Klaus Krambrock

Synthesis of C60(OH)18-20 in aqueous alkaline solution under O2-atmosphere

In this work we report on an alternative synthesis of water-soluble fullerenes known as fullerols, aiming for biomedical applications. The synthesis is based on a process in which polyethylene glycol (PEG400) is used as phase-transfer catalyst between fullerene/benzene and aqueous NaOH solutions. The polyhydroxylation of the fullerenes occurs in the NaOH solution under a continuous flow of O2 to enhance the reaction yield. The resulting compound was characterized with infrared spectroscopy, nuclear magnetic resonance, thermo-gravimetric analysis and optical absorption. The formation of C60(OH)18-20 in high yields was confirmed.

Structural and photophysical properties of peptide micro/nanotubes functionalized with hypericin.

Hypericin is a photosensitizer with promising applications in photodynamic therapy (PDT) for cancer and infectious diseases treatments. Herein, we present a basic research study of L-diphenylalanine micro/nanotubes (FF-NTs) functionalized with hypericin. The system has special properties according to the hypericin concentration, with direct consequences on both morphological and photophysical behaviors. A clear dependence between the size of the tubes and the concentration of hypericin is revealed. The generation of reactive oxygen species (ROS) is found to be improved by ∼57% in the presence of FF-NTs, as indirectly measured from the absorbance profile of 1,3-diphenylisobenzofuran (DPBF). In addition, when hypericin appears conjugated with FF-NTs, the characteristic fluorescence lifetime is significantly boosted, demonstrating the role of FF-NTs to enhance the photophysical properties and stabilizing the fluorophore in excited states. Electron paramagnetic resonance allows the proposition of a mechanism for the generation of ROS. Molecular dynamics simulations bring new insights into the interaction between hypericin and peptide assemblies, suggesting the spatial organization of the fluorophore onto the surface of the supramolecular structures as a key element to improve the photophysical properties reported here.

Raman and infrared study of hydroxyl sites in natural uvite, fluor-uvite, magnesio-foitite, dravite and elbaite tourmalines

We present the Raman and infrared spectra of different tourmaline species in the spectral range associated with the hydroxyl stretching modes, investigated through polarized Raman spectroscopy. Different lineshapes are observed for the OH spectra in uvite, fluor-uvite, magnesio-foitite, dravite and elbaite samples, and can be related to the coordination of OH in the two different structural V[O(3)]- and W[O(1)]-occupied sites. Local arrangements around the two different OH sites were assigned, and different ion substitutions for these five tourmaline species were identified. Our work with polarized Raman spectroscopy revealed that OH-stretching modes are described by totally symmetric, irreducible representations.

Identification of trivalent rare earth impurities in YF3, LuF3 and LiYF4 by electron paramagnetic resonance

Abstract Yttrium fluoride (YF3), lutetium fluoride (LuF3) and lithium yttrium fluoride (LiYF4) are considered as potential host materials for laser and scintillator ions. YF3 and LuF3 are orthorhombic with space group Pnma (D162h), while LiYF4 is tetragonal with space group I41/a (C64h) all with four molecules per unit cell. In the first class the trivalent Y-site is 9-fold coordinated by F ions and in the second 8-fold. Using electron paramagnetic resonance (EPR) in doped and undoped crystals different rare earth impurities have been identified from their typical hyperfine interaction and their spin Hamiltonian parameters have been determined. We show that trivalent rare earth impurities like Nd3+, Yb3+, Er3+ and Ce3+ substitute for Y3+ (Lu3+) in YF3 (LuF3) preserving the monoclinic local Cs site symmetry of Y (Lu) ion. The same holds for LiYF4 where the rare earth impurities maintain the local S4 symmetry. In the undoped crystals the rare earth impurities come from traces in the starting materials.

Quantification of fullerene nanoparticles suspensions in water based on optical scattering.

