Red-Light Activation of a Microtubule Polymerization Inhibitor via Amide Functionalization of the Ruthenium Photocage

Photoactivated chemotherapy (PACT) is a promising cancer treatment modality that kills cancer cells via photochemical uncaging of a cytotoxic drug. Most ruthenium-based photocages used for PACT are activated with blue or green light, which penetrates sub-optimally into tumor tissues. Here, we report amide functionalization as a tool to fine-tune the toxicity and excited states of a terpyridine-based ruthenium photocage. Due to conjugation of the amide group with the terpyridine π system in the excited state, the absorption of red light (630 nm) increased 8-fold, and the photosubstitution rate rose 5-fold. In vitro, red light activation triggered inhibition of tubulin polymerization, which led to apoptotic cell death both in normoxic (21 % O₂) and hypoxic (1 % O₂) cancer cells. In vivo, red light irradiation of tumor-bearing mice demonstrated significant tumor volume reduction (45 %) with improved biosafety, thereby demonstrating the clinical potential of this compound.     

Host-guest interactions at self-assembled monolayers of cyclodextrins on gold

We have developed synthesis routes for the introduction of short and long dialkylsulfides onto the primary side of alpha-, beta-, and gamma-cyclodextrins. Monolayers of these cyclodextrin adsorbates were characterized by electrochemistry, wettability studies, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), and atomic force microscopy (AFM). The differences in thickness and polarity of the outerface of the monolayers were measured by electro-chemistry and wettability studies. On average about 70% of the sulfide moieties were used for binding to the gold, as measured by XPS. Tof-SIMS measurements showed that the cyclodextrin adsorbates adsorb without any bond breakage. AFM measurements revealed for beta-cyclodextrin monolayers a quasi-hexagonal lattice with a lattice constant of 20.6 A, which matches the geometrical size of the adsorbate. The alpha-cyclodextrin and gamma-cyclodextrin monolayers are less ordered. Interactions of the anionic guests 1-anilinonaphthalene-8-sulfonic acid (1,8-ANS) and 2-(p-toluidinyl)naphthalene-6-sulfonic acid (2,6-TNS) and the highly ordered monolayers of heptapodant beta-cyclodextrin adsorbates were studied by surface plasmon resonance (SPR) and electrochemical impedance spectroscopy. The SPR measurements clearly showed interactions between a beta-cyclodextrin monolayer and 1,8-ANS. Electrochemical impedance spectroscopy measurements gave high responses even at low guest concentrations (< or = 5 microM). The association constant for the binding of 1,8-ANS (K = 289,000 +/- 13,000M-1) is considerably higher than the corresponding value in solution. (Partial) methylation of the secondary side of the beta-cyclodextrin strongly decreases the binding.     

Siderophore-Mediated Iron Uptake Promotes Yeast–Bacterial Symbiosis

In the present study, siderophore produced by the marine yeast Aureobasidium pullulans was characterized as hydroxamate by chemical and bioassays. The hydroxamate assignment was supported by the appearance of peaks at 1,647.21?C1,625.99?cm^?1 and at 1,435.04?cm^?1 in the infrared spectrum. The purified siderophore exhibited specific growth-promoting activity under iron-limited conditions for siderophore auxotrophic probiotic bacteria. Cross-utilization of siderophore indicates a symbiotic relationship between the yeast A. pullulans and the selected probiotic bacterial strains. Statistical optimization of medium components for improved siderophore production in A. pullulans was depicted by response surface methodology. The shift in UV?CVis spectroscopy indicates the photoreactive property and subsequent oxidative cleavage of purified siderophore on exposure to sunlight.     

Micromagnetic study of magnetic domain structure and magnetization reversal in amorphous wires with circular anisotropy

In this work we present a detailed numerical investigation on the magnetic domain formation and magnetization reversal mechanism in sub-millimeter amorphous wires with negative magnetostriction by means of micromagnetic calculations. The formation of circular magnetic domains surrounding a multidomain axially oriented central nucleus was observed for the micromagnetic model representing the amorphous wire. The magnetization reversal explained by micromagnetic computations for the M-H curve is described in terms of a combined nucleation-propagation−rotational mechanism after the saturated state. Results are interpreted in terms of the effective magnetic anisotropy.     

