Determination of the active metabolite of molsidomine in human plasma by reversed-phase high-performance liquid chromatography

A reversed-phase high-performance liquid chromatographic method, with ultraviolet detection, is proposed for the plasma determination of SIN-1, the active metabolite of molsidomine, which involves propoxycarbonyl derivatization. The internal standard is the ethoxycarbonyl derivative of SIN-1 (i.e. molsidomine). Derivatization and extraction are each performed in one step (2 min) with 70% yield. The nature of a by-product is discussed. The method provides rapid elution (less than 15 min), linearity over the range 0.4-200 ng/ml, day-to-day precision between 2.5 and 11.3% and a limit of determination of 0.5 ng/ml. This method is also suitable for the simultaneous determination of molsidomine and SIN-1. In this case the internal standard is an ethoxycarbonyl derivative of a piperazino-3-sydnonimine, a SIN-1 analogue.     

Selective Double Functionalization of meso‐Tetraphenylporphyrin Complexes on the Same Pyrrole Unit by Tandem Electrophilic/Nucleophilic Aromatic Substitution

The mono‐nitrated meso‐tetraphenylporphyrin (TPP) complex 2 could be readily functionalized on the substituted pyrrole ring with yields of up to 83%. These transformations were achieved via aromatic substitution with carbanions generated from diverse functionalized compounds containing different leaving groups ( 3a – g , Scheme 1). The resulting TPP compounds 4a – g , bearing two different β‐substituents on the same pyrrole ring, may be further manipulated. This, in turn, should allow one to tune the solubility of TPP derivatives used in photodynamic cancer therapy.     

ELEMENTAL SELENIUM GENERATED BY THE PHOTOBLEACHING OF SELENOMEROCYANINE PHOTOSENSITIZERS FORMS CONJUGATES WITH SERUM MACROMOLECULES THAT ARE TOXIC TO TUMOR CELLS

Elemental selenium generated by the photobleaching of selenomerocyanine dyes forms conjugates with serum albumin and serum lipoproteins that are toxic to leukemia and selected solid tumor cells but well tolerated by normal CD34-positive hematopoietic stem and progenitor cells. Serum albumin and lipoproteins act as Trojan horses that deliver the cytotoxic entity (elemental selenium) to tumor cells as part of a physiological process. They exploit the fact that many tumors have an increased demand for albumin and/or low-density lipoprotein. Se(0)-protein conjugates are more toxic than selenium dioxide, sodium selenite, selenomethionine, or selenocystine. They are only minimally affected by drug resistance mechanism, and they potentiate the cytotoxic effect of ionizing radiation and several standard chemotherapeutic agents. The cytotoxic mechanism of Se(0)-protein conjugates is not yet fully understood. Currently available data are consistent with the notion that Se(0)-protein conjugates act as air oxidation catalysts that cause a rapid depletion of intracellular glutathione and induce apoptosis. Drugs modeled after our Se(0)-protein conjugates may prove useful for the local and/or systemic therapy of cancer.     

Solution of the10Li-Puzzle

The mass of¹⁰Li has been measured with two different reactions:⁹Be(¹³C,¹²N)¹⁰Li,E _Lab=336 MeV, and¹³C(¹⁴C,¹⁷F)¹⁰Li,E _Lab=337 MeV. The mass excess of 33.445(50) MeV is deduced from theQ-value measurement.¹⁰Li is found to be particle-unstable with respect to one-neutron emission by 0.42(5) MeV. In the analysis of the first reaction a low lying excited state is found at 0.38(8) MeV. This state and the ground state can be most probably identified as the 1⁺/2⁺-doublet coupled from the [π 1p3/2 ?ν 1p 1/2] configuration, the 1⁺-state being the ground state. The (¹³C,¹²N)-reaction populates the 1⁺-state strongly due to a spin-isospin-flip character of the dominant part of the transition amplitude. The 2⁺-member corresponds to the mass given by Wilcox et al. A second excited state is observed at 4.05(10) MeV with a width of 0.7(2) MeV, it can be associated with theν 1d 5/2-strength. The second reaction is fully supporting the interpretation of the ground state doublet. The excited state at 4.05 MeV is not observed in this reaction and indeed it should not, because the reaction does not populate in first order excited neutron configurations. The levels are well described by mean field calculations including pairing correlations. The lowest resonance in the calculations is theν 1/2^?-configuration, whereas theν 1/2⁺-configuration shows at the neutron threshold a strong non-resonant contribution.     

N=82 shell quenching of the classical r-process "waiting-point" nucleus 130Cd

First beta- and gamma-spectroscopic decay studies of the N=82 r-process "waiting-point" nuclide 130Cd have been performed at CERN/ISOLDE using the highest achievable isotopic selectivity. Several nuclear-physics surprises have been discovered. The first one is the unanticipatedly high energy of 2.12 MeV for the [pi g(9/2) multiply sign in circle nu g(7/2)] 1(+) level in 130In, which is fed by the main Gamow-Teller transition. The second surprise is the rather high Q(beta) value of 8.34 MeV, which is in agreement only with recent mass models that include the phenomenon of N=82 shell quenching. Possible implications of these new results on the formation of the A approximately 130 r-process abundance peak are presented.     

Femtosecond vibrational dynamics of self-trapping in a quasi-one-dimensional system

We have directly time resolved the lattice motions associated with the formation of the self-trapped exciton in the quasi-one-dimensional system [Pt(en)(2)] [Pt(en)2Br2];(PF6)(4) ( en = ethylene-diamine, C2H8N2), using femtosecond impulsive excitation techniques. A strongly damped, low-frequency wave packet modulation at approximately 110 cm(-1) accompanies the formation of the self-trapped exciton on a approximately 200 fs time scale following excitation of the intervalence charge-transfer transition. Coherent oscillations at the ground state vibrational frequency and its harmonics are also detected.     

On a theorem by Kronecker

Aequationes mathematicae -