Proton magnetic resonance spectroscopy of a boron neutron capture therapy 10B-carrier, L-p-boronophenylalanine-fructose complex

Boron neutron capture therapy (BNCT) is a radiotherapy that has mainly been used to treat malignant brain tumours, melanomas, and head and neck cancer. In BNCT, the patient receives an intravenous infusion of a 10B-carrier, which accumulates in the tumour area. The tumour is irradiated with epithermal or thermal neutrons, which result in a boron neutron capture reaction that generates heavy particles to damage tumour cells. In Finland, boronophenylalanine fructose (BPA-F) is used as the 10B-carrier. Currently, the drifting of boron from blood to tumour as well as the spatial and temporal accumulation of boron in the brain, are not precisely known. Proton magnetic resonance spectroscopy (1H MRS) could be used for selective BPA-F detection and quantification as aromatic protons of BPA resonate in the spectrum region, which is clear of brain metabolite signals. This study, which included both phantom and in vivo studies, examined the validity of 1H MRS as a tool for BPA detection. In the phantom study, BPA quantification was studied at 1.5 and 3.0 T with single voxel 1H MRS, and at 1.5 T with magnetic resonance imaging (MRSI). The detection limit of BPA was determined in phantom conditions at 1.5 T and 3.0 T using single voxel 1H MRS, and at 1.5 T using MRSI. In phantom conditions, BPA quantification accuracy of ± 5% and ± 15% were achieved with single voxel MRS using external or internal (internal water signal) concentration references, respectively. For MRSI, a quantification accuracy of <5% was obtained using an internal concentration reference (creatine). The detection limits of BPA in phantom conditions for the PRESS sequence were 0.7 (3.0 T) and 1.4 mM (1.5 T) mM with 20 × 20 × 20 mm3 single voxel MRS, and 1.0 mM with acquisition-weighted MRSI (nominal voxel volume 10(RL) × 10(AP) × 7.5(SI) mm3), respectively. In the in vivo study, an MRSI or single voxel MRS or both was performed for ten patients (patients 1-10) on the day of BNCT. Three patients had glioblastoma multiforme (GBM), and five patients had a recurrent or progressing GBM or anaplastic astrocytoma gradus III, and two patients had head and neck cancer. For nine patients (patients 1-9), MRS/MRSI was performed 70-140 min after the second irradiation field, and for one patient (patient 10), the MRSI study began 11 min before the end of the BPA-F infusion and ended 6 min after the end of the infusion. In comparison, single voxel MRS was performed before BNCT, for two patients (patients 3 and 9), and for one patient (patient 9), MRSI was performed one month after treatment. For one patient (patient 10), MRSI was performed four days before infusion. Signals from the tumour spectrum aromatic region were detected on the day of BNCT in three patients, indicating that in favourable cases, it is possible to detect BPA in vivo in the patient’s brain after BNCT treatment or at the end of BPA-F infusion. However, because the shape and position of the detected signals did not exactly match the BPA spectrum detected in the in vitro conditions, assignment of BPA is difficult. The opportunity to perform MRS immediately after the end of BPA-F infusion for more patients is necessary to evaluate the suitability of 1H MRS for BPA detection or quantification for treatment planning purposes. However, it could be possible to use MRSI as criteria in selecting patients for BNCT.

Coexistence of para and ferromagnetic phases of Fe3+ in undoped CdZnTe (Zn similar to 4%) crystals

The signatures of the coexistence of para and ferromagnetic phases for the Fe3+ charge state of iron have been identified in the low temperature electron spin resonance (ESR) spectra in undoped CdZnTe (Zn similar to 4%) crystals and independently verified by superconducting quantum interference device (SQUID) and AC susceptibility measurements. In the paramagnetic phase the inverse of AC susceptibility follows the Curie-Weiss law. In the ferromagnetic phase the thermal evolution of magnetization follows the well-known Bloch T-3/2 law. This is further supported by the appearance of hysteresis in the SQUID measurements at 2 K below T-c which is expected to lie in between 2 and 2.5 K. (C) 2010 Elsevier Ltd. All rights reserved.

