Reactions of metal carbonyl cluster complexes with multidentate phosphine ligands; reactions with bis(diphenylphosphino)methane

Reactions of Rh₆(CO)₁₆ with bis(diphenylphosphino)methane (dppm) gave Rh₆(CO)₁₄(dppm), Rh₆(CO)₁₂(dppm)₂, or Rh₆(CO)₁₀(dppm)₃, depending upon the reaction conditions. Rh₄(CO)₁₀(dppm) may be obtained from the reaction of Rh₄(CO)₁₂ with dppm, but this derivative rapidly decomposes in solution to give Rh₄(CO)₈(dppm)₂, Rh₆(CO)₁₄(dppm), and Rh₆(CO)₁₂(dppm)₂. Ir₄(CO)₁₀(dppm) and Ir₄(CO)₈(dppm)₂ have also been prepared, and their structures are discussed on the basis of infrared and ³¹P NMR spectroscopic data.     

Carbon nanohorns grown from ruthenium nanoparticles

A nanoscale ruthenium/gold bimetallic cluster of clusters has been used as a molecular precursor to produce pure ruthenium nanoparticles (seeds) as catalysts for the growth of carbon nanohorns (CNHs).     

High-yield solvothermal formation of magnetic CoPt alloy nanowires

One-dimensional (1D) magnetic nanomaterials have attracted much attention recently because of their applications in magnetic recording and spintronics. Nevertheless, it remains a challenge to prepare free-standing magnetic nanowires in high yield. This Communication reports the successful high-yield synthesis of an interesting 1D ferromagnetic CoPt alloy by direct decomposition of platinum acetylacetonate and cobalt carbonyl compound in ethylenediamine solvent through a solvothermal reaction. The CoPt alloy nanowires obtained have a tunable diameter of 10-50 nm and a length along the longitudinal axis of up to several microns, depending on crystallization temperature and reaction time. A unique formation mechanism involving coarsening and ripening under solvothermal conditions was discovered. This research opens new opportunities in synthesizing nanomaterials through low-temperature solvothermal processes.     

THREE EXPONENTIAL FLUORESCENCE DECAY OF HORSE LIVER ALCOHOL DEHYDROGENASE REVEALED BY IODIDE QUENCHING

Abstract— The time resolved fluorescence decay of horse liver alcohol dehydrogenase was measured using a frequency doubled picosecond dye laser and time-correlated single-photon counting detection. A flow-cell technique is described which eliminates the photodegradation artifacts which commonly occur with laser excitation. A procedure is introduced which uses fluorescence quenching to reveal minor fluorescence lifetime components. The decay of the unquenched tryptophanyl fluorescence could be described by a double exponential decay law, but experiments conducted in the presence of iodide ion showed that the fluorescence decay must be more complex than this. A model is presented in which the fluorescence decay consists of three exponential components, only two of which are susceptible to quenching by iodide ion. Several possibilities are presented for the origin of this minor decay component, the most reasonable of which is that it arises from conformational heterogeneity in the solvent-exposed tryptophanyl residue.     

Multiple sprayer system for high-throughput electrospray ionization mass spectrometry

A multiple sprayer electrospray ion source for high-throughput analysis is described. The ion source is comprised of multiple electrospray capillaries, each with an ion lens located near the tip. The electric potentials applied to the ion lenses are used to control the sprayers. The use of ion lenses eliminates the need for mechanical blocking devices to selectively enable or disable the sprayers, and results in a less expensive and more reliable set-up. Sprayers can be enabled or disabled within approximately 50-250 ms when the lens potentials are controlled manually. For simultaneous operation of multiple electrospray capillaries, it is advantageous to orient the capillaries so that the spray from each passes directly in front of the entrance aperture of the mass spectrometer.     

PHOTODYNAMIC THERAPY INDUCED ULTRASTRUCTURAL ALTERATIONS IN MICROVASCULATURE OF THE RAT CREMASTER MUSCLE

Abstract— Photodynamic therapy disrupts blood flow to tumors and produces tumor necrosis. These effects may be due to a localized generation of singlet oxygen. The current studies used direct observations of the rat cremaster microvasculature to examine the vascular effects of PDT. The objective of the morphological examination was to delineate the structural basis for the altered blood flow in photodynamic therapy. Dihematoporphyrin ether given 30 min or 48 h prior to the experiment was activated with green light (wavelength530–560 nm, 120 J/cm²). After the in vivo activation the tissues were prepared for electron microscopy. Light alone induced little or no change in the luminal content or vessel wall. On exposure to activating light both acute (30 min) and long term (48 h) dihematoporphyrin ether pretreated samples displayed formation of luminal aggregates, granulocyte margination and migration, and endothelial cell and smooth muscle cell damage. The latter was more pronounced in the arterioles than the venules. Perivascular changes included interstitial edema and damage to striated myocytes. Some of the alterations such as interstitial edema may be transient; however, smooth and skeletal muscle cell injury are important in normal and tumor tissue necrosis after photodynamic therapy.     

Time-resolved fluorescence spectra using time-correlated photon counting: Picosecond fluorescence in aqueous solutions of Cr(III) complexes at room temperature

A new procedure for measuring time-resolved emission spectra has been implemented. This technique has subnanosecond time resolution combined with the sensitivity and dynamic range needed to cope with extremely weak luminescence. Using this method the emissions of Cr(NH₃)₂ (NCS)₄^? and Cr(NCS)₆^3- in aqueous solution at room temperature have each been analyzed into two components. The fast component has a broad spectrum and is assigned to prompt fluorescence with lifetime below 100 ps. The slow component is dominated by phosphorescence but may include some delayed fluorescence. The phosphorescence lifetime is 5.5 ± 0.5 ns in Cr(NH₃)₂ (NCS)₄^? and 1.65 ± 0.1 ns in Cr(NCS)₆^3-. Order of magnitude estimates have been derived for other photophysical parameters.     

Sequential cycloaddition approach to the tricyclic core of vibsanin E. Total synthesis of (+/-)-5-epi-10-epi-vibsanin E

[chemical reaction: see text]. A direct access to (+/-)-5-epi-10-epi-vibsanin E is described, based on three key cycloaddition steps, a rhodium-catalyzed [4 + 3] cycloaddition, a heteronuclear [4 + 2] cycloaddition, and a photochemically induced [4 + 2] cycloaddition.     

Straightforward synthesis of sphinganines via a serine-derived Weinreb amide

Sphinganines can be synthesized in just three steps from easily prepared serine-derived Weinreb amide 4. Pre-deprotonation of the acidic (N-H and O-H) protons of 4 allows for its efficient conversion to amino ketones 5. Such ketones can be selectively reduced to either erythro- or threo-sphinganines. Partially protected sphinganines 11 are also readily accessible in five steps from 4. Thus, Weinreb amide 4 represents one of the most versatile templates described to date for sphinganine synthesis.     

Fluoride-facilitated deuterium exchange from DMSO-d6 to polyamide-based cryptands

Multiple deuterium exchange between DMSO-d6 and amide hydrogens in two hexaamido cryptand fluoride receptors has been verified by 19F and 2H NMR and FAB mass spectral studies. Structural results for one of the complexes indicate a tricapped trigonal prism hydrogen bond coordination geometry around an encapsulated fluoride, with hydrogen bonds from fluoride to six amide and three phenyl hydrogens.