A Push-Button Molecular Switch

The preparation, characterization, and switching mechanism of a unique single-station mechanically switchable hetero[2]catenane are reported. The facile synthesis utilizing a “threading-followed-by-clipping” protocol features Cu^(2+)-catalyzed Eglinton coupling as a mild and efficient route to the tetrathiafulvalene-based catenane in high yield. The resulting mechanically interlocked molecule operates as a perfect molecular switch, most readily described as a “push-button” switch, whereby two discrete and fully occupied translational states are toggled electrochemically at incredibly high rates. This mechanical switching was probed using a wide variety of experimental techniques as well as quantum-mechanical investigations. The fundamental distinctions between this single-station [2]catenane and other more traditional bi- and multistation molecular switches are significant

A solid-state switch containing an electrochemically switchable bistable poly[n]rotaxane

Electrochemically switchable bistable main-chain poly[n]rotaxanes have been synthesised using a threading-followed-by-stoppering approach and were incorporated into solid-state, molecular switch tunnel junction devices. In contrast to single-station poly[n]rotaxanes of similar structure, the bistable polymers do not fold into compact conformations held together by donor–acceptor interactions between alternating stacked p-electron rich and p-electron deficient aromatic systems. Films of the poly[n]rotaxane were incorporated into the devices by spin-coating, and their thickness was easily controlled. The switching functionality was characterised both (1) in solution by cyclic voltammetry and (2) in devices containing either two metal electrodes or one metal and one silicon electrode. Devices with one silicon electrode displayed hysteretic responses with applied voltage, allowing the devices to be switched between two conductance states, whereas devices containing two metal electrodes did not exhibit switching behaviour. The electrochemically switchable bistable poly[n]rotaxanes offer significant advantages in synthetic efficiency and ease of device fabrication as compared to bistable small-molecule [2]rotaxanes

CYP83B1 Is the Oxime-metabolizing Enzyme in the Glucosinolate Pathway in \u3ci\u3eArabidopsis\u3c/i\u3e

CYP83B1 from Arabidopsis thaliana has been identified as the oxime-metabolizing enzyme in the biosynthetic pathway of glucosinolates. Biosynthetically active microsomes isolated from Sinapis alba converted p-hydroxyphenylacetaldoxime and cysteine into S-alkylated p-hydroxyphenylacetothiohydroximate, S-(p-hydroxyphenylacetohydroximoyl)-L-cysteine, the next proposed intermediate in the glucosinolate pathway. The production was shown to be dependent on a cytochrome P450 monooxygenase. We searched the genome of A. thaliana for homologues of CYP71E1 (P450ox), the only known oxime-metabolizing enzyme in the biosynthetic pathway of the evolutionarily related cyanogenic glucosides. By a combined use of bioinformatics, published expression data, and knock-out phenotypes, we identified the cytochrome P450 CYP83B1 as the oxime-metabolizing enzyme in the glucosinolate pathway as evidenced by characterization of the recombinant protein expressed in Escherichia coli. The data are consistent with the hypothesis that the oxime-metabolizing enzyme in the cyanogenic pathway (P450ox) was mutated into a “P450mox” that converted oximes into toxic compounds that the plant detoxified into glucosinolates

Observations and Implications of the Star Formation History of the LMC

We present derivations of star formation histories based on color-magnitude diagrams of three fields in the LMC from HST/WFPC2 observations. A significant component of stars older than 4 Gyr is required to match the observed color-magnitude diagrams. Models with a dispersion-free age-metallicity relation are unable to reproduce the width of the observed main sequence; models with a range of metallicity at a given age provide a much better fit. Such models allow us to construct complete ``population boxes'' for the LMC based entirely on color-magnitude diagrams; remarkably, these qualitatively reproduce the age-metallicity relation observed in LMC clusters. We discuss some of the uncertainties in deriving star formation histories. We find, independently of the models, that the LMC bar field has a larger relative component of older stars than the outer fields. The main implications suggested by this study are: 1) the star formation history of field stars appears to differ from the age distribution of clusters, 2) there is no obvious evidence for bursty star formation, but our ability to measure bursts shorter in duration than $\sim$ 25% of any given age is limited by the statistics of the observed number of stars, 3) there may be some correlation of the star formation rate with the last close passage of the LMC/SMC/Milky Way, but there is no dramatic effect, and 4) the derived star formation history is probably consistent with observed abundances, based on recent chemical evolution models.Comment: Accepted by AJ, 36 pages including 12 figure

