Sari Granroth

Smart Porous Silicon Nanoparticles with Polymeric Coatings for Sequential Combination Therapy

In spite of the advances in drug delivery, the preparation of smart nanocomposites capable of precisely controlled release of multiple drugs for sequential combination therapy is still challenging. Here, a novel drug delivery nanocomposite was prepared by coating porous silicon (PSi) nanoparticles with poly(beta-amino ester) (PAE) and Pluronic F-127, respectively. Two anticancer drugs, doxorubicin (DOX) and paclitaxel (PTX), were separately loaded into the core of PSi and the shell of F127. The nanocomposite displayed enhanced colloidal stability and good cytocompatibility. Moreover, a spatiotemporal drug release was achieved for sequential combination therapy by precisely controlling the release kinetics of the two tested drugs. The release of PTX and DOX occurred in a time-staggered manner; PTX was released much faster and earlier than DOX at pH 7.0. The grafted PAE on the external surface of PSi acted as a pH-responsive nanovalve for the site-specific release of DOX. In vitro cytotoxicity tests demonstrated that the DOX and PTX coloaded nanoparticles exhibited a better synergistic effect than the free drugs in inducing cellular apoptosis. Therefore, the present study demonstrates a promising strategy to enhance the efficiency of combination cancer therapies by precisely controlling the release kinetics of different drugs.

Optimization of Pr0.9Ca0.1MnO3 thin films and observation of coexisting spin-glass and ferromagnetic phases at low temperature

Optimization of thin films of small bandwidth manganite, Pr(1-x)Ca(x)MnO3 (for x = 0.1), and their magnetic properties are investigated. Using different pulsed laser deposition (PLD) conditions, several films were deposited from the stoichiometric target material on SrTiO3 (001) substrate and their thorough structural and magnetic characterizations were carried out using x-ray diffraction, atomic force microscopy, x-ray photoelectron spectroscopy (XPS), SQUID magnetometry and ac susceptibility measurements. A systematic investigation shows that irrespective of the growth temperature (between 550 and 750 °C), all the as-deposited films have twin boundaries and magnetic double phases. Post-annealing in partial or full oxygen pressure removes the extra phase and the twin boundaries. Zero-field-cooled magnetization data show an antiferromagnetic to paramagnetic transition at around 100 K whereas the field-cooled magnetization data exhibit a paramagnetic to ferromagnetic transition close to 120 K. However, depending on the oxygen treatments, the saturation magnetization and Curie temperature of the films change significantly. Redistribution of oxygen vacancies due to annealing treatments leading to a change in ratio of Mn3+ and Mn4+ in the films is observed from XPS measurements. Low temperature (below 100 K) dc magnetization of these films shows metamagnetic transition, high coercivity and irreversibility magnetizations, indicating the presence of a spin-glass phase at low temperature. The frequency dependent shift in spin-glass freezing temperature from ac susceptibility measurement confirms the coexistence of spin-glass and ferromagnetic phases in these samples at low temperature.

Persistent photoinduced magnetization in the coexisting spin-glass and ferromagnetic phases of Pr0.9Ca0.1MnO3 thin film

The persistent photoinduced magnetization (PPM) in the low bandwidth material Pr(1-x)Ca(x)MnO₃ at the low hole doping level of x = 0.1 is reported. Upon zero-field cooling under photoexcitation, significant improvement of the ferromagnetic (FM) ordering was observed in the low temperature spin-glass phase. However, upon field cooling, the FM ordering was found to be suppressed due to weakening of the double-exchange interaction. High kinetic energy x-ray photoelectron spectroscopy measurements indicated a slight increase in the Mn³⁺ peak under photoexcitation which clarifies the weakening of the FM interaction. The fast relaxation of the PPM is discussed in view of localization of spin polarons in sites of magnetic disorders and the results are compared with previous reports of PPM in intermediate bandwidth Pr₀.₉Ca₀.₁MnO₃ samples.

Evolution of structural and magnetic properties with varying oxygen content in low-bandwidth manganite Pr0.9Ca0.1MnO3 thin films.

The effects of ex situ vacuum and oxygen annealing treatments on thin films of the low-bandwidth compound Pr(1-x)Ca(x)MnO(3) (PCMO) are investigated. Structural and magnetic measurements reveal that increased ferromagnetism can be achieved by oxygen annealing treatment, which is linked to the increased Mn(4+) ion content, as observed from x-ray photoelectron spectroscopy (XPS) measurements, as well as relaxation of the substrate-induced tensile strain of the PCMO unit cell. The increased number of Mn(4+) ions and partial release of strain lead to stronger double-exchange interaction in the system. Vacuum annealing increases the ferromagnetic (FM) interaction as well; however, the increased FM ordering is not directly related to the improved double-exchange interaction, as XPS measurement reveals an indication of a slight increase in Mn(3+) ions in this case. Trapping of carriers in the oxygen vacancies and formation of magnetic polarons have been suggested as the causes of the increase in ferromagnetic ordering, and this is also supported by the large coercivity and longer spin memory in the vacuum annealed PCMO.

