Electron-impact fragmentation of penta-fluorophenyldimethylsilyl ethers of some sterols of biological importance

The mass spectral properties under medium and high resolution of a new protecting group for sterols is described and its ability to direct fragmentation is compared with established derivatives. The mass spectra obtained are characterised by strong molecular ions which fragment to produce a more even ion distribution than the familiar TMS ethers. This results in enhanced abundance of hydrocarbon fragments, with molecular structural details given greater prominence than is found with other derivatives.     

Computing the electric potential of biomolecules: Application of a new method of molecular surface triangulation

A new method is presented for defining a smooth, triangulated analytic surface for biological molecules. The surface produced by the algorithm is well-suited for use with a recently developed polarizationcharge technique¹ for the computation of the electrostatic potential of solvated molecules, and may also be used for calculations of molecular surface areas and volumes. The new method employs Connolly's definitions of contact, reentrant and saddle surface,² but includes modifications that preclude the presence of self-interesting reentrant surface, and also insure a rigorous decomposition of contact regions into curvilinear finite elements. The triangulation algorithm may be used in conjunction with the electrostatic methods described previously to compute the electric potential of molecules of arbitrary shape in solution. Applications include the estimation of hydration enthalpies, computation of the electrostatic forces associated with solvation, estimation of interactions between separate charged species in solution, and computation of the three-dimensional form of the molecular electric potential. Test calculations are presented for a double-stranded dinucleotide, the polypeptide enkephalin, and the protein ferredoxin.     

Chemical fractionation in the solar system

The cosmochemical and geochemical history of planetary material is reflected in relative and absolute abundances of two groups of trace elements; siderophiles and volatiles. Many of these elements can be determined at the requires levels only by radiochemical neutron activation analysis. The abundance patterns of elements in chondritic meteorites result from condensation processes in the solar nebula. The composition of planetisimals which bombarded the Moon is characterized from trace elements in lunar breccias, and is also related to nebula processes. Trace elements in anorthosites and basalts from Earth and Moon suggest that the Moon is refractory-rich and volatile-poor relative to the Earth.     

A one-step synthesis of γ-pyrones

The potassium enolate of 4-methoxy-3-buten-2-one reacts with acid chlorides anhydrides and acylimidazoles by C-acylation and $\text{in situ}$ cyclization to afford 2-substituted γ-pyrones directly.     

Treatment of the transplantable FANFT induced bladder tumors with the purpurin SnET2 and red light emitted by a pulsed frequency doubled Nd:YAG laser

Photodynamic therapy of transplantable N-[4-(5-nitro-2-furyl)-2-thiazolyl] formamide-induced tumors engrafted onto Fischer CDF (F-344)/CrlBR rats that had been sensitized with the photosensitizer tin (ll) etiopurpurin dichloride was performed in combination with visible light (approximately equal to 660 nm) emitted by either a continuous wave argon-dye laser or a pulsed, frequency-doubled Nd:Yag laser. Tumor control was assessed either by tumor dry-weight 12 days after treatment or by the palpatory absence of tumor at 60 days after treatment. Both laser sources were effective in creating the desired photodynamic effect. This study demonstrates the potential for the use of a solid-state pulsed laser for photodynamic therapy when used in combination with the tumor sensitizer tin (ll) etiopurpurin dichloride.     

High-performance liquid chromatographic analysis of vancomycin in plasma, bone, atrial appendage tissue and pericardial fluid

Solid-phase extraction coupled with reversed-phase high-performance liquid chromatography and UV detection was employed for the analysis of the antibiotic vancomycin in patient plasma, bone, atrial appendage, and pericardial fluid. Vancomycin was quantitated in samples from patients undergoing cardiac surgery. Calibrations were linear in the range 3-100 micrograms/ml vancomycin; the lower limit of detection was approximately 3 micrograms/ml in fluids with an absolute limit of detection in bone samples of 0.75 microgram per injection.     

METALLOPURPURINS and LIGHT: EFFECT ON TRANSPLANTABLE RAT BLADDER TUMORS and MURINE SKIN

Purpurins are modified chlorins with photodynamic properties. Their strong absorption in the red region of the visible spectrum makes them candidates for use in photodynamic cancer therapy. A series of metal derivatives of the free base purpurins have been synthesized and shown to cause tumor necrosis in transplantable tumors when exposed to visible light. In the following set of experiments, the effects of two metallo-derivatives (tin and zinc) of two purpurins, octaethylpurpurin (NT2) and etiopurpurin (ET2), and light on the N-[4-(5-nitro-2-furyl)-2-thiazolyl] formamide transplantable tumors in Fischer CDF(F344)/CrlBr rats were studied. The photodynamic activity was assessed by a short term assay using tumor dry weight 12 days after purpurin-PDT as a criterion of response. From these experiments it appears that SnET2 greater than SnNT2 greater than ZnET2 greater than ZnNT2 in photodynamic activity. SnET2 was further characterized by attempting to determine the time interval after systemic injection at which maximum therapeutic effect occurred. These studies shown that 24 h after metallopurpurin injection was the optimum time for treatment of tumors with visible light. In a final set of experiments, the effect of solar light on the skin of hairless mice injected with SnET2 was found to be much less injurious than with hematoporphyrin derivative.     

Growth factors and gangliosides: a possible new perspective in neuronal growth control.

For many permanent cell lines the transition from a growing (P) to a resting (R) state is reversibly controlled by growth factors present in serum. This P-to-R transition was studied in a neuronal cell line (B104) with respect to the action of serum, dibutyryl cyclic AMP (DBcAMP), gangliosides, and a glioma cell-produced growth factor GGF. In this cell system gangliosides seem to act as differentiation and survival factors. The kinetics of uptake of radioactively labeled gangliosides and survival experiments both support the idea of the stable incorporation of exogenously added gangliosides into the cells. Based on the experimental evidence a new model of cell development is proposed. Thus in addition to the R or Go state, which in this cell system is rather unstable and probably regulated by cyclic nucleotides, we postulate a differentiated D state, which is controlled by gangliosides and which is characterized by its stability (survival time). This D compartment seems to be closer to the in vivo differentiated neuron than does the R or P state. tthe possible mechanisms for the action of gangliosides are discussed.