Cobalt(II) complexes of terpyridine bases as photochemotherapeutic agents showing cellular uptake and photocytotoxicity in visible light

Cobalt(II) complexes of terpyridine bases Co(L)(2)](ClO4)(2) (1-3), where L is 4'-phenyl-2,2':6',2''-terpyridine (ph-tpy in 1), 4'-(9-anthracenyl)-2,2':6',2''-terpyridine (an-tpy in 2) and 4'-(1-pyrenyl)-2,2':6',2''-terpyridine (py-tpy in 3), are prepared and their photo-induced DNA and protein cleavage activity and photocytotoxic property in HeLa cells studied. The 1 : 2 electrolytic and three-electron paramagnetic complexes show a visible band near 550 nm in DMF-Tris-HCl buffer. The complexes 1-3 show emission spectral bands at 355, 421 and 454 nm, respectively, when excited at 287, 368 and 335 nm. The quantum yield values for 1-3 in DMF-H2O (2 : 1 v/v) are 0.025, 0.060 and 0.28, respectively. The complexes are redox active in DMF-0.1 M TBAP. The Co(III)-Co(II) and Co(II)-Co(I) couples appear as quasi-reversible cyclic voltammetric responses near 0.2 and -0.7 V vs. SCE, respectively. Complexes 2 and 3 are avid binders to calf thymus DNA giving K-b value of similar to 10(6) M-1. The complexes show chemical nuclease activity. Complexes 2 and 3 exhibit oxidative cleavage of pUC19 DNA in UV-A and visible light. The DNA photocleavage reaction of 3 at 365 nm shows formation of singlet oxygen and hydroxyl radical species, while only hydroxyl radical formation is evidenced in visible light. Complexes 2 and 3 show non-specific photo-induced bovine serum albumin protein cleavage activity at 365 nm. The an-tpy and py-tpy complexes exhibit significant photocytotoxicity in HeLa cervical cancer cells on exposure to visible light giving IC50 values of 24.2 and 7.6 mu M, respectively. Live cell imaging study shows accumulation of the complexes in the cytosol of HeLa cancer cells.

Charge-transfer interaction of picolines with iodine and pi-accepters- A spectroscopic study

The interaction of 2-amino-6-methylpyridine, 2-picoline and 4-picoline as donors with iodine, 7,7',8,8'-tetracyanoquinodimethane,2,3-dichloro-5,6-dicyano-1,4-benzoquinone, p-chloranil, o-chloranil, 2,4,7-trinitro-9-fluorenone and 2,4,5,7-tetranitro-9-fluorenone as acceptors has been studied by measuring visible and ultraviolet spectra. Infrared, electron paramagnetic and nuclear magnetic resonance spectra have also been obtained. Kinetic parameters have been derived. The results indicate that the charge transfer interaction occurs through the formation of free radicals which is followed by a slow reaction to give a diamagnetic product. However, with iodine, the charge transfer complex formation occurs without the formation of free radicals. The donor site is inferred to be the lone pair of electrons of the amino nitrogen of 2-amino-6-methylpridine whereas for 2- and 4-picolines, the preferred site is lone pair of electrons on the pyridine nitrogen.

The effect of Sb on the electrical and magnetic properties of Ni-Zn ferrites prepared by sol-gel autocombustion method

Polycrystalline Ni-Zn ferrites with a well-defined composition of Ni0.4Zn0.6Fe2-xSbxO4 synthesized using sol-gel method. Morphological characterizations on the prepared samples were performed by high resolution transmission electron and field emission scanning electron microscopy. The powders were densified using microwave sintering method. The room temperature complex permittivity (epsilon' and epsilon aEuro(3)) and permeability (mu' and mu aEuro(3)) were measured over a wide frequency range from 1 MHz-1.8 GHz. The real part of permittivity varies as `x' concentration increases and the resonance frequency was observed at much higher frequencies and there is a significant decrease in the loss factor (tan delta). The electrical resistivity and permeability of NiZn ferrites increased with an increase of Sb content. As the concentration of `x' increases from 0 to 0.08 the saturation magnetisation decreases. The saturation magnetization (M-s) a parts per thousand aEuro parts per thousand 52.211 A.m(2)/Kg for x = 0 at room temperature. The room temperature electro paramagnetic resonance (EPR) were studied.

