how this different architecture besides the variation of the polymers' molecular weight gives us the opportunity to control the size of the built constructs in water between 24 and 53 nm. Because of this size control, an upper limit of the construct's diameter for the cellular uptake could be determined by a systemic study with human alveolar epithelial cells (A549) and murine macrophage leukemia cell (RAW-264.7). Furthermore, fluorescence quenching experiments with copper(II) and iron(III) ions show a strong influence of the used polymer on the shielding against these ions. This enables us to control the permeability of the polymer shell from very porous shells, which allow an almost complete cation exchange up to very dense shells. These even offer the possibility to perform copper(I) catalyzed click reactions while keeping the fluorescence of the QDs. All these results underline the huge variability and controllability of the PI-b-PEO diblock copolymer system for the encapsulation and functionalization of nanoparticles for biological applications. As a general trend, it can be stated that those coatings, which were most stable against quenchers, also showed the best resistivity with respect to unspecific cellular uptake.

CdSe/CdS-Quantum-dots-quantum-rods (QDQRs) with an aspect ratio of ∼ 6 are prepared via the seeded growth method, encapsulated within a shell of crosslinked poly(isoprene)-block-poly(ethylene glycol) (PI-b-PEG) diblock copolymer, and transferred from the organic phase into aqueous media. Their photoluminescence quantum yield (PLQY) of 78% is not compromised by the phase transfer. Within a period of two months the PLQY of QDQRs in aqueous solution at neutral pH decreases only slightly (to ∼ 65%). The two-photon (TP) action cross sections of QDQRs (∼ 10(5) GM) are two orders of magnitude higher than those of CdSe/CdS/ZnS-core/shell/shell quantum dots (QDs, ∼ 10(3) GM) with comparable diameter (∼ 5 nm). After applying PI-b-PEG encapsulated QDQRs onto the small intestinal mucosa of mice in vivo, their strong red fluorescence can easily be observed by two-photon laser scanning microscopy (TPLSM) and clearly distinguished from autofluorescent background. Our results demonstrate that PI-b-PEG encapsulated CdSe/CdS-QDQRs are excellent probes for studying the uptake and fate of nanoparticles by two-photon imaging techniques in vivo.

Using the x-ray magnetic circular dichroism effect, the soft x-ray range provides powerful detection capabilities concerning element specific structural, chemical, and magnetic properties. We present the implementation of a variable 0.22 T magnet system based on permanent magnets into the new UHV scanning microscope "MAXYMUS" at HZB/BESSY II, allowing surface sensitive and simultaneous standard transmission microscopic investigations in a variable external magnetic field. The outstanding potential of these new investigation possibilities will be demonstrated showing the development of the magnetic domain structure concurrently at the surface and in the bulk, providing a profound understanding of fundamental mechanisms in coupled magnetic systems.

Seeded emulsion polymerization is a powerful universal method to produce ultrasmall multifunctional magnetic nanohybrids. In a two-step procedure, iron oxide nanocrystals were initially encapsulated in a polystyrene (PS) shell and subsequently used as beads for a controlled assembly of elongated quantum dots/quantum rods (QDQRs). The synthesis of a continuous PS shell allows the whole construct to be fixed and the composition of the nanohybrid to be tuned. The fluorescence of the QDQRs and magnetism of iron oxide were perfectly preserved, as confirmed by single-particle investigation, fluorescence decay measurements, and relaxometry. Bio-functionalization of the hybrids was straightforward, involving copolymerization of appropriate affinity ligands as shown by immunoblot analysis. Additionally, the universality of this method was shown by the embedment of a broad scale of NPs.

The combination of superstructure-forming amphiphilic block copolymers and superparamagnetic iron oxide nanoparticles produces new nano/microcomposites with unique size-dependent properties. Herein, we demonstrate the controlled clustering of superparamagnetic iron oxide nanoparticles (SPIOs) ranging from discretely encapsulated SPIOs to giant clusters, containing hundreds or even more particles, using an amphiphilic polyisoprene-block-poly(ethylene glycol) diblock copolymer. Within these clusters, the SPIOs interact with each other and show new collective properties, neither obtainable with singly encapsulated nor with the bulk material. We observed cluster-size-dependent magnetic properties, influencing the blocking temperature, the magnetoviscosity of the liquid suspension, and the r2 relaxivity for magnetic iron oxide nanoparticles. The clustering methodology can be expanded also to other nanoparticle materials [CdSe/CdS/ZnS core/shell/shell quantum dots (QDs), CdSe/CdS quantum dots/quantum rods (QDQRs), gold nanoparticles, and mixtures thereof].

The fluorescence quantum yield (QY) of CdSe dot/ CdS rod (DR) nanoparticle ensembles is dependent on the shell growth and excitation wavelength. We analyze the origin of this dependency by comparing the optical properties of DR ensembles to the results obtained in single-particle experiments. On the ensemble level, we find that the QY of DRs with shell lengths shorter than 40 nm exhibits no dependence on the excitation wavelength, whereas for DRs with shell lengths longer than 50 nm, the QY significantly decreases for excitation above the CdS band gap. Upon excitation in the CdSe core, the ensemble QY, the fluorescence wavelength, and the fluorescence blinking behavior of individual particles are only dependent on the radial CdS shell thickness and not on the CdS shell length. If the photogenerated excitons can reach the CdSe core region, the fluorescence properties will be dependent only on the surface passivation in close vicinity to the CdSe core. The change in QY upon excitation above the band gap of CdS for longer DRs cannot be explained by nonradiative particles because the ratio of emitting DRs is found to be independent of the DR length. We propose a model after which the decrease in QY for longer CdS shells is due to an increasing fraction of nonradiative exciton recombination within the elongated shell. This is supported by an effective-mass-approximation-based calculation, which suggests an optimum length of DRs of about 40 nm, to combine the benefit of high CdS absorption cross section with a high fluorescence QY.

We investigate clustered CdSe/CdS quantum dots/quantum rods, ranging from single to multiple encapsulated rods within amphiphilic diblock copolymer micelles, by time-resolved optical spectroscopy. The effect of the clustering and the cluster size on the optical properties is addressed. The clusters are bright and stable and show no blinking while retaining the fundamental optical properties of the individual quantum dots/quantum rods. Cell studies show neither unspecific uptake nor morphological changes of the cells, despite the increased sizes of the clusters.