Fullerenes, and in particular the C60, have been intensively investigated in the last decades mainly because of their vast range of potential applications in biomedicine and materials science. These molecules are inherently hydrophobic, tending thus to form clusters and aggregates in polar solvents resulting in colloidal suspensions. In this work was developed a quantification method for C60 nanoparticles (nano-C60) in colloidal aqueous suspensions based on optical light scattering (nephelometry). This method can be done in a conventional spectrofluorimeter either on the excitation wavelengths or on the second-order satellite lines that arise from the diffraction gratings. The detection limit of the proposed method was about (0.0090+/-0.0008) mg L(-1), in a linear concentration range from 0.007 to 0.360 mg L(-1). A comparison of this scattering technique with spectrophotometry based on molecular absorption shows that for the former, even at the second-order lines, the threshold concentrations detected are about 20 times lower that the latter.

Metavivianite, Fe2+Fe23+(PO4)2(OH)2·6H2O: new data and formula revision

Abstract The composition, structure, X-ray powder diffraction pattern, optical properties, density, infrared, Raman and Mössbauer spectra, and thermal properties of a homogeneous sample of metavivianite from the Boa Vista pegmatite, near Galiléia, Minas Gerais, Brazil are reported for the first time. Metavivianite is biaxial (+) with α = 1.600(3), β = 1.640(3), γ = 1.685(3) and 2Vmeas = 85(5)°. The measured and calculated densities are D meas = 2.56(2) and D calc = 2.579 g cm-3. The chemical composition, based on electronmicroprobe analyses, Mössbauer spectroscopy (to determine the Fe2+:Fe3+ ratio) and gas chromatography (to determine H2O) is MgO 0.70, MnO 0.92, FeO 17.98, Fe2O3 26.60, P2O5 28.62, H2O 26.5; total 101.32 wt.%. The empirical formula is (Fe3+1.64Fe2+1.23Mg0.085Mn0.06)Σ3.015(PO4)1.98(OH)1.72·6.36H2O. Metavivianite is triclinic, P1, a = 7.989(1), b = 9.321(2), c = 4.629(1) Å, α = 97.34(1), β = 95.96(1), γ = 108.59(2)°, V = 320.18(11) Å3 and Z = 1. The crystal structure was solved using a single-crystal techniques to an agreement index R = 6.0%. The dominant cations in the independent sites are Fe2+ and Fe3+, with multiplicities of 1 and 2, respectively. The simplified crystal-chemical formula for metavivianite is Fe2+ (Fe3+, Fe2+)2(PO4)2(OH,H2O)2·6H2O; the endmember formula is Fe2+Fe3+2(PO4)2(OH)2·6H2O, which is dimorphous with ferrostrunzite.

The reduction of oxidative stress by nanocomposite Fullerol decreases mucositis severity and reverts leukopenia induced by Irinotecan.

Irinotecan is a useful chemotherapeutic agent for the treatment of several solid tumors. However, this therapy is associated with side effects, including leukopenia and mucositis. Reactive oxygen species (ROS) activate inflammatory pathways and contribute to Irinotecan-induced mucositis. Fullerol is a nanocomposite with anti-oxidant properties that may reduce tissue damage after inflammatory stimuli. In this paper, the effects of Fullerol and mechanisms of protection were investigated in a model of Irinotecan-induced mucositis. Mucositis was induced by an injection of Irinotecan per 4 days in C57BL/6. Fullerol or a vehicle was injected every 12h. On day 7, the intestines were removed to evaluate histological changes, leukocyte influx, and the production of cytokines and ROS. Irinotecan therapy resulted in weight loss, an increased clinical score and intestinal injury. Treatment with Fullerol attenuated weight loss, decreased clinical score and intestinal damage. Irinotecan also induced increased ROS production in enterocytes, oxidative stress, IL-1β production, neutrophil and eosinophil influx in the ileum. Fullerol treatment decreased production of ROS in the enterocytes, oxidative stress, IL-1β production, neutrophil and eosinophil influx in the ileum. Irinotecan therapy also induced leukopenia in an ROS-dependent manner because leukopenia reverted in WT mice treated with Fullerol or Apocynin or in Gp91phox(-/-) mice. Mice treated with Irinotecan presented less melanoma tumor growth compared to the control group. Fullerol does not interfere in the anti-tumor action of Irinotecan. Fullerol has a great pharmacology potential to decreases the severity of mucositis and of leukopenia during chemotherapy treatment.

