Polymorphic microstructure of MDI/BD-block polyurethane as determined by temperature-sensitive conformation variation.

MDI/BD-block thermoplastic polyurethanes (TPUs) crystallized at different isothermal temperatures and different cooling rates were investigated using multiple techniques. The MDI/BD blocks crystallized in form II when the isothermal temperature was equal to or higher than 150 °C, and in form I at lower isothermal temperatures. Form II had a higher crystal elastic modulus of 6.75 GPa than form I of 1.31 GPa. Form I exhibited contracted conformation, while form II exhibited an extended conformation when viewed from the length of the c-axis in the crystalline state. Based on an analysis of the second derivative in FTIR spectroscopy and simple modeling, the conformation differences were considered to stem from the urethane group's internal bond rotation concerning the phenyl ring and the opening bond angle of phenyl-CH2-phenyl. The generation of form II above 150 °C may be due to the activation of urethane and the flexible methylene elevated by the high temperature. Overall, it was seen that the crystallization of MDI/BD blocks involved a physicochemical change.

Cross-examining Polyurethane Nanodomain Formation and Internal Structure.

Structural and morphological interplay between hard and soft phases determine the bulk properties of thermoplastic polyurethanes. Commonly employed techniques rely on different physical or chemical phenomena for characterizing the organization of domains, but detailed structural information can be difficult to derive. Here, total scattering pair distribution function (PDF) analysis is used to determine atomic-scale insights into the connectivity and molecular ordering and compared to the domain size and morphological characteristics measured by AFM, TEM, SAXS, WAXS, and solid-state NMR 1H-1H spin-diffusion. In particular, density distribution functions are highlighted as a means to bridging the gap from the domain morphology to intradomain structural ordering. High real-space resolution PDFs are shown to provide a sensitive fingerprint for indexing aromatic, aliphatic, and polymerization-induced bonding characteristics, as well as the hard phase structure, and indicate that hard phases coexist in both ordered and disordered states.

Fluorescence spectroscopy of individual semiconductor nanoparticles in different ethylene glycols.

The optical properties of single colloidal semiconductor nanoparticles (NPs) are considerably influenced by the direct environment of the NPs. Here, the influence of different liquid and solid glycol matrices on CdSe-based NPs is investigated. Since the fluorescence of individual NPs varies from one NP to another, it is highly desirable to study the very same individual NPs in different matrices. This was accomplished by immobilizing NPs in a liquid cell sample holder or in microfluidic devices. The samples have been investigated by space-resolved wide-field fluorescence microscopy and energy- and time-resolved confocal scanning fluorescence microscopy with respect to fluorescence intensities, emission energies, blinking behavior, and fluorescence decay dynamics of individual NPs. During the measurements the NPs were exposed to air, to liquid ethylene glycols H(OCH2CH2)nOH (also called EGn) with different chain lengths (1 ≤ n ≤ 7), to liquid 2-methylpentane-2,3-diol, or to solid polyethylene oxide. It was found that EG6-7 (also known as PEG 300) is very well suited as a liquid matrix or solvent for experiments that correlate chemical and physical modifications of the surface and of the immediate environment of individual NPs to their fluorescence properties since it leads to intense and stable fluorescence emission of the NPs.

Amphiphilic, cross-linkable diblock copolymers for multifunctionalized nanoparticles as biological probes.

Nanoparticles (NPs) play an increasingly important role in biological labeling and imaging applications. However, preserving their useful properties in an aqueous biological environment remains challenging, even more as NPs therein have to be long-time stable, biocompatible and nontoxic. For in vivo applications, size control is crucial in order to route excretion pathways, e.g. renal clearance vs. hepato-biliary accumulation. Equally necessary, cellular and tissue specific targeting demands suitable linker chemistry for surface functionalization with affinity molecules, like peptides, proteins, carbohydrates and nucleotides. Herein, we report a three stage encapsulation process for NPs comprised of (1) a partial ligand exchange by a multidentate polyolefinic amine ligand, PI-N3, (2) micellar encapsulation with a precisely tuned amphiphilic diblock PI-b-PEG copolymer, in which the PI chains intercalate to the PI-N3 prepolymer and (3) radical cross-linking of the adjacent alkenyl bonds. As a result, water-soluble NPs were obtained, which virtually maintained their primal physical properties and were exceptionally stable in biological media. PEG-terminal functionalization of the diblock PI-b-PEG copolymer with numerous functional groups was mostly straightforward by chain termination of the living anionic polymerization (LAP) with the respective reagents. More complex affinity ligands, e.g. carbohydrates or biotin, were introduced in a two-step process, prior to micellar encapsulation. Advantageously, this pre-assembly approach opens up rapid access to precisely tuned multifunctional NPs, just by using mixtures of diverse functional PI-b-PEG polymers in a combinatorial manner. All constructs showed no toxicity from 0.001 to 1 µM (particle concentration) in standard WST and LDH assays on A549 cells, as well as only marginal unspecific cellular uptake, even in serum-free medium.

