Luminescence and Nonlinear Optical Properties in Copper(I) Halide Extended Networks.

The syntheses, structures, and luminescence properties of a series of copper(I) halide coordination polymers, prepared with mono- and bidentate N-heteroaromatic ligands, are reported. These metal-organic coordination networks form [Cu2I2L]n for bidentate ligands (where L = pyrazine (1), quinazoline (2)) and [CuIL]n for monodentate ligands (where L = 3-benzoylpyridine (3) and 4-benzoylpyridine(4)). Both sets of compounds exhibit a double-stranded stair-Cu2I2-polymer, or "ladder" structure with the ligand coordinating to the metal in a bidentate (bridging two stairs) or monodentate mode. The copper bromide analogues for the bidentate ligands were also targeted, [Cu2Br2L]n for L = pyrazine (5) with the same stair structure, as well as compositions of [CuBr(L)]n for L = pyrazine (6) and quinazoline (7), which have a different structure type, where the -Cu-Br- forms a single-stranded "zigzag" chain. These copper halide polymers were found to be luminescent at room temperature, with emission peaks ranging from ∼550 to 680 nm with small shifts at low temperature. The structure (stair or chain), the halide (I or Br), as well as the ligand play an important role in determining the position and intensity of emission. Lifetime measurements at room and low temperatures confirm the presence of thermally activated delayed fluorescence, or singlet harvesting for compounds 1, 2, and 7. We also investigated the nonlinear optical properties and found that, of this series, [CuBr(quinazoline)]n shows a very strong second harmonic generating response that is ∼150 times greater than that of α-SiO2.

Magnetic nanobeads as potential contrast agents for magnetic resonance imaging.

Metal-oxo clusters have been used as building blocks to form hybrid nanomaterials and evaluated as potential MRI contrast agents. We have synthesized a biocompatible copolymer based on a water stable, nontoxic, mixed-metal-oxo cluster, Mn8Fe4O12(L)16(H2O)4, where L is acetate or vinyl benzoic acid, and styrene. The cluster alone was screened by NMR for relaxivity and was found to be a promising T2 contrast agent, with r1 = 2.3 mM(-1) s(-1) and r2 = 29.5 mM(-1) s(-1). Initial cell studies on two human prostate cancer cell lines, DU-145 and LNCap, reveal that the cluster has low cytotoxicity and may be potentially used in vivo. The metal-oxo cluster Mn8Fe4(VBA)16 (VBA = vinyl benzoic acid) can be copolymerized with styrene under miniemulsion conditions. Miniemulsion allows for the formation of nanometer-sized paramagnetic beads (~80 nm diameter), which were also evaluated as a contrast agent for MRI. These highly monodispersed, hybrid nanoparticles have enhanced properties, with the option for surface functionalization, making them a promising tool for biomedicine. Interestingly, both relaxivity measurements and MRI studies show that embedding the Mn8Fe4 core within a polymer matrix decreases r2 effects with little effect on r1, resulting in a positive T1 contrast enhancement.

Magnetic particle imaging: advancements and perspectives for real-time in vivo monitoring and image-guided therapy.

Magnetic particle imaging (MPI) is an emerging biomedical imaging technology that allows the direct quantitative mapping of the spatial distribution of superparamagnetic iron oxide nanoparticles. MPI's increased sensitivity and short image acquisition times foster the creation of tomographic images with high temporal and spatial resolution. The contrast and sensitivity of MPI is envisioned to transcend those of other medical imaging modalities presently used, such as magnetic resonance imaging (MRI), X-ray scans, ultrasound, computed tomography (CT), positron emission tomography (PET) and single photon emission computed tomography (SPECT). In this review, we present an overview of the recent advances in the rapidly developing field of MPI. We begin with a basic introduction of the fundamentals of MPI, followed by some highlights over the past decade of the evolution of strategies and approaches used to improve this new imaging technique. We also examine the optimization of iron oxide nanoparticle tracers used for imaging, underscoring the importance of size homogeneity and surface engineering. Finally, we present some future research directions for MPI, emphasizing the novel and exciting opportunities that it offers as an important tool for real-time in vivo monitoring. All these opportunities and capabilities that MPI presents are now seen as potential breakthrough innovations in timely disease diagnosis, implant monitoring, and image-guided therapeutics.