Phosphoramidite Gold(I)-Catalyzed Diastereo- and Enantioselective Synthesis of 3,4-Substituted Pyrrolidines

In this article the utility of phosphoramidite ligands in enantioselective AuI catalysis was explored in the development of highly diastereo- and enantioselective AuI-catalyzed cycloadditions of allenenes. A Au^I-catalyzed synthesis of 3,4-disubstituted pyrrolidines and γ-lactams is described. This reaction proceeds through the enantioselective AuI-catalyzed cyclization of allenenes to form a carbocationic intermediate that is trapped by an exogenous nucleophile, resulting in the highly diastereoselective construction of three contiguous stereogenic centers. A computational study (DFT) was also performed to gain some insight into the underlying mechanisms of these cycloadditions. The utility of this new methodology was demonstrated through the formal synthesis of (−)-isocynometrine

Mechanistic Study of Gold(I)-Catalyzed Intermolecular Hydroamination of Allenes

The intermolecular hydroamination of allenes occurs readily with hydrazide nucleophiles, in the presence of 3-12% Ph_3PAuNTf_2. Mechanistic studies have been conducted to establish the resting state of the gold catalyst, the kinetic order of the reaction, the effect of ligand electronics on the overall rate, and the reversibility of the last steps in the catalytic cycle. We have found the overall reaction to be first order in gold and allene and zero order in nucleophile. Our studies suggest that the rate-limiting transition state for the reaction does not involve the nucleophile and that the active catalyst is monomeric in gold(I). Computational studies support an “outersphere” mechanism and predict that a two-step, no intermediate mechanism may be operative. In accord with this mechanistic proposal, the reaction can be accelerated with the use of more electron-deficient phosphine ligands on the gold(I) catalyst

A Molecular-Rotor Device for Nonvolatile High-Density Memory Applications

A novel memory device based on an electrically driven molecular rotor was fabricated and demonstrated to have bistable switching effects. The device showed an on/off ratio of approximately 10^4, a read window of about 2.5 V, and retention performance of greater than 10^4 s. The analysis of the device I–V characteristics suggests the source of the observed switching effects to be the redox-induced ligand rotation around the copper metal center, which is consistent with the observed temperature dependence of the switching behavior. This organic monolayer device holds a potential for nonvolatile high-density memory applications due to its scalability and reduced cost

Room temperature negative differential resistance of a monolayer molecular rotor device

An electrically driven molecular rotor device comprised of a monolayer of redox-active ligated copper compounds sandwiched between a gold electrode and a highly doped P+Si substrate was fabricated. Current-voltage spectroscopy revealed a temperature-dependent negative differential resistance (NDR) associated with the device. Time-dependent density functional theory suggests the source of the observed NDR to be redox-induced ligand rotation around the copper metal center, an explanation consistent with the proposed energy diagram of the device. An observed temperature dependence of the NDR behavior further supports this hypothesis

K*(892)0 Production in Relativistic Heavy Ion Collisions at sqrt(s_NN) = 130 GeV

Preliminary results on the K*(892)0 -> pi + K production using the mixed-event technique are presented. The measurements are performed at mid-rapidity by the STAR detector in sqrt(s_NN) = 130 GeV Au-Au collisions at RHIC. The K*0 to negative hadron, kaon and phi ratios are obtained and compared to the measurements in e+e-, pp and pbarp at various energies.Comment: 8 pages, 3 figures, proceedings of Strange Quarks in Matter (SQM2001), Frankfurt am Main, Germany, to be published in J. Phys.

Folding of a donor–acceptor polyrotaxane by using noncovalent bonding interactions

Mechanically interlocked compounds, such as bistable catenanes and bistable rotaxanes, have been used to bring about actuation in nanoelectromechanical systems (NEMS) and molecular electronic devices (MEDs). The elaboration of the structural features of such rotaxanes into macromolecular materials might allow the utilization of molecular motion to impact their bulk properties. We report here the synthesis and characterization of polymers that contain π electron-donating 1,5-dioxynaphthalene (DNP) units encircled by cyclobis(paraquat-p-phenylene) (CBPQT4+), a π electron-accepting tetracationic cyclophane, synthesized by using the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC). The polyrotaxanes adopt a well defined “folded” secondary structure by virtue of the judicious design of two DNP-containing monomers with different binding affinities for CBPQT4+. This efficient approach to the preparation of polyrotaxanes, taken alongside the initial investigations of their chemical properties, sets the stage for the preparation of a previously undescribed class of macromolecular architectures

Signals of Disoriented Chiral Condensate

If a disoriented chiral condensate is created over an extended space-time region following a rapid cooling in hadronic or nuclear collisions, the misalignment of the condensate with the electroweak symmetry breaking can generate observable effects in the processes which involve both strong and electromagnetic interactions. We point out the relevance of the dilepton decay of light vector mesons as a signal for formation of the disoriented condensate. We predict that the decay \rho^0 to dileptons will be suppressed and/or the \rho resonance peak widens, while the decay \omega to dileptons will not be affected by the condensate.Comment: 13 pages in LaTeX, UCB-PTH-94/05, LBL-3533

Plantar fascia thickness is longitudinally associated with retinopathy and renal dysfunction: A prospective study from adolescence to adulthood

Aim: The aim was to study the longitudinal relationship between plantar fascia thickness (PFT) as a measure of tissue glycation and microvascular (MV) complications in young persons with type 1 diabetes (T1DM). Methods: We conducted a prospective longitudinal cohort study of 152 (69 male) adolescents with T1DM who underwent repeated MV complications assessments and ultrasound measurements of PFT from baseline (1997-2002) until 2008. Retinopathy was assessed by 7-field stereoscopic fundal photography and nephropathy by albumin excretion rate (AER) from three timed overnight urine specimens. Longitudinal analysis was performed using generalized estimating equations (GEE). Results: Median (interquartile range) age at baseline was 15.1 (13.4-16.8) years, and median follow-up was 8.3 (7.0-9.5) years, with 4 (3-6) visits per patient. Glycemic control improved from baseline to final visit [glycated hemoglobin (HbA1c) 8.5% to 8.0%, respectively; p = .004]. Prevalence of retinopathy increased from 20% to 51% (p \u3c .001) and early elevation of AER (\u3e7.5 μg/min) increased from 26% to 29% (p = .2). A greater increase in PFT (mm/year) was associated with retinopathy at the final assessment (ΔPFT 1st vs. 2nd-4th quartiles, χ2 = 9.87, p = .02). In multivariate GEE, greater PFT was longitudinally associated with retinopathy [odds ratio (OR) 4.6, 95% confidence interval (CI) 2.0-10.3] and early renal dysfunction (OR 3.2, CI 1.3-8.0) after adjusting for gender, blood pressure standard deviation scores, HbA1c, and total cholesterol. Conclusions: In young people with T1DM, PFT was longitudinally associated with retinopathy and early renal dysfunction, highlighting the importance of early glycemic control and supporting the role of metabolic memory in MV complications. Measurement of PFT by ultrasound offers a noninvasive estimate of glycemic burden and tissue glycation. © Diabetes Technology Society