Crystal asymmetry and low-angle grain boundary governed persistent photoinduced magnetization in small bandwidth manganites

Persistent photo-induced magnetization (PPM) in low bandwidth manganite Pr1−xCaxMnO3 (PCMO) thin film is reported in the low hole doped regime (x = 0.1). X-ray diffraction, x-ray photoelectron spectroscopy, and magnetic measurements in dark and under illumination on the as-grown, vacuum, and oxygen annealed thin films of PCMO showed that the PPM effect is strongly dependent on the crystal symmetry, low angle grain boundaries, and the Mn valence states in the material. Compared with the as-grown and vacuum annealed film, the oxygen annealed film shows much less low-angle grain boundaries, higher crystal symmetry, and long range ferromagnetic (FM) ordering and in this sample PPM is not significant. These results clearly indicate that in this large band gap material PCMO, photo-induced FM interaction mainly arises due to improved domain-wall movement of the short range FM clusters. Significant PPM can be obtained for films with higher amount of grain boundaries, oxygen vacancies, and strain related defects.

An aging effect and its origin in GdBCO thin films

An aging effect investigation was made for GdBa2Cu3O7 (GdBCO) thin films grown on SrTiO3 (001) substrates with pulsed laser deposition (PLD) method from nanograined targets. The films were cut into two pieces where one piece was coated with gold cap layer while the other was left without coating. Both pieces were kept in ambient air during the half year measurement period. Magnetization measurements as well as phase purity, lattice parameter, oxygen effect and depth structure determination with x-ray diffraction (XRD) were made in one month interval. For structure and oxygen content, x-ray photoelectron spectroscopy measurements (XPS) were done in the beginning and in the end of the period. A reduction of the critical temperature and the critical current density, Jc, was found in the gold coated GdBCO film in ambient air in course of time. A smaller decrease of Jc was detected in uncoated GdBCO. No development of impurity phase, increase of a-orientation or reduction of the pinning structure was detected in uncoated GdBCO. However, a small development of impurity phase was found in gold coated GdBCO. The diminution of Tc and Jc is concluded to originate from oxygen release. No such a phenomenon was found in YBa2Cu3O7. We conclude that gold is not a proper cap layer at least for some applications.

Fragmentation patterns of doubly charged acrylonitrile molecule following carbon core ionization

Dissociation of acrylonitrile into pairs of cations and neutral fragments following molecular core ionization was investigated using the photoelectron-photoion-photoion coincidence (PEPIPICO) technique. The fragment ion mass spectra were recorded in coincidence with the carbon 1s photoelectrons. Deuterated and (13)C-substituted samples were used for resolving fragment mass ambiguities. Slope analysis of the PEPIPICO patterns was used in determining the fragment separation sequences in case of multiparticle processes. The results show that there are several fragmentation channels producing a wide range of charged coincident fragments. The dynamics of the dominant fragmentation processes is investigated in detail.

Toward Versatile Sr2FeMoO6-Based Spintronics by Exploiting Nanoscale Defects

To actualize the high spintronic application potential of complex magnetic oxides, it is essential to fabricate these materials as thin films with the best possible magnetic and electrical properties. Sr2FeMoO6 is an outstanding candidate for such applications, but presently no thin film synthesis route, which would preserve the magnetic properties of bulk Sr2FeMoO6, is currently known. In order to address this problem, we present a comprehensive experimental and theoretical study where we link the magnetic and half metallic properties of Sr2FeMoO6 thin films to lattice strain, Fe-Mo antisite disorder and oxygen vacancies. We find the intrinsic effect of strain on the magnetic properties to be very small, but also that an increased strain will significantly stabilize the Sr2FeMoO6 lattice against the formation of antisite disorder and oxygen vacancies. These defects, on the other hand, are recognized to drastically influence the magnetism of Sr2FeMoO6 in a nonlinear manner. On the basis of the findings, we propose strain manipulation and reductive annealing as optimization pathways for improving the spintronic functionality of Sr2FeMoO6.

VUV-induced dissociation of methylchlorosilanes, studied by electron–ion coincidence spectroscopy

Fragmentation patterns of gas-phase trimethylchlorosilane and methyltrichlorosilane molecules were investigated using the electron-energy-resolved photoelectron–photoion coincidence technique. The production of parent ions and the dominant fragments by 30 eV synchrotron radiation was followed as a function of the photoelectron binding energy. Ion appearance energies were determined from these coincident ion yield curves. The fragmentation patterns and their development are discussed in terms of available internal excess energy as well as the molecular orbital character of the parent molecules. A common dissociation scenario is proposed for both molecules, producing methyl- and chlorine-loss fragments at lower excess energies and smaller fragments through second-step processes at sufficiently high energies.

Resonant Auger electron-photoion coincidence study of the fragmentation dynamics of an acrylonitrile molecule

Monochromatic synchrotron radiation was used to promote K-shell electrons of nitrogen and carbon from the cyano group (C ≡ N) of gaseous acrylonitrile (C2H3–CN) to the unoccupied antibonding π*C ≡ N orbital. Photofragmentation of acrylonitrile molecules following selective resonant core excitations of carbon and nitrogen core electrons to the π*C ≡ N orbital was investigated using the electron-energy-resolved photoelecton–photoion coincidence technique. The fragment ion mass spectra were recorded in coincidence with the resonant Auger electrons, emitted in the decay process of the core-excited states. Singly and triply deuterated samples were used for fragment identification. The results showed the initial core-hole localization to be of minor importance in determining the dissociation pattern of the molecular cation. The participator and spectator Auger transitions produce entirely different fragmentation patterns and the latter indicates that complex nuclear rearrangements take place. It is suggested that the calculated kinetic energy releases are caused by the existence of metastable states, which appear with the opening of the spectator Auger channels.