Diagenesis of the Clay-Sulfate Stratigraphic Transition, Mount Sharp Group, Gale Crater, Mars.

The diversity and abundance of diagenetic textures observed in sedimentary rocks of the clay-sulfate transition recorded in the stratigraphic record of Gale crater are distinctive within the rover's traverse. This study catalogs all textures observed by the MAHLI instrument, including their abundances, morphologies, and cross-cutting relationships in order to suggest a paragenetic sequence in which multiple episodes of diagenetic fluid flow were required to form co-occurring color variations, pits, and nodules; secondary nodule populations; and two generations of Ca sulfate fracture-filling vein precipitation. Spatial heterogeneities in the abundance and diversity of these textures throughout the studied stratigraphic section loosely correlate with stratigraphic unit, suggesting that grain size and compaction controls on fluid pathways influenced their formation; these patterns are especially prevalent in the Pontours member, where primary stratigraphy is entirely overprinted by a nodular fabric, and the base of the stratigraphic section, where increased textural diversity may be influenced by the underlying less permeable clay-bearing rocks of the Glen Torridon region.

Environmental Changes Recorded in Sedimentary Rocks in the Clay-Sulfate Transition Region in Gale Crater, Mars: Results From the Sample Analysis at Mars-Evolved Gas Analysis Instrument Onboard the Mars Science Laboratory Rover.

The rover explored the region between the orbitally defined phyllosilicate-bearing Glen Torridon trough and the overlying layered sulfate-bearing unit, called the "clay-sulfate transition region." Samples were drilled from the top of the fluviolacustrine Glasgow member of the Carolyn Shoemaker formation (CSf) to the eolian Contigo member of the Mirador formation (MIf) to assess in situ mineralogical changes with stratigraphic position. The Sample Analysis at Mars-Evolved Gas Analysis (SAM-EGA) instrument analyzed drilled samples within this region to constrain their volatile chemistry and mineralogy.

Simultaneous Infrared Observations of the Jovian Auroral Ionosphere and Thermosphere.

Simultaneous observations of and in Jupiter's northern infrared aurora were conducted on 02 June 2017 using Keck-NIRSPEC to produce polar projection maps of radiance, rotational temperature, column density, and radiance. The temperature variations within the auroral region are K, generally consistent with previous studies, albeit with some structural differences. Known auroral heating sources including particle precipitation, Joule heating, and ion drag have been examined by studying the correlations between each derived quantity, yet no single dominant mechanism can be identified as the main driver for the energetics in Jupiter's northern auroral region.

Magnetospheric Control of Ionospheric TEC Perturbations via Whistler-Mode and ULF Waves.

The weakly ionized plasma in the Earth's ionosphere is controlled by a complex interplay between solar and magnetospheric inputs from above, atmospheric processes from below, and plasma electrodynamics from within. This interaction results in ionosphere structuring and variability that pose major challenges for accurate ionosphere prediction for global navigation satellite system (GNSS) related applications and space weather research. The ionospheric structuring and variability are often probed using the total electron content (TEC) and its relative perturbations (dTEC).

NADH Analogues Enable Metal- and Light-Free Decarboxylative Functionalization.

Here we report a metal- and light-free decarboxylative functionalization approach enabled by reduced nicotinamide adenine dinucleotide (NADH) analogues. The efficient and operationally simple approach, conducted in 5 minutes from in situ preparation of aryliodine (III) dicarboxylates under open-air and ambient conditions, enables diverse bond formation and exhibits a broad substrate scope of over 70 examples. Late-stage functionalization of drug molecules and natural products further demonstrates the synthetic utility of this method.

Climate-Induced Saltwater Intrusion in 2100: Recharge-Driven Severity, Sea Level-Driven Prevalence.

Saltwater intrusion is a critical concern for coastal communities due to its impacts on fresh ecosystems and civil infrastructure. Declining recharge and rising sea level are the two dominant drivers of saltwater intrusion along the land-ocean continuum, but there are currently no global estimates of future saltwater intrusion that synthesize these two spatially variable processes. Here, for the first time, we provide a novel assessment of global saltwater intrusion risk by integrating future recharge and sea level rise while considering the unique geology and topography of coastal regions.

