SELF-ASSEMBLED HETEROLEPTIC CHIRAL LIGANDS, ASYMMETRIC CATALYST SYSTEMS AND METHODS

A method of synthesizing a heteroleptic, multiple metal containing metallocyclic catalyst, particularly Suited for asymmetric catalysis, comprising combining a plurality of plural functional group-containing, monodentate ligands of complementary chirality, said plural functional groups being tethered to each other by tethers in the presence of a scaffold structural metal Ms or derivative thereof, wherein at least one functional group on each ligand combines to ligate M to form a bidentate, Ms centered ligand scaffold containing the remaining functional groups and combining said bidentate ligand scaffold with a catalytic metal Mc or derivative thereof whereby the remaining functional groups combine to ligate Mc, thereby forming said catalyst

Facile access to functionalized chiral secondary benzylic boronic esters via catalytic asymmetric hydroboration

Allylic and homoallylic phosphonates bearing an aryl or heteroaryl substituent at the γ- or δ-position undergo rhodium-catalyzed asymmetric hydroboration by pinacolborane to give functionalized chiral secondary benzylic boronic esters in yields up to 86% and enantiomer ratios up to 99 : 1. Compared to minimally-functionalized terminal and 1,1-disubstituted vinyl arenes, there are relatively few reports of efficient catalytic asymmetric hydroboration (CAHB) of more highly functionalized internal alkenes. Phosphonate substrates bearing a variety of common heterocyclic ring systems, including furan, indole, pyrrole and thiophene derivatives, as well as those bearing basic nitrogen substituents (e.g., morpholine and pyrazine) are tolerated, although donor substituents positioned in close proximity of the alkene can influence the course of the reaction. Stereoisomeric (E)- and (Z)-substrates afford the same major enantiomer of the borated product. Deuterium-labelling studies reveal that rapid (Z)- to (E)-alkene isomerization accounts for the observed (E/Z)-stereoconvergence during CAHB. The synthetic utility of the chiral boronic ester products is illustrated by stereospecific C–B bond transformations including stereoretentive electrophile promoted 1,2-B-to-C migrations, stereoinvertive SE2 reactions of boron-ate complexes with electrophiles, and stereoretentive palladium- and rhodium-catalyzed cross-coupling protocols

Towards Precision LSST Weak-Lensing Measurement - I: Impacts of Atmospheric Turbulence and Optical Aberration

The weak-lensing science of the LSST project drives the need to carefully model and separate the instrumental artifacts from the intrinsic lensing signal. The dominant source of the systematics for all ground based telescopes is the spatial correlation of the PSF modulated by both atmospheric turbulence and optical aberrations. In this paper, we present a full FOV simulation of the LSST images by modeling both the atmosphere and the telescope optics with the most current data for the telescope specifications and the environment. To simulate the effects of atmospheric turbulence, we generated six-layer phase screens with the parameters estimated from the on-site measurements. For the optics, we combined the ray-tracing tool ZEMAX and our simulated focal plane data to introduce realistic aberrations and focal plane height fluctuations. Although this expected flatness deviation for LSST is small compared with that of other existing cameras, the fast f-ratio of the LSST optics makes this focal plane flatness variation and the resulting PSF discontinuities across the CCD boundaries significant challenges in our removal of the systematics. We resolve this complication by performing PCA CCD-by-CCD, and interpolating the basis functions using conventional polynomials. We demonstrate that this PSF correction scheme reduces the residual PSF ellipticity correlation below 10^-7 over the cosmologically interesting scale. From a null test using HST/UDF galaxy images without input shear, we verify that the amplitude of the galaxy ellipticity correlation function, after the PSF correction, is consistent with the shot noise set by the finite number of objects. Therefore, we conclude that the current optical design and specification for the accuracy in the focal plane assembly are sufficient to enable the control of the PSF systematics required for weak-lensing science with the LSST.Comment: Accepted to PASP. High-resolution version is available at http://dls.physics.ucdavis.edu/~mkjee/LSST_weak_lensing_simulation.pd

