Anna Cristina S. Samia

Quantum Dot‐based Energy Transfer: Perspectives and Potential for Applications in Photodynamic Therapy

Abstract Quantum dots have emerged as an important class of material that offers great promise to a diverse range of applications ranging from energy conversion to biomedicine. Here, we review the potential of using quantum dots and quantum dot conjugates as sensitizers for photodynamic therapy (PDT). The photophysics of singlet oxygen generation in relation to quantum dot-based energy transfer is discussed and the possibility of using quantum dots as photosensitizer in PDT is assessed, including their current limitations to applications in biological systems. The biggest advantage of quantum dots over molecular photosensitizers that comes into perspective is their tunable optical properties and surface chemistries. Recent developments in the preparation and photophysical characterization of quantum dot energy transfer processes are also presented in this review, to provide insights on the future direction of quantum dot-based photosensitization studies from the viewpoint of our ongoing research.

Delivery and efficacy of a cancer drug as a function of the bond to the gold nanoparticle surface.

In this feature article, gold nanoparticle conjugates loaded with phthalocyanine-based PDT drugs are prepared and tested for delivery efficiency and PDT efficacy on HeLa cancer cells. It could be shown that the delivery and PDT outcome are strongly affected by the bond that links the drug load to the nanoparticle surface. Whereas labile amino adsorption to the Au nanoparticle surface allows for efficient drug release into the cancer cells and for efficient PDT, a covalent thiol bond to the Au nanoparticle leads to the delivery of the drug into cell vesicles, and no PDT effect is observed. This work highlights the importance of carefully choosing the interaction between drug molecules and the nanoparticle surface.

Characterizing the magnetic anisotropy constant of spinel cobalt ferrite nanoparticles

Superconducting quantum interference device (SQUID) magnetometry and Mossbauer spectroscopy have been combined to determine the magnetic anisotropy constant K of spinel CoFe2O4 nanoparticles. The anisotropy constant is 2.23×106 erg/cm3 for CoFe2O4 nanoparticles with a mean diameter of 8.5 nm. A relaxation-time constant of τ0=1.90×10−14 s has also been obtained. The magnetic anisotropy distribution function of the nanoparticles has been extracted from the temperature dependence of remanence decay in SQUID measurements. The population percentage of the superparamagnetically relaxed nanoparticles at each temperature can be calculated from this anisotropy distribution function. Such a population calculation from SQUID measurements can also fit the results from Mossbauer spectroscopic measurements even though these two measuring methods are fundamentally distinct. Such a successful fit implies that the anisotropy distribution function from our SQUID measurement is truly an intrinsic feature of the nanoparticles.

Identification and characterization of the intermediate phase in hybrid organic–inorganic MAPbI3 perovskite

Perovskite films were prepared using single step solution deposition at different annealing temperatures and annealing times. The crystal structure, phases and grain size were investigated with XRD, XPS and SEM/EDX. The prepared films show a typical orientation of tetragonal perovskite phase and a gradual transition at room temperature from the yellow intermediate phase to the black perovskite phase. Films with high purity were obtained by sintering at 100 °C. In addition, the chemical composition and crystal structure of intermediate phase were investigated in detail. FTIR, UV-vis and NMR spectra revealed the occurance of DMF complexes. Interestingly, the intermediate phase could be transformed to the black perovskite phase upon X-ray irradiation. In addition, the recovery of the aged perovskite films from a yellow intermediate phase back to the black perovskite was shown to be viable via heating and X-ray irradiation.

Evaluation of the photoinduced electron relaxation dynamics of Cu1.8S quantum dots

Cu1.8S quantum dots were prepared by using a single-source-precursor type method and investigated in the light of opto-electronic applications. With femtosecond time-resolved transient absorption measurements, the electron relaxation as well as their trapping dynamics could be evaluated. The measurements reveal that the largest and the smallest QD samples prepared exhibit the longest mobility lifetimes, and that the electron-hole relaxation dynamics is strongly dependent on the occurrence of trapping sites. Based on the argument of optical response, it appears that the largest prepared Cu1.8S QDs with band gap energy of 2.35 eV are preferred candidates for opto-electronic device fabrication.