Biological effects of sodium phenylbutyrate and taurursodiol in Alzheimer's disease.

Introduction: Sodium phenylbutyrate and taurursodiol (PB and TURSO) is hypothesized to mitigate endoplasmic reticulum stress and mitochondrial dysfunction, two of many mechanisms implicated in Alzheimer's disease (AD) pathophysiology.

Methods: The first-in-indication phase 2a PEGASUS trial was designed to gain insight into PB and TURSO effects on mechanistic targets of engagement and disease biology in AD. The primary clinical efficacy outcome was a global statistical test combining three endpoints relevant to disease trajectory (cognition [Mild/Moderate Alzheimer's Disease Composite Score], function [Functional Activities Questionnaire], and total hippocampal volume on magnetic resonance imaging).

Divergent total syntheses of pyrroloiminoquinone alkaloids enabled by the development of a Larock/Buchwald-Hartwig annulation/cyclization.

Pyrroloiminoquinone alkaloids are a large class of natural products that display a wide range of biological activities. Synthetic approaches to these natural products typically rely on a common late-stage C10-oxygenated pyrroloiminoquinone intermediate, but these strategies often lead to lengthy synthetic sequences that are not amenable to divergent syntheses. We devised an alternative approach aimed at the early introduction of the C10 nitrogen, which we hypothesized would enable late-stage diversification.

Combining spaceborne lidar from the Global Ecosystem Dynamics Investigation with local knowledge for monitoring fragmented tropical landscapes: A case study in the forest-agriculture interface of Ucayali, Peru.

Improving our ability to monitor fragmented tropical ecosystems is a critical step in supporting the stewardship of these complex landscapes. We investigated the structural characteristics of vegetation classes in Ucayali, Peru, employing a co-production approach. The vegetation classes included three agricultural classes (mature oil palm, monocrop cacao, and agroforestry cacao plantations) and three forest regeneration classes (mature lowland forest, secondary lowland forest, and young lowland vegetation regrowth).

Interactions of peroxy radicals from monoterpene and isoprene oxidation simulated in the radical volatility basis set.

Isoprene affects new particle formation rates in environments and experiments also containing monoterpenes. For the most part, isoprene reduces particle formation rates, but the reason is debated. It is proposed that due to its fast reaction with OH, isoprene may compete with larger monoterpenes for oxidants.

Biocatalytic, Enantioenriched Primary Amination of Tertiary C-H Bonds.

Intermolecular functionalization of tertiary C-H bonds to construct fully substituted stereogenic carbon centers represents a formidable challenge: without the assistance of directing groups, state-of-the-art catalysts struggle to introduce chirality to racemic tertiary s -carbon centers. Direct asymmetric functionalization of such centers is a worthy reactivity and selectivity goal for modern biocatalysis. Here we present an engineered nitrene transferase (P411-TEA-5274), derived from a bacterial cytochrome P450, that is capable of aminating tertiary C-H bonds to provide chiral -tertiary primary amines with high efficiency (up to 2300 total turnovers) and selectivity (up to >99% enantiomeric excess (e.

A guide to troubleshooting metal sacrificial anodes for organic electrosynthesis.

The development of reductive electrosynthetic reactions is often enabled by the oxidation of a sacrificial metal anode, which charge-balances the reductive reaction of interest occurring at the cathode. The metal oxidation is frequently assumed to be straightforward and innocent relative to the chemistry of interest, but several processes can interfere with ideal sacrificial anode behavior, thereby limiting the success of reductive electrosynthetic reactions. These issues are compounded by a lack of reported observations and characterization of the anodes themselves, even when a failure at the anode is observed.

Validation of a Suprasystolic Cuff System for Static and Dynamic Representation of the Central Pressure Waveform.

Background: Noninvasive pulse waveform analysis is valuable for central cardiovascular assessment, yet controversies persist over its validity in peripheral measurements. Our objective was to compare waveform features from a cuff system with suprasystolic blood pressure hold with an invasive aortic measurement.

Methods And Results: This study analyzed data from 88 subjects undergoing concurrent aortic catheterization and brachial pulse waveform acquisition using a suprasystolic blood pressure cuff system.

Satellite Remote Sensing: A Tool to Support Harmful Algal Bloom Monitoring and Recreational Health Advisories in a California Reservoir.