Electronic Structure Evidence for All-Trans Poly(methylvinylidene cyanide)

On the basis of a comparison of theoretical quantum calculations, by both semiempirical and ab initio methods, with photoemission and inverse photoemission results, we suggest that polymethylvinylidenecyanide (PMVC) adopts an all-trans conformation with few, if any, alternating trans-gauche carbon–carbon bond arrangements. The comparison of theory with the available photoemission and inverse photoemission excludes the presence of a significant fraction of gauche bonds in the polymer chains, indicative of the all-trans conformation, with dipoles all aligned

ƴ-Selective directed catalytic asymmetric hydroboration of 1,1-disubstituted alkenes

Directed catalytic asymmetric hydroborations of 1,1-disubstituted alkenes afford ƴ -dioxaborato amides and esters in high enantiomeric purity (90–95% ee)

A Next-generation Marker Genotyping Platform (AmpSeq) in Heterozygous Crops: A Case Study for Marker-assisted Selection in Grapevine

Marker-assisted selection (MAS) is often employed in crop breeding programs to accelerate and enhance cultivar development, via selection during the juvenile phase and parental selection prior to crossing. Next-generation sequencing and its derivative technologies have been used for genome-wide molecular marker discovery. To bridge the gap between marker development and MAS implementation, this study developed a novel practical strategy with a semi-automated pipeline that incorporates traitassociated single nucleotide polymorphism marker discovery, low-cost genotyping through amplicon sequencing (AmpSeq) and decision making. The results document the development of a MAS package derived from genotyping-by-sequencing using three traits (flower sex, disease resistance and acylated anthocyanins) in grapevine breeding. The vast majority of sequence reads ( ⩾99%) were from the targeted regions. Across 380 individuals and up to 31 amplicons sequenced in each lane of MiSeq data, most amplicons (83 to 87%) had o10% missing data, and read depth had a median of 220–244 × . Several strengths of the AmpSeq platform that make this approach of broad interest in diverse crop species include accuracy, flexibility, speed, high-throughput, lowcost and easily automated analysis

LSST: from Science Drivers to Reference Design and Anticipated Data Products

(Abridged) We describe here the most ambitious survey currently planned in the optical, the Large Synoptic Survey Telescope (LSST). A vast array of science will be enabled by a single wide-deep-fast sky survey, and LSST will have unique survey capability in the faint time domain. The LSST design is driven by four main science themes: probing dark energy and dark matter, taking an inventory of the Solar System, exploring the transient optical sky, and mapping the Milky Way. LSST will be a wide-field ground-based system sited at Cerro Pach\'{o}n in northern Chile. The telescope will have an 8.4 m (6.5 m effective) primary mirror, a 9.6 deg$^2$ field of view, and a 3.2 Gigapixel camera. The standard observing sequence will consist of pairs of 15-second exposures in a given field, with two such visits in each pointing in a given night. With these repeats, the LSST system is capable of imaging about 10,000 square degrees of sky in a single filter in three nights. The typical 5$\sigma$ point-source depth in a single visit in $r$ will be $\sim 24.5$ (AB). The project is in the construction phase and will begin regular survey operations by 2022. The survey area will be contained within 30,000 deg$^2$ with $\delta<+34.5^\circ$, and will be imaged multiple times in six bands, $ugrizy$, covering the wavelength range 320--1050 nm. About 90\% of the observing time will be devoted to a deep-wide-fast survey mode which will uniformly observe a 18,000 deg$^2$ region about 800 times (summed over all six bands) during the anticipated 10 years of operations, and yield a coadded map to $r\sim27.5$. The remaining 10\% of the observing time will be allocated to projects such as a Very Deep and Fast time domain survey. The goal is to make LSST data products, including a relational database of about 32 trillion observations of 40 billion objects, available to the public and scientists around the world.Comment: 57 pages, 32 color figures, version with high-resolution figures available from https://www.lsst.org/overvie