Using Classifiers To Predict Catalyst Design for Polyketone Microstructure.

We applied a classifier method to predict palladium catalysts for the formation of nonalternating polyketones via the copolymerization of CO and ethylene; current examples are limited to using phosphine sulfonate and diphosphazane monoxide supporting ligands. With the reported workflow, we discovered two new classes of palladium complexes capable of achieving the synthesis of nonalternating polyketones with a lower CO content than those made by known palladium catalysts. Our results show that we doubled the number of classes of palladium compounds that can catalyze the formation of this type of polymer.

Transcriptome-wide outlier approach identifies individuals with minor spliceopathies.

RNA-sequencing has improved the diagnostic yield of individuals with rare diseases. Current analyses predominantly focus on identifying outliers in single genes that can be attributed to cis-acting variants within the gene locus. This approach overlooks causal variants with trans-acting effects on splicing transcriptome-wide, such as variants impacting spliceosome function.

Room-Temperature Formate Ester Transfer Hydrogenation Enables an Electrochemical/Thermal Organometallic Cascade for Methanol Synthesis from CO.

The reduction of CO to synthetic fuels is a valuable strategy for energy storage. However, the formation of energy-dense liquid fuels such as methanol remains rare, particularly under low-temperature and low-pressure conditions that can be coupled to renewable electricity sources via electrochemistry. Here, a multicatalyst system pairing an electrocatalyst with a thermal organometallic catalyst is introduced, which enables the reduction of CO to methanol at ambient temperature and pressure.

Strategies, Technologies, and Tips for Successful Cecal Intubation.

Successful cecal intubation is crucial in ensuring a complete evaluation of the colonic mucosa. Although completion of colonoscopies should be successful in close to 100% of all examinations in the hands of experienced gastroenterologists, there are some patients with colons which can be difficult to navigate. Factors such as older age, presence of diverticular disease, as well as high or low body mass index can present challenges for endoscopists.

The COMPASS scale for the assessment of individuals with first episode psychotic disorders.

Background: Psychosis symptom assessment instruments are rarely used in US mental health community clinical practice despite the advantages of measurement-based care. Barriers include the length of typical scales and that data for scale evaluation often come from researcher and not clinician raters.

Study Design: The 12-item COMPASS symptom assessment was designed for the RAISE-ETP study of early phase psychosis.

Gastric Tube Volvulus Occurring Years After Esophagectomy and Its Successful Treatment Via Endoscopic Stenting.

Esophageal cancer is frequently treated with esophagectomy, which is associated with distinct complications. Delayed gastric conduit emptying is a well-recognized complication that usually occurs within the postoperative period. By contrast, gastric tube volvulus is a rarer complication with a more variable time course of onset after esophagectomy and can be mistaken for delayed gastric conduit emptying.

Kinetic Isotope Effects and the Mechanism of CO Insertion into the Metal-Hydride Bond of -(bpy)Re(CO)H.

The 1,2-insertion reaction of CO into metal-hydride bonds of d-octahedral complexes to give κ--metal-formate products is the key step in various CO reduction schemes and as a result has attracted extensive mechanistic investigations. For many octahedral catalysts, CO insertion follows an associative mechanism in which CO interacts directly with the coordinated hydride ligand instead of the more classical dissociative mechanism that opens an empty coordination site to bind the substrate to the metal prior to a hydride migration step. To better understand the associative mechanism, we conducted a systematic quantum chemical investigation on the reaction between CO and -(bpy)Re(CO)H (-Re-H; bpy = 2,2'-bipyridine) starting with the gas phase and then moving to THF and other solvents with increased dielectric constants.

Sex-Dependent Effects on Influenza-Specific Antibody Quantity and Neutralizing Activity following Vaccination of Newborn Non-Human Primates Is Determined by Adjuvants.

A number of studies have demonstrated the role of sex in regulating immune responses to vaccination. However, these findings have been limited to adults for both human and animal models. As a result, our understanding of the impact of sex on vaccine responses in the newborn is highly limited.

Updates on coding in dermatology.