In situ functionalization and PEO coating of iron oxide nanocrystals using seeded emulsion polymerization.

Herein we demonstrate that seeded emulsion polymerization is a powerful tool to produce multiply functionalized PEO coated iron oxide nanocrystals. Advantageously, by simple addition of functional surfactants, functional monomers, or functional polymerizable linkers-solely or in combinations thereof-during the seeded emulsion polymerization process, a broad range of in situ functionalized polymer-coated iron oxide nanocrystals were obtained. This was demonstrated by purposeful modulation of the zeta potential of encapsulated iron oxide nanocrystals and conjugation of a dyestuff. Successful functionalization was unequivocally proven by TXRF. Furthermore, the spatial position of the functional groups can be controlled by choosing the appropriate spacers. In conclusion, this methodology is highly amenable for combinatorial strategies and will spur rapid expedited synthesis and purposeful optimization of a broad scope of nanocrystals.

Ultrasmall biocompatible nanocomposites: a new approach using seeded emulsion polymerization for the encapsulation of nanocrystals.

We report a novel approach of seeded emulsion polymerization in which nanocrystals are used as seeds. Ultrasmall biocompatible polymer-coated nanocrystal with sizes between 15 and 110 nm could be prepared in a process that avoids any treatment with high shear forces or ultrasonication. The number of nanocrystals per seed, the size of the seeds, and the shell thickness can be independently adjusted. Single encapsulated nanocrystals in ultrasmall nanobeads as well as clusters of nanocrystals can be obtained. Polysorbat-80 was used as surfactant. It consists of poly(ethylene glycol) (PEG) chains, giving the particles outstanding biofunctional characteristics such as a minimization of unspecific interactions.

Tailor-made quantum dot and iron oxide based contrast agents for in vitro and in vivo tumor imaging.

The biofunctionalization of CdSe/CdS/ZnS quantum dots and Fe(3)O(4) nanocrystals using a novel ligand system based on polyisoprene-block-poly(ethylene oxide) ligands is described. The synthesis includes a partial ligand exchange of the hydrophobic nanocrystals with amino-functionalized polyisoprene ligands, followed by seeded micelle formation of the diblock-copolymers in water. The resulting water-soluble quantum dots showed fluorescence quantum efficiencies in the 40 to 50% range and extraordinary fluorescence stability in the biological environment after cross-linking of the polyisoprene moiety of the ligand shell. No toxicity was detected by water-soluble tetrazolium (WST8) and lactate dehydrogenase (LDH) assays, even at very high nanoparticle concentrations, and almost no nonspecific cell adhesion was detected. The ligand shell was further coupled to the antigen-related cell adhesion molecule (CEACAM) specific monoclonal antibody T84.1. The so-conjugated Fe(3)O(4) nanocrystals allowed in vitro and in vivo tumor targeting by magnetic resonance imaging.

Relaxivity optimization of a PEGylated iron-oxide-based negative magnetic resonance contrast agent for T2-weighted spin-echo imaging.

Concerning the outer sphere relaxation theory, the sensitivity of a T(2) MRI contrast agent, expressed by the transverse relaxivity r(2), depends on the diffusion length of water molecules relative to the particle size. For T(2)-weighted spin-echo imaging, theoretical concepts reveal three regimes regarding the r(2) relaxivity depending on the nanocrystal size: the motional averaging regime (MAR), the static dephasing regime (SDR), and the echo-limiting regime (ELR). The r(2) maximum corresponds to the SDR, which represents a small size regime. To verify the theoretical concepts and to adjust the SDR, tailor-made T(2) contrast agents were synthesized by controlled self-assembly of superparamagnetic iron oxide nanocrystals (SPIOs) into raspberry-like nanoclusters with diameters of 30-200 nm using a PEG-based ligand. The results highlight an opportunity to optimize the relaxivity of T(2) contrast agents by tuning the cluster size of SPIO nanocrystals.

Highly stable biocompatible inorganic nanoparticles by self-assembly of triblock-copolymer ligands.

A novel type of ligand for biofunctionalization of nanoparticles is presented that comprises tailor-made triblock-copolymers consisting of a polyethylene imine binding block, a hydrophobic polycaprolactone and a terminal functionalized polyethelene oxide block. Phase transfer to water occurs simply by ligand and water addition and removal of the organic solvents. It is shown that the intermediate polycaprolacton block favors the attachment to the particle surface and shields the binding groups effectively from the solution. As a consequence, the particles exhibit an outstanding stability in various aqueous media for biological studies and give easy access to specific coupling reactions at the terminal end groups of the polyethylene oxide block. Controlling the ligand exchange parameters leads to self-assembly to either individual encapsulated nanoparticles or to multifunctional nanobeads.