Synthesis, Characterization, and Nuclear Magnetic Resonance Study of Chitosan-Coated Mn1-xZnxFe2O4 Nanocrystals

Ultra-fine crystallites of Mn1-xZnxFe2O4 series (0 <= x <= 1) were synthesized through wet chemical co- precipitation method followed by calcination at 200 degrees C for 4 hours. Formation of ferrites was confirmed by X-ray diffraction, TEM selected area diffraction (SAD) and Fourier Transform Infra-red Spectroscopy (FTIR). Nanocrystallites of different compositions in the series were coated with biocompatible chitosan in order to investigate their possible application as contrast agent for magnetic resonance imaging (MRI). Chitosan coating examined by FTIR, revealed a strong bonding of chitosan molecules to the surface of the ferrite nanocrystallites. Spin-spin, tau(2) relaxivities of nuclear spins of hydrogen protons of the solutions for different ferrites were measured from concentration dependence of relaxation time by nuclear magnetic resonance (NMR). All the compositions of Mn1-xZnxFe2O4 series possess higher values of tau(2) relaxivity thus making them suitable as contrast agents for tau(2) weighted imaging by MRI.

Mitochondria targeting Photocytotoxic Oxidovanadium( IV) Complexes of Curcumin and ( Acridinyl) dipyridophenazine in Visible Light

Oxidovanadium(IV) complexes, VO(acac)(L)Cl] (1), VO(cur)(L)Cl] (2), and VO(scur)(L)Cl] (3) {acac = acetylacetonate, cur = curcumin monoanion, scur = diglucosylcurcumin monoanion, L = 11-(9-acridinyl)dipyrido3, 2-a:2',3'-c]phenazine (acdppz)}, were prepared and characterized. The complexes are non-electrolytic in DMF and 1:1 electrolytic in aqueous DMF. The one-electron paramagnetic complexes showed a d-d band near 725 nm in aqueous DMF and green emission near 520 nm in aqueous DMSO. The complexes exhibited an irreversible V-IV/V-III redox response near -0.85 V versus SCE in aqueous DMF. The complexes showed good binding strengths to calf thymus DNA (K-b: 3.1x10(5)-9.6x10(5) M-1) and efficient pUC19 DNA photocleavage activity in red light of 705 and 785 nm by singlet oxygen (O-1(2)) pathway. Complexes 1 and 2 exhibited significant photocytotoxicity (IC50: 0.1-1.0 M) in visible light (400-700 nm) with low dark toxicity (IC50: >20 M) in HeLa and HaCaT cells. Complex 3 was cytotoxic in both light and dark. DNA ladder formation experiments indicated cell death via apoptotic pathway. Confocal microscopy done with 1 and 2 revealed primarily cytosolic localization of the complexes with significant presence of the complex in the mitochondria as evidenced from the imaging data using mitotracker red.

Advances in Image Reconstruction Methods for Real-Time Magnetic Resonance Thermometry

Magnetic Resonance Imaging (MRI) has been widely used in cancer treatment planning, which takes the advantage of high-resolution and high-contrast provided by it. The raw data collected in the MRI can also be used to obtain the temperature maps and has been explored for performing MR thermometry. This review article describes the methods that are used in performing MR thermometry, with an emphasis on reconstruction methods that are useful to obtain these temperature maps in real-time for large region of interest. This article also proposes a prior-image constrained reconstruction method for temperature reconstruction in MR thermometry, and a systematic comparison using ex-vivo tissue experiments with state of the art reconstruction method is presented.

