Highly convergent three component benzyne coupling: the total synthesis of ent-clavilactone B

The first total synthesis of (+)-clavilactone B, a potent antifungal agent and novel tyrosine kinase inhibitor, is described. The absolute configuration of clavilactones has been unambiguously established by using Sharpless asymmetric epoxidation to generate the enantiomerically pure substrate. The strategy highlights the use of a powerful and convergent three-component benzyne coupling with a methylallyl Grignard and a chiral epoxy-aldehyde to generate two C-C bonds and install the carbon skeleton of clavilactone. Oxidative lactonization, ten-membered ring construction by ring closing metathesis, and oxidation gave clavilactone B.     

Virtual retractions,conjugacy separability and omnipotence

We use wreath products to provide criteria for a group to be conjugacy separable or omnipotent. These criteria are in terms of virtual retractions onto cyclic subgroups. We give two applications: a straightforward topological proof of the theorem of Stebe that infinite-order elements of Fuchsian groups (of the first type) are conjugacy distinguished, and a proof that surface groups are omnipotent.     

Electronic spectral detection in liquid chromatography

The use of absorbance and fluorescence spectrometers as liquid chromatography detectors is described. These detectors offer sensitive detection that can also identify the peaks in a chromatogram. Many examples, mainly from the separation of polycyclic aromatic hydrocarbons, are given that show the selectivity and usefulness of these detectors.     

Elementarily free groups are subgroup separable

Elementarily free groups are the finitely generated groups withthe same elementary theory as free groups. We prove that elementarilyfree groups are subgroup separable, answering a question ofZlil Sela.     

Spectral signatures of inter-system crossing mediated by energetically distant doorway levels: examples from the acetylene S1 state

We review recent research on the acetylene S(1) state that illustrates how mechanistic rather than phenomenological information about intersystem crossing (ISC) may be obtained directly from frequency-domain spectra. The focus is on the dynamically rich "doorway-mediated" ISC domain that lies between isolated spectroscopic spin-orbit perturbations and statistical-limit interactions between one singlet "bright state" and a quasi-continuum of triplet "dark states". New and improved experimental and data processing techniques permit the statistical-model curtain to be drawn back to reveal mechanistically explicit pathways via one or more identifiable, hence, manipulatable, doorway states, between a user-selected bright state and the undifferentiated bath of dark states.     

Conjugacy separability of 1-acylindrical graphs of free groups

We use the theory of group actions on profinite trees to prove that the fundamental group of a finite, 1-acylindrical graph of free groups with finitely generated edge groups is conjugacy separable. This has several applications: we prove that positive, C′(1/6) one-relator groups are conjugacy separable; we provide a conjugacy separable version of the Rips construction; we use this latter to provide an example of two finitely presented, residually finite groups that have isomorphic profinite completions, such that one is conjugacy separable and the other does not even have solvable conjugacy problem.     

Current and charge collector as e beam energy and dose meter for industrial use

Many parameters of interest for characterizing a high power processing electron beam in air can be measured using a charge density detector system.

A rugged detector head placed in or moved through an electron beam may be used to measure the effective beam energy, current density within the beam and charge delivered to the product plane.

The liquid cooled detector may also be used to calibrate routine dosimeter for electron beam use over the full range of doses and dose rates currently used for industrial purposes.

Further uses for the detector as an accelerator control sensor element are also discussed.     

Photophysical hole burning in the resonance Raman excitation profile of the chlorophyll a dimer in solution

The Raman excitation profiles of normal modes of chlorophyll a dimers in hexane exhibit sharp minima between 427 and 450 nm. In this spectral range, a non-linear relationship between the Raman intensifies and the intensity of the pulsed laser is observed. These non-linearities indicate population of lower-lying excited states of the chlorophyll a dimer. The Raman scaterring from these excited states is weaker than the rigorous resonance-enhanced Raman scattering from the ground states, which leads to the observed minima.     

The permanent electric dipole moments of WN and ReN and nuclear quadrupole interaction in ReN

The high-resolution laser induced fluorescence spectra of tungsten mononitride WN and rhenium mononitride ReN have been recorded in a laser ablation/molecular beam spectrometer. The field free spectrum of the (0,0)A (4)Pi(3/2)-X (4)Sigma(1/2) (-) band system of (186)WN has been analyzed to produce B("), B('), and gamma(") values of 0.4659(2), 0.4554(2), and 0.0518(1) cm(-1), respectively. The permanent electric dipole moments mu for the X (4)Sigma(1/2) (-) and A (4)Pi(3/2) state were determined to be 3.77(18) and 2.45(3) D, respectively, from the analysis of the optical Stark effect. The (0,0)[26.0]0(+)-X0(+) band system of ReN was recorded in the presence of a variable static electric field. The ground and excited state electric dipole moments of (187)ReN were determined to be mu(X0(+))=1.96(8) D and mu([26.0]0(+))=3.53(4) D. Splittings in the field free (187)ReN spectrum were analyzed to produce (187)Re (I=5/2) nuclear electric quadrupole coupling constants e(2)Qq(0) of -0.0304(8) and 0.0328(9) cm(-1) for the X0(+) and [26.0]0(+) states, respectively. A molecular orbital correlation model is used to interpret the observation and a comparison is made to CrN and MoN.