Synthesis of substituted carbazoles by a vinylic to aryl palladium migration involving domino C-H activation processes

Substituted carbazoles are readily prepared in good yields by the palladium-catalyzed cross-coupling of alkynes and N-(3-iodophenyl)anilines. This process proceeds by carbopalladation of the alkyne, heteroatom-directed vinylic to aryl palladium migration, and ring closure involving two consecutive C-H activation processes. The process has also been expanded to the synthesis of an indole. [Structure: see text]     

Regio- and stereoselective oxetane formation via paterno-buchi photocycloaddition

Carbonyl 2 + 2 photoaddition occurs selectively to the alkene moiety of 3-(4-methyl-3-pentenoxy)pyridine. Photolysis of alkene containing pyridines in acetophenone gives rise to an oxetane which is obtained with extremely high diastereoselectivity as shown by analysis of the major 2 + 2 photoproduct. A second photoproduct, 2,3-dihydroxy-2,3-diphenylbutane, is obtained as a result of acetophenone coupling.     

Improved detection of multi-phosphorylated peptides in the presence of phosphoric acid in liquid chromatography/mass spectrometry

In contrast to lower phosphorylation states (e.g. the tryptic monophosphopeptide FQpSEEQQQTEDELQDK from bovine beta-casein), the specific detection of multi-phosphorylated peptides (e.g. the tetraphosphopeptide RELEELNVPGEIVEpSLpSpSpSEESITR from tryptic digestion of bovine beta-casein) has often been problematic for liquid chromatographic mass spectrometric (LC/MS) analysis owing to their high affinity for adsorption to exposed surfaces. We observed an enhancement in the overall detection of phosphopeptides on addition of phosphoric acid (0.1-1.0%) to the sample solution; a 10-fold increase in sensitivity was determined for the detection of two tryptic phosphopeptides and also a significant improvement in the detection of the tetraphosphopeptide. Using capillary LC with ion trap tandem MS for detection and identification, the achievable detection limits were 50 fmol and 50 pmol for the monophosphopeptide and the tetraphosphopeptide, respectively. Phosphoric acid is believed to act as a blocking agent to available silanol groups on both the silica capillary surface and the C(18)-bonded stationary phase silica surface.     

Fluorescence polarization assays in signal transduction discovery

Fluorescence polarization (FP) has become widely employed for high throughput screening used in pharmaceutical drug discovery. Assays of important signal transduction targets are now adapted to FP. In this review we examine assays for cyclic adenosine monophosphate, phosphodiesterases, and protein kinases and phosphatases using FP competitive immunoassays and a direct enzymatic method called IMAP.     

An investigation of the triplet state dynamics of zinc chlorophyll b by microwave-induced changes in the intensity of fluorescence and singlet-singlet absorption

Optical detection of magnetic resonance experiments on the triplet state of zinc-substitution chlorophyll b has provided the zero-field splitting and depopulation rate constants for the individual triplet spin sublevels. The zero field triplet state EPR transitions could be observed at 890 MHz and 1085 MHz as either microwave-induced changes in the fluorescence intensity or in the intensity of S₀ → S_n absorption. The dynamics experiments show that intersystem crossing from the Zn chlorophyll b triplet state into the ground state occurs primarily through the out-of-plane (lowest energy) spin sublevel.     

Determination of fluoride by analate additions potentiometry

Summary A novel direct potentiometric technique called analate additions potentiometry has been applied to the determination of fluoride using a fluoride ion selective indicator electrode. As expected, the analytical results are comparable to those obtained by the standard additions technique. An error of less than 1 part in 1000 and a precision of about 0.5% was achieved. The technique should be most useful in the determination of small sample volumes which cannot be done by the standard additions method without prior dilution.

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Zusammenfassung Ein neues, direktes potentiometrisches Verfahren wurde für die Fluoridbestimmung angewendet, wobei eine für Fluoridionen selektive Indikatorelektrode verwendet wurde. Wie erwartet sind die Ergebnisse dieses Probenzusatzverfahrens mit denen der Standardzusatzmethode vergleichbar. Der Fehler ist kleiner als l, die Genauigkeit beträgt etwa 0,5%. Das angegebene Verfahren eignet sich vor allem zur Analyse kleiner Probevolumina, die ohne vorherige Verdünnung mit der Standardzusatzmethode nicht analysiert werden können.

     

Solution-based assembly of conductive gold film on flexible polymer substrates

Conductive films of gold were assembled on flexible polymer substrates such as Kapton and polyethylene using a solution-based process. The polymer substrates were modified by using argon plasma and subsequent coupling of silanes with amino- or mercapto- terminal groups. These modified surfaces were examined by X-ray photoelectron spectroscopy and contact angle measurements. Colloidal gold was assembled onto the silane-modified surface from solution. The gold particles are attached to the surface by covalent interactions with the thiol or amine group. Formation of a conductive film is achieved by increasing the coverage of gold by using a "seeding" method to increase the size of the attached gold particles. Field emission scanning electron microscopy was used to follow the growth of the film. The surface resistance of the films, measured using a four-point probe, was about 1 Omega/sq.     

Mechanism for collision-induced transitions between Λ-doublets in 1Π molecules: Reduction to a single scattering potential

The theory is presented for rotational excitation of ¹Π molecules by collisions with rare gas atoms. It is shown that collision dynamics are described by the two electronic potential energy surfaces which correlate with the electronically degenerate Λ components (doublets) in the diatomic molecule. Because the ±Λ degeneracy can alternatively be described as being in the rotational rather than in the electronic degree of freedom, one can reformulate the collision dynamics in terms of a single effective electronic potential which then depends on Φ, the angle of rotation about the diatomic axis. The form of this Φ dependence is found to be identical to that postulated to explain experimental data for collisional transfer of laser-induced fluorescence.     

Simple instrument for titrimetry without visual indicators. gasometric titrations: Cerimetry,chlorometry, nitrate,nitrite, hydroxide and carbonate determination

It was shown in previous papers, that many titrimetric problems can be solved by observing the pressure change of a closed system above the solution titrated at the equivalence point. This principle was made the basis of a gasometric titration method in which the end-point is found graphically. The titrant is added to the sample solution in measured increments at fixed intervals of time and the corresponding gas pressure or volume of the system is recorded and then plotted against the volume of added titrant. Half a dozen readings are sufficient to establish the end-point of a titration, which is found at the intersection of two straight lines. This graphical method was applied to cerimetry and chlorometry, as well as to some other analytical reactions (determination of nitrite, nitrate, hydroxide and carbonate) already described in previous papers on the gas pressure end-point technique. The results are comparable in precision and accuracy to the values obtained by the conventional visual end-point titrations. A gasometric titration takes about 10 minutes. The presence of other substances in the sample capable of reacting with the titrant does not necessarily cause interference.