Remarkable Selectivity and Photo-Cytotoxicity of an Oxidovanadium(IV) Complex of Curcumin in Visible Light

Oxidovanadium(IV) complexes of 2-(2'-pyridyl)-1,10-phenanthroline (pyphen), viz. VO(pyphen)(acac)](ClO4) (1), VO(pyphen)(anacac)](ClO4) (2) and VO(pyphen)(cur)](ClO4) (3), where acac is acetylacetonate (in 1), anacac is anthracenylacetylacetonate (in 2) and cur is curcumin monoanion (in 3) were synthesized, characterized and their photo-induced DNA cleavage activities and photo-cytotoxicities studied. The complexes are 1: 1 electrolytes in DMF. The one-electron paramagnetic complexes show a d-d band near 760 nm in DMF. Complexes 2 and 3 are blue and green emissive, respectively, in DMSO. The complexes exhibit irreversible V-IV/V-III reductive responses near -1.1 V and V-V/V-IV oxidative responses near 0.85 V vs. SCE in DMF-0.1 M TBAP. Complexes 2 and 3 display significant and selective photo-cytotoxicity upon irradiation with visible light giving an IC50 value of about 5 mu M against HeLa and MCF-7 cancer cells; they are significantly less-toxic against normal 3T3 control cells and in the absence of light. Complex 1 was used as a control. Both cytosolic and nuclear localization of the complexes were observed on the basis of fluorescence imaging. The complexes, avid binders to calf thymus (ct) DNA, were found to photocleave supercoiled pUC19 DNA upon irradiation with near-IR light (785 nm) by generating hydroxyl radical (OH) as the reactive oxygen species (ROS). Cell death events noted with HeLa and MCF-7 cell lines likely are attributable to apoptotic pathways involving light-assisted generation of intracellular ROS.

Design and synthesis of biofunctional magnetic/fluorescent glyco-nanoparticles and quantum dots and their application as specific molecular imaging probes

206 p.

Trapped ion magnetic resonance: concepts and designs

A novel spectroscopy of trapped ions is proposed which will bring single-ion detection sensitivity to the observation of magnetic resonance spectra. The approaches developed here are aimed at resolving one of the fundamental problems of molecular spectroscopy, the apparent incompatibility in existing techniques between high information content (and therefore good species discrimination) and high sensitivity. Methods for studying both electron spin resonance (ESR) and nuclear magnetic resonance (NMR) are designed. They assume established methods for trapping ions in high magnetic field and observing the trapping frequencies with high resolution (<1 Hz) and sensitivity (single ion) by electrical means. The introduction of a magnetic bottle field gradient couples the spin and spatial motions together and leads to a small spin-dependent force on the ion, which has been exploited by Dehmelt to observe directly the perturbation of the ground-state electron's axial frequency by its spin magnetic moment.

A series of fundamental innovations is described m order to extend magnetic resonance to the higher masses of molecular ions (100 amu = 2x 10^5 electron masses) and smaller magnetic moments (nuclear moments = 10^(-3) of the electron moment). First, it is demonstrated how time-domain trapping frequency observations before and after magnetic resonance can be used to make cooling of the particle to its ground state unnecessary. Second, adiabatic cycling of the magnetic bottle off between detection periods is shown to be practical and to allow high-resolution magnetic resonance to be encoded pointwise as the presence or absence of trapping frequency shifts. Third, methods of inducing spindependent work on the ion orbits with magnetic field gradients and Larmor frequency irradiation are proposed which greatly amplify the attainable shifts in trapping frequency.

The dissertation explores the basic concepts behind ion trapping, adopting a variety of classical, semiclassical, numerical, and quantum mechanical approaches to derive spin-dependent effects, design experimental sequences, and corroborate results from one approach with those from another. The first proposal presented builds on Dehmelt's experiment by combining a "before and after" detection sequence with novel signal processing to reveal ESR spectra. A more powerful technique for ESR is then designed which uses axially synchronized spin transitions to perform spin-dependent work in the presence of a magnetic bottle, which also converts axial amplitude changes into cyclotron frequency shifts. A third use of the magnetic bottle is to selectively trap ions with small initial kinetic energy. A dechirping algorithm corrects for undesired frequency shifts associated with damping by the measurement process.