Magnetic nanoparticles: material engineering and emerging applications in lithography and biomedicine

We present an interdisciplinary overview of material engineering and emerging applications of iron oxide nanoparticles. We discuss material engineering of nanoparticles in the broadest sense, emphasizing size and shape control, large-area self-assembly, composite/hybrid structures, and surface engineering. This is followed by a discussion of several nontraditional, emerging applications of iron oxide nanoparticles, including nanoparticle lithography, magnetic particle imaging, magnetic guided drug delivery, and positive contrast agents for magnetic resonance imaging. We conclude with a succinct discussion of the pharmacokinetics pathways of iron oxide nanoparticles in the human body—an important and required practical consideration for any in vivo biomedical application, followed by a brief outlook of the field.

Adsorption of Cd2+ on Carboxyl-Terminated Superparamagnetic Iron Oxide Nanoparticles

The affinity of Cd(2+) toward carboxyl-terminated species covalently bound to monodisperse superparamagnetic iron oxide nanoparticles, Fe(3)O(4)(np)-COOH, was investigated in situ in aqueous electrolytes using rotating disk electrode techniques. Strong evidence that the presence of dispersed Fe(3)O(4)(np)-COOH does not affect the diffusion limiting currents was obtained using negatively and positively charged redox active species in buffered aqueous media (pH = 7) devoid of Cd(2+). This finding made it possible to determine the concentration of unbound Cd(2+) in solutions containing dispersed Fe(3)O(4)(np)-COOH, 8 and 17 nm in diameter, directly from the Levich equation. The results obtained yielded Cd(2+) adsorption efficiencies of ~20 μg of Cd/mg of Fe(3)O(4)(np)-COOH, which are among the highest reported in the literature employing ex situ methods. Desorption of Cd(2+) from Fe(3)O(4)(np)-COOH, as monitored by the same forced convection method, could be accomplished by lowering the pH, a process found to be highly reversible.

Iron Oxide and Titanium Dioxide Nanoparticle Effects on Plant Performance and Root Associated Microbes

In this study, we investigated the effect of positively and negatively charged Fe3O4 and TiO2 nanoparticles (NPs) on the growth of soybean plants (Glycine max.) and their root associated soil microbes. Soybean plants were grown in a greenhouse for six weeks after application of different amounts of NPs, and plant growth and nutrient content were examined. Roots were analyzed for colonization by arbuscular mycorrhizal (AM) fungi and nodule-forming nitrogen fixing bacteria using DNA-based techniques. We found that plant growth was significantly lower with the application of TiO2 as compared to Fe3O4 NPs. The leaf carbon was also marginally significant lower in plants treated with TiO2 NPs; however, leaf phosphorus was reduced in plants treated with Fe3O4. We found no effects of NP type, concentration, or charge on the community structure of either rhizobia or AM fungi colonizing plant roots. However, the charge of the Fe3O4 NPs affected both colonization of the root system by rhizobia as well as leaf phosphorus content. Our results indicate that the type of NP can affect plant growth and nutrient content in an agriculturally important crop species, and that the charge of these particles influences the colonization of the root system by nitrogen-fixing bacteria.

Magnetic Particle Imaging Tracers: State-of-the-Art and Future Directions.

Magnetic particle imaging (MPI) is an emerging imaging modality with promising applications in diagnostic imaging and guided therapy. The image quality in MPI is strongly dependent on the nature of its iron oxide nanoparticle-based tracers. The selection of potential MPI tracers is currently limited, and the underlying physics of tracer response is not yet fully understood. An in-depth understanding of the magnetic relaxation processes that govern MPI tracers, gained through concerted theoretical and experimental work, is crucial to the development of optimized MPI tracers. Although tailored tracers will lead to improvements in image quality, tailored relaxation may also be exploited for biomedical applications or more flexible image contrast, as in the recent demonstration of color MPI.

Effect of the Functionalization of the Axial Phthalocyanine Ligands on the Energy Transfer in QD-based Donor-Acceptor Pairs

This study examines the electronic coupling between quantum dots (QDs) and molecules on their surfaces as a function of the modality of their interaction. As a probe, the energy transfer (ET) between CdSe QDs and phthalocyanines (Pcs) was monitored and evaluated with regard to the functionalization of the axial phthalocyanine ligand, bulkiness of the functional group bridging the QD donor and Pc acceptor, and the number of the functionalized axial ligands. New silicon PCs and their conjugates with CdSe QDs were synthesized. The ET efficiency and kinetics were studied by steady state and femtosecond time‐resolved absorption spectroscopy. We observed a decrease in ET efficiency with the increase in functional group bulkiness, which could be explained by increasing steric hindrance between the ET pair. In addition, a higher ET efficiency was observed for amino and thiol functionalized Pcs compared to Pcs without functional group on the axial alkyl chain.