PHOTODYNAMIC GENERATION OF HYDROXYL RADICALS BY HEMATOPORPHYRIN DERIVATIVE AND LIGHT

In a reaction mixture containing hematoporphyrin derivative, deoxyribose, Fe³⁺-EDTA and either methionine or tryptophan, hydroxyl radicals were formed during illumination with visible light. When either hematoporphyrin derivative, Fe³⁺-EDTA or the amino acid was omitted from the reaction mixture, the generation of hydroxyl radicals ceased. These observations suggest an iron-catalyzed Haber-Weiss reaction, involving superoxide and hydrogen peroxide in the generation of hydroxyl radicals. It could be shown that with methionine H₂O₂ was indeed an essential intermediate in the reaction sequence. With tryptophan, however, H₂O₂, was not generated. Apparently a photooxidation product of tryptophan could replace H₂O₂ in the OH-generating reaction with Fe²⁺-EDTA. Although superoxide was generated in the reaction mixture, it was not an indispensable intermediate. Apparently a porphyrin radical, formed via photoexcitation of hematoporphyrin derivative, could replace superoxide in the Haber-Weiss reaction.     

The Reaction of 2-Methylindole with Pyruvic Acid

The reaction of 2-methylindole with pyruvic acid was studied. Two products are found to be depending on experimental conditions, including the 2:2 condensation adduct and the 2:1 condensation adduct. The reaction mechanism evidently involves a 1:1 adduct of 2-hydroxy-2-(2-methylindol-3-yl)-propionic acid as an intermediate.     

Discreteness and the origin of probability in quantum mechanics

Attempts to derive the Born rule, either in the Many Worlds or Copenhagen interpretation, are unsatisfactory for systems with only a finite number of degrees of freedom. In the case of Many Worlds this is a serious problem, since its goal is to account for apparent collapse phenomena, including the Born rule for probabilities, assuming only unitary evolution of the wavefunction. For finite number of degrees of freedom, observers on the vast majority of branches would not deduce the Born rule. However, discreteness of the quantum state space, even if extremely tiny, may restore the validity of the usual arguments.     

Magnetic resonance imaging features in melanoma

T1 and T2 relaxation time shortening secondary to paramagnetic compounds has been described in melanoma. The purpose of this paper is to evaluate the signal behavior of melanoma involved in various body areas using short TR, TE and long TR, TE sequences. Twenty-seven sites of melanoma were evaluated with MR using T1 weighted and T2-weighted techniques. Using fat and muscle signal intensities as references tissues, lesions were graded into high, low or intermediate intensity categories for each of the sequences. Four signal patterns emerged. The typical pattern characterized by high signal on T1-weighted images and low signal on T2-weighted images reflected T1 and T2 shortening. The other pattern categories comprised of lesions demonstrating low signal T1-weighted images and high signal on T2-weighted images, high signal on both T1- and T2-weighted images and lesions showing intermediate signal on either T1- or T2-weighted images. We observed a tendency away from the typical signal pattern in extraocular melanoma cases with only one of 14 demonstrating this pattern. Moreover, only seven of thirteen ocular melanomas exhibited such behavior. Possible explanations for this findings as well as the existence of a variety of MR appearances to melanoma are offered. We conclude that while signal patterns showing T1 and T2 shortening are typical of melanoma, the absence of these does not exclude the diagnosis.     

Performance of a collimating L‐shaped laterally graded multilayer mirror for the IXS analyzer system at NSLS‐II

The L‐shaped laterally graded multilayer mirror is a vital part of the ultrahigh‐energy and momentum‐resolution inelastic X‐ray scattering spectrometer at the National Synchrotron Light Source II. This mirror was designed and implemented as a two‐dimensional collimating optic for the analyzer system. Its performance was characterized using a secondary large‐divergence source at the 30‐ID beamline of the Advanced Photon Source, which yielded an integrated reflectivity of 47% and a collimated beam divergence of 78 µrad with a source size of 10 µm. Numerical simulations of the mirror performance in tandem with the analyzer crystal optics provided details on the acceptance sample volume in forward scattering and defined the technical requirements on the mirror stability and positioning precision. It was shown that the mirror spatial and angular stability must be in the range <8.4 µm and <21.4 µrad, respectively, for reliable operation of the analyzer.     

The private Higgs

We introduce Higgs democracy in the Yukawa sector by constructing a model with a private Higgs and a dark scalar for each fermion thus addressing the large hierarchy among fermion masses. The model has interesting implications for the LHC, while the Standard Model phenomenology is recovered at low energies. We discuss some phenomenological implications such as FCNC, new Higgses at the TeV scale and dark matter candidates.     

Mechanism of thermal elimination of ethane from iodotrimethylbis(dimethylphenylphosphine)platinum(IV)

The isotope content of ethane formed by pyrolysis of the complex (Me₂PPh)₂PtMe₃I and its deuterated derivatives shows that the reaction is both intramolecular and first order with respect to substrate and gives the activation parameter ΔH3 = 129 ± 5 kJ · mol^?1.     

Investigations into the Manzamine Alkaloid Biosynthetic Hypothesis

The biomimetic synthesis of a pentacyclic alkaloid (keramaphidin B, 1 ), an intermediate in the biogenetic pathway to the manzamine alkaloids, has been achieved. Compound 1 was formed by an intramolecular Diels–Alder reaction of macrocycle 2 in buffer followed by reduction with NaBH₄. This reaction provides the first direct expeimental evidence for the authors' biosynthetic hypothesis.     

Bond and mode selectivity in the reaction of atomic chlorine with vibrationally excited CH2D2

The title reaction is investigated by co-expanding a mixture of Cl2 and CH2D2 into a vacuum chamber and initiating the reaction by photolyzing Cl2 with linearly polarized 355 nm light. Excitation of the first C-H overtone of CH2D2 leads to a preference for hydrogen abstraction over deuterium abstraction by at least a factor of 20, whereas excitation of the first C-D overtone of CH2D2 reverses this preference by at least a factor of 10. Reactions with CH2D2 prepared in a local mode containing two quanta in one C-H oscillator /2000>- or in a local mode containing one quantum each in two C-H oscillators /1100> lead to products with significantly different rotational, vibrational, and angular distributions, although the vibrational energy for each mode is nearly identical. The Cl+CH2D2/2000>- reaction yields methyl radical products primarily in their ground state, whereas the Cl+CH2D2/1100> reaction yields methyl radical products that are C-H stretch excited. The HCl(v=1) rotational distribution from the Cl+CH2D2/2000>- reaction is significantly hotter than the HCl(v=1) rotational distribution from the Cl+CH2D2/1100> reaction, and the HCl(v=1) differential cross-section (DCS) of the Cl+CH2D2/2000>- reaction is more broadly side scattered than the HCl(v=1) DCS of the Cl+CH2D2/1100> reaction. The results can be explained by a simple spectator model and by noting that the /2000>- mode leads to a wider cone of acceptance for the reaction than the /1100> mode. These measurements represent the first example of mode selectivity observed in a differential cross section, and they demonstrate that vibrational excitation can be used to direct the reaction pathway of the Cl+CH2D2 reaction.