Identification of rhenium donors and sulfur vacancy acceptors in layered MoS2 bulk samples

MoS2 monolayers, a two-dimensional (2D) direct semiconductor material with an energy gap of 1.9 eV, offer many opportunities to be explored in different electronic devices. Defects often play dominant roles in the electronic and optical properties of semiconductor devices. However, little experimental information about intrinsic and extrinsic defects or impurities is available for this 2D system, and even for macroscopic 3D samples for which MoS2 shows an indirect bandgap of 1.3 eV. In this work, we evaluate the nature of impurities with unpaired spins using electron paramagnetic resonance (EPR) in different geological macroscopic samples. Regarding the fact that monolayers are mostly obtained from natural crystals, we expect that the majority of impurities found in macroscopic samples are also randomly present in MoS2 monolayers. By EPR at low temperatures, rhenium donors and sulfur vacancy acceptors are identified as the main impurities in bulk MoS2 with a corresponding donor concentration of about 108–...

Spectroscopic characterization of transition metal impurities in natural montebrasite/amblygonite

Abstract Natural single-crystal specimens of the montebrasite/amblygonite series from Brazil, with general formula LiAlPO4(F,OH), were investigated by electron microprobe, Raman spectroscopy, X-ray diffraction, and infrared absorption. Since little is known about impurities and their local symmetries, electron paramagnetic resonance (EPR) was applied. Six different paramagnetic impurities and radiation defects were detected by EPR. Three of them, all substituting for Al3+ ions, namely, iron (Fe3+), vanadium (V4+), and niobium (Nb4+) impurities were characterized in this work. The Fe3+ (3d5)-related EPR spectra and angular dependencies show occupation of low-symmetry sites that are revealed in the high asymmetry parameter of the electronic fine structure, E/D = 0.27. Vanadium and niobium impurities are identified through their typical strong hyperfine interactions. Both form interesting examples for which the properties of 3d1 ion (V4+) and 4d1 ion (Nb4+) in the same host matrix can be compared. It is shown that both ions form complex defects of type VO2+ (vanadyl) and NbO2+ (niobyl), showing superhyperfine interaction with two equivalent hydrogen ions and not to fluorine. The EPR rotation patterns are analyzed in detail for three mutually perpendicular crystal planes. Spin Hamiltonian parameters are calculated and discussed.

Radiation-induced centers in Cs-rich beryl studied by magnetic resonance, infrared and optical spectroscopy

Abstract Natural and γ-irradiated pink and colorless beryl from Brazil has been investigated by electron paramagnetic resonance (EPR), optical absorption and infrared absorption. Beryl has the chemical formula Be 3 Al 2 Si 6 O 18 and is hexagonal with space group P6/mcc. Electron microprobe analysis of the different samples shows that the beryl samples are rich in Cs (3.30 wt.%) and contain low concentrations of transition-metal ions, in total ∼0.03 wt.% Fe and ∼0.05 wt.% Mn. In addition to the transition-metal ions, beryl accommodates many molecules and alkalis in its channels, which lie parallel to the c -axis and which have large diameters with a maximum of 5.1 A. Infrared absorption measurements in the different samples indicate the presence of type-I and type-II water together with OH − . Other molecules in the channels with not yet associated infrared absorptions are NO 3 0 and CO 3 − which have been observed by EPR. In this work we focus on the EPR identification of the different molecules and discuss their relation to color.