Cyanobacterial harmful algal blooms (cyanoHABs) can harm people, animals, and affect consumptive and recreational use of inland waters. Monitoring cyanoHABs is often limited. However, chlorophyll- (chl-) is a common water quality metric and has been shown to have a relationship with cyanobacteria.

Determining the key vibrations for spin relaxation in ruffled Cu(ii) porphyrins resonance Raman spectroscopy.

Pinpointing vibrational mode contributions to electron spin relaxation () constitutes a key goal for developing molecular quantum bits (qubits) with long room-temperature coherence times. However, there remains no consensus to date as to the energy and symmetry of the relevant modes that drive relaxation. Here, we analyze a series of three geometrically-tunable = ½ Cu(ii) porphyrins with varying degrees of ruffling distortion in the ground state.

Incorporation of a self-immolative spacer enables mechanically triggered dual payload release.

Polymers that release functional small molecules in response to mechanical force are promising materials for a variety of applications including drug delivery, catalysis, and sensing. While many different mechanophores have been developed that enable the triggered release of a variety of small molecule payloads, most mechanophores are limited to one specific payload molecule. Here, we leverage the unique fragmentation of a 5-aryloxy-substituted 2-furylcarbinol derivative to design a novel mechanophore capable of the mechanically triggered release of two distinct cargo molecules.

Machine learning-directed electrical impedance tomography to predict metabolically vulnerable plaques.

The characterization of atherosclerotic plaques to predict their vulnerability to rupture remains a diagnostic challenge. Despite existing imaging modalities, none have proven their abilities to identify metabolically active oxidized low-density lipoprotein (oxLDL), a marker of plaque vulnerability. To this end, we developed a machine learning-directed electrochemical impedance spectroscopy (EIS) platform to analyze oxLDL-rich plaques, with immunohistology serving as the ground truth.

Enabling Al sacrificial anodes in tetrahydrofuran electrolytes for reductive electrosynthesis.

Al is widely used as a sacrificial anode in organic electrosynthesis. However, there remains a notable knowledge gap in the understanding of Al anode interface chemistry under electrolysis conditions. We hypothesize that Al interfacial chemistry plays a pivotal role in the discernible bias observed in solvent selections for reductive electrosynthesis.

A heterologous expression platform in for the elucidation of cryptic secondary metabolism biosynthetic gene clusters: discovery of the sartorypyrone biosynthetic pathway.

is a serious human pathogen causing life-threatening Aspergillosis in immunocompromised patients. Secondary metabolites (SMs) play an important role in pathogenesis, but the products of many SM biosynthetic gene clusters (BGCs) remain unknown. In this study, we have developed a heterologous expression platform in , using a newly created genetic dereplication strain, to express a previously unknown BGC from and determine its products.

Anomalous photochromism and mechanochromism of a linear naphthopyran enabled by a polarizing dialkylamine substituent.

In contrast to common angular naphthopyrans that exhibit strong photochromic and mechanochromic behavior, constitutionally isomeric linear naphthopyrans are typically not photochromic, due to the putative instability of the completely dearomatized merocyanine product. The photochemistry of linear naphthopyrans is thus relatively understudied compared to angular naphthopyrans, while the mechanochromism of linear naphthopyrans remains completely unexplored. Here we demonstrate that the incorporation of a polarizing dialkylamine substituent enables photochromic and mechanochromic behavior from polymers containing a novel linear naphthopyran motif.

Naphthopyran molecular switches and their emergent mechanochemical reactivity.

Naphthopyran molecular switches undergo a ring-opening reaction upon external stimulation to generate intensely colored merocyanine dyes. Their unique modularity and synthetic accessibility afford exceptional control over their properties and stimuli-responsive behavior. Commercial applications of naphthopyrans as photoswitches in photochromic ophthalmic lenses have spurred an extensive body of work exploring naphthopyran-merocyanine structure-property relationships.

Designing an Observing System to Study the Surface Biology and Geology (SBG) of the Earth in the 2020s.

Observations of planet Earth from space are a critical resource for science and society. Satellite measurements represent very large investments and United States (US) agencies organize their effort to maximize the return on that investment. The US National Research Council conducts a survey of Earth science and applications to prioritize observations for the coming decade.