Non-Covalent Interactions Enforce Conformation in Switchable and Water-Soluble Diketopiperazine-Pyridine Foldamers

To reach their potential as mimics of the dynamic molecules present in biological systems, foldamers must be designed to display stimulus-responsive behavior. Here we report such a foldamer architecture based on alternating pyridine-diketopiperazine linkers. Epimerization is conveniently prevented through a copper-catalyzed coupling protocol. The compounds’ native unswitched conformation is first discovered in the solid and solution state. The foldamers can be solubilized in DMSO and pH 9.5 buffer, retaining conformational control to a large degree. Lastly, dynamic switching is demonstrated through treatment with acid, leading to behaviour we describe as stimulus-responsive sidechain reconfiguration.     

Electrophilic C12 building blocks for alkaloids: formal total synthesis of (+/-)-maritidine

Silyl-protected benzyl alcohol derivatives and the salt 1 are used to form ortho-substituted C12 electrophilic organoiron building blocks which are converted into a spirocyclic cyclohexenone to complete a formal total synthesis of (+/-)-maritidine (5). The choice of TBDPS protection was shown to be better than TIPS and compatible with ipso nucleophile addition to form a quaternary center. The reaction sequence is the first example of a successful application in the synthesis of an arylcyclohexadienyliron complex with an ortho-carbon substituent in the position required for Amaryllidaceae alkaloids of this type.     

Mappings between inverse limits of continua with multivalued bonding functions

We investigate the limit mappings between inverse limits of continua with upper semi-continuous bonding functions. Results are obtained when the coordinate mappings are surjective, one-to-one or homeomorphisms. We construct examples showing the hypothesis of the theorems are essential. Further, we construct an example showing that, unlike for the inverse limits with single valued maps, properties of being monotone, confluent or weakly confluent mappings between factor spaces are not preserved in the inverse limit map.     

Measurements of branching fraction, polarization, and charge asymmetry of B(+/-)-->rho(+/-)rho(0) and a search for B(+/-)-->rho(+/-)f(0)(980)

We measure the branching fraction (B), polarization (f(L)), and CP asymmetry (A(CP)) of B(+/-)-->rho(+/-)rho(0) decays and search for the decay B(+/-)-->rho(+/-)f(0)(980) based on a data sample of 231.8 x 10(6) Upsilon(4S)-->BB decays collected with the BABAR detector at the SLAC PEP-II asymmetric-energy B factory. In B(+/-)-->rho(+/-)rho(0) decays we measure B=(16.8+/-2.2+/-2.3) x 10(-), f(L)=0.905+/-0.042(-0.027)(+0.023), and A(CP)=-0.12+/-0.13+/-0.10, and find an upper limit on the branching fraction of B(+/-)-->rho(+/-)f(0)(980)(-->pi(+)pi(-)) decays of 1.9 x 10(-6) at 90% confidence level.     

Search for D0-D0 mixing and branching-ratio measurement in the decay D0-->K+ pi- pi0

We analyze 230.4 fb;{-1} of data collected with the BABAR detector at the PEP-II e;{+}e;{-} collider at SLAC to search for evidence of D0-D[over ];{0} mixing using regions of phase space in the decay D;{0}-->K;{+}pi;{-}pi;{0}. We measure the time-integrated mixing rate R_{M}=(0.023_{-0.014};{+0.018}(stat.)+/-0.004(syst.))%, and R_{M}<0.054% at the 95% confidence level, assuming CP invariance. The data are consistent with no mixing at the 4.5% confidence level. We also measure the branching ratio for D;{0}-->K;{+}pi;{-}pi;{0} relative to D;{0}-->K;{-}pi;{+}pi;{0} to be (0.214+/-0.008(stat.)+/-0.008(syst.))%.     

Observation of B+ --> K0K+ and B0 --> K0K0

We report observations of the b --> d penguin-dominated decays B+ --> K0K+ and B0 --> K0K0 in 316 fb(-1) of e+ e- collision data collected with the BABAR detector. We measure the branching fractions B(B+ --> K0K+) = (1.61+/-0.44+/-0.09) x 10(-6) and B(B0 --> K0K0 = (1.08+/-0.28+/-0.11) x 10(-6) and the CP-violating charge asymmetry A(CP)(K0K+) = 0.10+/-0.26+/-0.03. Using a vertexing technique previously employed in several analyses of all-neutral final states containing kaons, we report the first measurement of time-dependent CP-violating asymmetries in B0 --> K(S)0K(S)0, obtaining S = -1.28(-0.73-0.16)(+0.80+0.11) and C = -0.40+/-0.41+/-0.06. We also report improved measurements of the branching fraction B(B+ --> K0 pi+) = (23.9+/-1.1+/-1.0) x 10(-6) and CP-violating charge asymmetry A(CP)(K0 pi+) = -0.029+/-0.039+/-0.010.     

Functional magnetic resonance imaging of awake monkeys: some approaches for improving imaging quality

Functional magnetic resonance imaging (fMRI) at high magnetic field strength can suffer from serious degradation of image quality because of motion and physiological noise, as well as spatial distortions and signal losses due to susceptibility effects. Overcoming such limitations is essential for sensitive detection and reliable interpretation of fMRI data. These issues are particularly problematic in studies of awake animals. As part of our initial efforts to study functional brain activations in awake, behaving monkeys using fMRI at 4.7 T, we have developed acquisition and analysis procedures to improve image quality with encouraging results.We evaluated the influence of two main variables on image quality. First, we show how important the level of behavioral training is for obtaining good data stability and high temporal signal-to-noise ratios. In initial sessions, our typical scan session lasted 1.5 h, partitioned into short (<10 min) runs. During reward periods and breaks between runs, the monkey exhibited movements resulting in considerable image misregistrations. After a few months of extensive behavioral training, we were able to increase the length of individual runs and the total length of each session. The monkey learned to wait until the end of a block for fluid reward, resulting in longer periods of continuous acquisition. Each additional 60 training sessions extended the duration of each session by 60 min, culminating, after about 140 training sessions, in sessions that last about 4 h. As a result, the average translational movement decreased from over 500 μm to less than 80 μm, a displacement close to that observed in anesthetized monkeys scanned in a 7-T horizontal scanner.Another major source of distortion at high fields arises from susceptibility variations. To reduce such artifacts, we used segmented gradient-echo echo-planar imaging (EPI) sequences. Increasing the number of segments significantly decreased susceptibility artifacts and image distortion. Comparisons of images from functional runs using four segments with those using a single-shot EPI sequence revealed a roughly twofold improvement in functional signal-to-noise-ratio and 50% decrease in distortion. These methods enabled reliable detection of neural activation and permitted blood-oxygenation-level-dependent-based mapping of early visual areas in monkeys using a volume coil.In summary, both extensive behavioral training of monkeys and application of segmented gradient-echo EPI sequence improved signal-to-noise ratio and image quality. Understanding the effects these factors have is important for the application of high field imaging methods to the detection of submillimeter functional structures in the awake monkey brain.