Radically enhanced molecular recognition

The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host–guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication

Definition of a Structured Training Curriculum for Robot-assisted Radical Cystectomy with Intracorporeal Ileal Conduit in Male Patients: A Delphi Consensus Study Led by the ERUS Educational Board

Robot-assisted radical cystectomy (RARC) continues to expand, and several surgeons start training for this complex procedure. This calls for the development of a structured training program, with the aim to improve patient safety during RARC learning curve. A modified Delphi consensus process was started to develop the curriculum structure. An online survey based on the available evidence was delivered to a panel of 28 experts in the field of RARC, selected according to surgical and research experience, and expertise in running training courses. Consensus was defined as ≥80% agreement between the responders. Overall, 96.4% experts completed the survey. The structure of the RARC curriculum was defined as follows: (1) theoretical training; (2) preclinical simulation-based training: 5-d simulation-based activity, using models with increasing complexity (ie, virtual reality, and dry- and wet-laboratory exercises), and nontechnical skills training session; (3) clinical training: modular console activity of at least 6 mo at the host center (a RARC case was divided into 11 steps and steps of similar complexity were grouped into five modules); and (4) final evaluation: blind review of a video-recorded RARC case. This structured training pathway will guide a starting surgeon from the first steps of RARC toward independent completion of a full procedure. Clinical implementation is urgently needed

LSST Science Book, Version 2.0

A survey that can cover the sky in optical bands over wide fields to faint magnitudes with a fast cadence will enable many of the exciting science opportunities of the next decade. The Large Synoptic Survey Telescope (LSST) will have an effective aperture of 6.7 meters and an imaging camera with field of view of 9.6 deg^2, and will be devoted to a ten-year imaging survey over 20,000 deg^2 south of +15 deg. Each pointing will be imaged 2000 times with fifteen second exposures in six broad bands from 0.35 to 1.1 microns, to a total point-source depth of r~27.5. The LSST Science Book describes the basic parameters of the LSST hardware, software, and observing plans. The book discusses educational and outreach opportunities, then goes on to describe a broad range of science that LSST will revolutionize: mapping the inner and outer Solar System, stellar populations in the Milky Way and nearby galaxies, the structure of the Milky Way disk and halo and other objects in the Local Volume, transient and variable objects both at low and high redshift, and the properties of normal and active galaxies at low and high redshift. It then turns to far-field cosmological topics, exploring properties of supernovae to z~1, strong and weak lensing, the large-scale distribution of galaxies and baryon oscillations, and how these different probes may be combined to constrain cosmological models and the physics of dark energy.Comment: 596 pages. Also available at full resolution at http://www.lsst.org/lsst/sciboo

Unified Structural Representation of the southern California crust and upper mantle

We present a new, 3D description of crust and upper mantle velocity structure in southern California implemented as a Unified Structural Representation (USR). The USR is comprised of detailed basin velocity descriptions that are based on tens of thousands of direct velocity (Vp, Vs) measurements and incorporates the locations and displacement of major fault zones that influence basin structure. These basin descriptions were used to developed tomographic models of crust and upper mantle velocity and density structure, which were subsequently iterated and improved using 3D waveform adjoint tomography. A geotechnical layer (GTL) based on Vs30 measurements and consistent with the underlying velocity descriptions was also developed as an optional model component. The resulting model provides a detailed description of the structure of the southern California crust and upper mantle that reflects the complex tectonic history of the region. The crust thickens eastward as Moho depth varies from 10 to 40 km reflecting the transition from oceanic to continental crust. Deep sedimentary basins and underlying areas of thin crust reflect Neogene extensional tectonics overprinted by transpressional deformation and rapid sediment deposition since the late Pliocene. To illustrate the impact of this complex structure on strong ground motion forecasting, we simulate rupture of a proposed M 7.9 earthquake source in the Western Transverse Ranges. The results show distinct basin amplification and focusing of energy that reflects crustal structure described by the USR that is not captured by simpler velocity descriptions. We anticipate that the USR will be useful for a broad range of simulation and modeling efforts, including strong ground motion forecasting, dynamic rupture simulations, and fault system modeling. The USR is available through the Southern California Earthquake Center (SCEC) website (http://www.scec.org)