Identified hadron compositions in p+p and Au+Au collisions at high transverse momenta at √S(NN)=200 GeV

We report transverse momentum (p(T)≤15 GeV/c) spectra of π(±), K(±), p, p[over ˉ], K(S)(0), and ρ(0) at midrapidity in p+p and Au+Au collisions at √S(NN)=200 GeV. Perturbative QCD calculations are consistent with π(±) spectra in p+p collisions but do not reproduce K and p(p[over ˉ]) spectra. The observed decreasing antiparticle-to-particle ratios with increasing p(T) provide experimental evidence for varying quark and gluon jet contributions to high-p(T) hadron yields. The relative hadron abundances in Au+Au at p(T)?8 GeV/c are measured to be similar to the p+p results, despite the expected Casimir effect for parton energy loss.     

Measurement of the bottom quark contribution to nonphotonic electron production in p + p collisions at √s=200 GeV

The contribution of B meson decays to nonphotonic electrons, which are mainly produced by the semileptonic decays of heavy-flavor mesons, in p + p collisions at √s=200 GeV has been measured using azimuthal correlations between nonphotonic electrons and hadrons. The extracted B decay contribution is approximately 50% at a transverse momentum of pT≥5 GeV/c. These measurements constrain the nuclear modification factor for electrons from B and D meson decays. The result indicates that B meson production in heavy ion collisions is also suppressed at high pT.     

Flux line lattice symmetries in the borocarbide superconductor LuNi2B2C

We compare the results of small angle neutron scattering on the flux line lattice (FLL) obtained in the borocarbide superconductor LuNi₂B₂C with the applied field along the c- and a-axes. For H‖c the temperature dependence of the FLL structural phase transition from square to hexagonal symmetry was investigated. Above 10 K the transition onset field. H ₂(T), rises sharply, bending away from H _c2(T) in contradiction to theoretical predictions of the two merging. For H‖a a first order FLL reorientation transition is observed at H _tr=3–3.5 kOe. Below H _tr the FLL nearest neighbor direction is parallel to the b-axis, and above H _tr to the c-axis. This transition cannot be explained using nonlocal corrections to the London model.     

On the Non-isothermal Precipitation of the and b phases in Al-12.6 mass% Mg alloys using dilatometric techniques

The non-isothermal kinetics of precipitation of an Al-12.6 mass% Mg alloy for different heating rates were studied using thermal expansion techniques. The structural changes associated with the precipitation of the and b phases were identified. The conversion degree of each phase was associated with the area under the derivative curve of the thermal expansion with respect to temperature. Using the Kissinger relation and an iso-conversional method we calculated the apparent activation energies associated with formation of the precipitated phases. We report an increasing dependence of the activation energy on the conversion degree, the values obtained being within the range reported in the literature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Rapid microwave assisted esterification method for the analysis of poly-3-hydroxybutyrate in Alcaligenes latus by gas chromatography

In the present study, we used microwave energy instead of conventional heating to transform poly-3-hydroxybutyrate (PHB) into methyl 3-hydroxybutyrate (Me-3HB) in acidified methanol (H2SO4, 10%, v/v) mixture in less than 4 min at 10% microwave power. The microwave assisted method was then applied to analyze PHB produced by Alcaligenes latus. The PHB content in the biomass determined using microwave heating was comparable to the amount found by conventional heating. Moreover, the new esterification method was at least 50 times faster than the conventional method, affording a significant saving of time and energy.     

Quantitative measurements of injections into porous media with contrast based MRI

Porous flow occurs in a wide range of materials and applies to many commercially relevant applications such as oil recovery, chemical reactors and contaminant transport in soils. Typically, breakthrough and pressure curves of column floods are used in the laboratory characterization of these materials. These characterization methods lack the detail to easily and unambiguously resolve flow mechanisms with similar effects at the core scale that can dominate at the aquifer or oil field scale, as well as the effects of geometry that control the flow at interfaces as in a perforated well or the inlet of an improperly designed column. Non-invasive imaging techniques such as MRI have been shown to provide a far more detailed characterization of the properties of the solid matrix and flow, but usually focus on the intrinsic flow properties of porous media or matching a numerical model to a complex flow system. We show that these MRI techniques, utilizing paramagnetic tagging in combination with a carefully controlled and ideal flow system, can quantitatively characterize the effects of geometry and intrinsic flow properties for a point injection into a core. The use of a carefully controlled and 'idealized' system is essential to be able to isolate and match predicted effects from geometry and extract subtle flow processes omitted in the model that would be hidden in a more heterogeneous system. This approach provides not only a tool to understand the behavior of intentional boundary effects, but also one to diagnose the unintentional ones that often degrade the data from routine column flood measurements.