Pyrrole synthesis catalyzed by AgOTf or cationic Au(I) complexes

Either silver trifluoromethanesulfonate or a mixture of gold(I) chloride, silver trifluoromethanesulfonate, and triphenylphosphine catalyze the formation of pyrroles from substituted beta-alkynyl ketones and amines. The reactions proceed by using 5 mol % of catalyst with yields of isolated pyrroles ranging from 13% to 92%. Sixteen examples are used to compare the effectiveness of each catalyst.     

Room‐Temperature Palladium‐Catalyzed C?H Activation: ortho‐Carbonylation of Aniline Derivatives

Pd and CO—ureally got me! The title reaction proceeds efficiently at 18 °C under CO (1 atm) with 5 % [Pd(OTs)₂(MeCN)₂] as precatalyst. Depending on the solvents used, either anthranilates or cyclic imides can be obtained in high yields (see picture, BQ=benzoquinone, Ts=4‐toluenesulfonyl).

     

A generalized power-law detection algorithm for humpback whale vocalizations

Conventional detection of humpback vocalizations is often based on frequency summation of band-limited spectrograms under the assumption that energy (square of the Fourier amplitude) is the appropriate metric. Power-law detectors allow for a higher power of the Fourier amplitude, appropriate when the signal occupies a limited but unknown subset of these frequencies. Shipping noise is non-stationary and colored and problematic for many marine mammal detection algorithms. Modifications to the standard power-law form are introduced to minimize the effects of this noise. These same modifications also allow for a fixed detection threshold, applicable to broadly varying ocean acoustic environments. The detection algorithm is general enough to detect all types of humpback vocalizations. Tests presented in this paper show this algorithm matches human detection performance with an acceptably small probability of false alarms (P(FA) < 6%) for even the noisiest environments. The detector outperforms energy detection techniques, providing a probability of detection P(D) = 95% for P(FA) < 5% for three acoustic deployments, compared to P(FA) > 40% for two energy-based techniques. The generalized power-law detector also can be used for basic parameter estimation and can be adapted for other types of transient sounds.     

Mid-infrared virtually imaged phased array spectrometer for rapid and broadband trace gas detection

We present and characterize a two-dimensional (2D) imaging spectrometer based on a virtually imaged phased array (VIPA) disperser for rapid, high-resolution molecular detection using mid-infrared (MIR) frequency combs at 3.1 and 3.8?μm. We demonstrate detection of CH₄ at 3.1?μm with >3750 resolution elements spanning >80 nm with ～600 MHz resolution in a <10 μs acquisition time. In addition to broadband detection, we also demonstrate rapid, time-resolved single-image detection by capturing dynamic concentration changes of CH₄ at a rate of ～375 frames per second. Changes in absorption above the noise floor of 5×10^-4 are readily detected on the millisecond time scale, leading to important future applications such as real-time monitoring of trace gas concentrations and detection of reactive intermediates.     

Subjective Information and Survival in a Simulated Biological System

Information transmission and storage have gained traction as unifying concepts to characterize biological systems and their chances of survival and evolution at multiple scales. Despite the potential for an information-based mathematical framework to offer new insights into life processes and ways to interact with and control them, the main legacy is that of Shannon’s, where a purely syntactic characterization of information scores systems on the basis of their maximum information efficiency. The latter metrics seem not entirely suitable for biological systems, where transmission and storage of different pieces of information (carrying different semantics) can result in different chances of survival. Based on an abstract mathematical model able to capture the parameters and behaviors of a population of single-celled organisms whose survival is correlated to information retrieval from the environment, this paper explores the aforementioned disconnect between classical information theory and biology. In this paper, we present a model, specified as a computational state machine, which is then utilized in a simulation framework constructed specifically to reveal emergence of a “subjective information”, i.e., trade-off between a living system’s capability to maximize the acquisition of information from the environment, and the maximization of its growth and survival over time. Simulations clearly show that a strategy that maximizes information efficiency results in a lower growth rate with respect to the strategy that gains less information but contains a higher meaning for survival.     

In Vivo Evaluation of (−)-Zampanolide Demonstrates Potent and Persistent Antitumor Efficacy When Targeted to the Tumor Site

Microtubule-stabilizing agents (MSAs) are a class of compounds used in the treatment of triple-negative breast cancer (TNBC), a subtype of breast cancer where chemotherapy remains the standard-of-care for patients. Taxanes like paclitaxel and docetaxel have demonstrated efficacy against TNBC in the clinic, however new classes of MSAs need to be identified due to the rise of taxane resistance in patients. (−)-Zampanolide is a covalent microtubule stabilizer that can circumvent taxane resistance in vitro but has not been evaluated for in vivo antitumor efficacy. Here, we determine that (−)-zampanolide has similar potency and efficacy to paclitaxel in TNBC cell lines, but is significantly more persistent due to its covalent binding. We also provide the first reported in vivo antitumor evaluation of (−)-zampanolide where we determine that it has potent and persistent antitumor efficacy when delivered intratumorally. Future work on zampanolide to further evaluate its pharmacophore and determine ways to improve its systemic therapeutic window would make this compound a potential candidate for clinical development through its ability to circumvent taxane-resistance mechanisms.     

Directly Bound Deuterons Increase X-Nuclei Hyperpolarization using Dynamic Nuclear Polarization

Deuterated ¹³C sites in sugars (D-glucose and 2-deoxy-D-glucose) showed 6.3-to-17.5-fold higher solid-state dynamic nuclear polarization (DNP) levels than their respective protonated sites at 3.35T. This effect was found to be unrelated to the protonation of the bath. Deuterated ¹⁵N in sites bound to exchangeable protons ([¹⁵N₂]urea) showed a 1.3-fold higher polarization than their respective protonated sites at the same magnetic field. This relatively smaller effect was attributed to incomplete deuteration of the ¹⁵N sites due to the solvent mixture. For a ¹⁵N site that is not bound to protons or deuterons ([¹⁵N]nitrate), deuteration of the bath did not affect the polarization level. These findings suggest a phenomenon related to DNP of X-nuclei directly bound to deuteron(s) as opposed to proton(s). It appears that direct binding to deuterons increases the solid-state DNP polarization level of X-nuclei which are otherwise bound to protons.     

The Effect of Surface Terminations on the Initial Stages of TiO2 Deposition on Functionalized Silicon

As atomic layer deposition (ALD) emerges as a method to fabricate architectures with atomic precision, emphasis is placed on understanding surface reactions and nucleation mechanisms. ALD of titanium dioxide with TiCl₄ and water has been used to investigate deposition processes in general, but the effect of surface termination on the initial TiO₂ nucleation lacks needed mechanistic insights. This work examines the adsorption of TiCl₄ on Cl−, H−, and HO− terminated Si(100) and Si(111) surfaces to elucidate the general role of different surface structures and defect types in manipulating surface reactivity of growth and non-growth substrates. The surface sites and their role in the initial stages of deposition are examined by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Density functional theory (DFT) computations of the local functionalized silicon surfaces suggest oxygen-containing defects are primary drivers of selectivity loss on these surfaces.