The most general approach presented is spin-locked internally resonant ion cyclotron excitation, a true continuous Stern-Gerlach effect. A magnetic field gradient modulated at both the Larmor and cyclotron frequencies is devised which leads to cyclotron acceleration proportional to the transverse magnetic moment of a coherent state of the particle and radiation field. A preferred method of using this to observe NMR as an axial frequency shift is described in detail. In the course of this derivation, a new quantum mechanical description of ion cyclotron resonance is presented which is easily combined with spin degrees of freedom to provide a full description of the proposals.

Practical, technical, and experimental issues surrounding the feasibility of the proposals are addressed throughout the dissertation. Numerical ion trajectory simulations and analytical models are used to predict the effectiveness of the new designs as well as their sensitivity and resolution. These checks on the methods proposed provide convincing evidence of their promise in extending the wealth of magnetic resonance information to the study of collisionless ions via single-ion spectroscopy.

Transmission properties of electron in quantum rings

We investigated the transmission probability of a single electron transmission through a quantum ring device based on the single-band effective mass approximation method and transfer matrix theory. The time-dependent Schrodinger equation is applied on a Gaussian wave packet passing through the quantum ring system. The electron tunneling resonance peaks split when the electron transmits through a double quantum ring. The splitting energy increases as the distance between the two quantum rings decreases. We studied the tunneling time through the single electron transmission quantum ring from the temporal evolution of the Gaussian wave packet. The electron probability density is sensitive to the thickness of the barrier between the two quantum rings. (C) 2008 American Institute of Physics.

Experimental measurement of microwave-induced electron spin-flip time

The electron spin resonance (ESR) is optically detected by monitoring the microwave-induced changes in the circular polarization of the neutral exciton (X) and the negatively charged exciton (X-) emission in CdTe quantum wells with low density of excess electrons. We find that the circular polarization of the X and X- emission is a mapping of the spin polarization of excess electrons. By analyzing the ESR-induced decrease in the circular polarization degree of the X emission, we deduce the microwave-induced electron spin-flip time >0.1 mus, which is much longer than the recombination time of X and X-. This demonstrates that the optically detected ESR in type I quantum wells with low density of excess electrons does not obey the prerequisite for the conventional optically detected magnetic resonance. (C) 2001 American Institute of Physics.

Cyclotron-resonance mass of two-dimensional electrons in GaN/AlxGa1-xN heterostructures

The electron cyclotron-resonance (CR) mass of quasi-two-dimensional electrons in GaN/AlxGa1-xN heterostructures is studied theoretically. The correction to the CR mass due to electron-phonon interaction is investigated, taking into account band nonparabolicity, the occupation effect, and the screening of the electron-phonon coupling. The dependence of the CR mass on the electron density and on the magnetic field strength is displayed in detail, and the calculated CR mass agrees well with a recent experiment. We found that the effective electron-phonon coupling strength in GaN heterostructures is reduced below the bulk value.

The electron emission yield induced by the interaction of highly charged argon ions with silicon surface

The electron emission yield of the interaction of highly charged argon ions with silicon surface is reported. The experiment was done at the Atomic Physics Research Platform on the Electron Cyclotron Resonance (ECR) Ion Source of the National Laboratory HIRFL (Heavy Ion Research Facility in Lanzhou). In the experiment, the potential energy and kinetic energy was selected by varying the projectile charge states and extracting voltage, thus the contributions of the projectile potential energy deposition and electronic energy loss in the solid are extensively investigated. The results show that, the two main factors leading to surface electron emission, namely the potential energy deposition and the electronic energy loss, are both approximately proportional to the electron emission yield per ion.