Correct coding is an important component of effective dermatology practice management. Over the past several years there have been updates to many commonly used codes within dermatology. This review highlights many of these updates, such as: the skin biopsy codes have been subdivided to reflect the different biopsy techniques.

Regulating Access to Active Sites via Hydrogen Bonding and Cation-Dipole Interactions: A Dual Cofactor Approach to Switchable Catalysis.

Hydrogen bonding networks are ubiquitous in biological systems and play a key role in controlling the conformational dynamics and allosteric interactions of enzymes. Yet in small organometallic catalysts, hydrogen bonding rarely controls ligand binding to the metal center. In this work, a hydrogen bonding network within a well-defined organometallic catalyst works in concert with cation-dipole interactions to gate substrate access to the active site.

Catalyst self-assembly accelerates bimetallic light-driven electrocatalytic H evolution in water.

Hydrogen evolution is an important fuel-generating reaction that has been subject to mechanistic debate about the roles of monometallic and bimetallic pathways. The molecular iridium catalysts in this study undergo photoelectrochemical dihydrogen (H) evolution via a bimolecular mechanism, providing an opportunity to understand the factors that promote bimetallic H-H coupling. Covalently tethered diiridium catalysts evolve H from neutral water faster than monometallic catalysts, even at lower overpotential.

On the genetic basis of tail-loss evolution in humans and apes.

The loss of the tail is among the most notable anatomical changes to have occurred along the evolutionary lineage leading to humans and to the 'anthropomorphous apes', with a proposed role in contributing to human bipedalism. Yet, the genetic mechanism that facilitated tail-loss evolution in hominoids remains unknown. Here we present evidence that an individual insertion of an Alu element in the genome of the hominoid ancestor may have contributed to tail-loss evolution.

Nickel-catalyzed ester carbonylation promoted by imidazole-derived carbenes and salts.

Millions of tons of acetyl derivatives such as acetic acid and acetic anhydride are produced each year. These building blocks of chemical industry are elaborated into esters, amides, and eventually polymer materials, pharmaceuticals, and other consumer products. Most acetyls are produced industrially using homogeneous precious metal catalysts, principally rhodium and iridium complexes.

Synthesis and bonding analysis of pentagonal bipyramidal rhenium carboxamide oxo complexes.

Seven-coordinate rhenium oxo complexes supported by a tetradentate bipyridine carboxamide/carboxamidate ligand are reported. The neutral dicarboxamide Hbpy-da ligand initially coordinates in an L (ONNO) fashion to an octahedral rhenium oxo precursor, yielding a seven-coordinate rhenium oxo complex. Subsequent deprotonation generates a new oxo complex featuring the dianionic (LX) carboxamidate (NNNN) form of the ligand.

Ultrafast X-Ray Scattering Reveals Composite Amplitude Collective Mode in the Weyl Charge Density Wave Material (TaSe_{4})_{2}I.

We report ultrafast x-ray scattering experiments of the quasi-1D charge density wave (CDW) material (TaSe_{4})_{2}I following ultrafast infrared photoexcitation. From the time-dependent diffraction signal at the CDW sidebands we identify a 0.11 THz amplitude mode derived primarily from a transverse acoustic mode of the high-symmetry structure.

Making ends meet - relating a self-reported indicator of financial hardship to health status.

Background: Area-based index of multiple deprivation (IMD) indicators of financial hardship lack individual specificity and sensitivity. This study compared self-reports of hardship with area measures in relation to health status.

Methods: Interviews in one London Borough, reported financial hardship and health status.

Closure of a distal splenorenal shunt as a therapy for refractory hyperammonaemia in setting of neuropsychiatric symptoms.

Before the widespread use of the transjugular intrahepatic portosystemic shunt, portal hypertension was addressed by the creation of an operative distal splenorenal shunt (DSRS). DSRS was largely regarded as a safe and effective therapy, though it did have a risk of precipitating hyperammonaemia and hepatic encephalopathy.A woman suffered a gunshot wound to the abdomen.

Recruitment of grid-like responses in human entorhinal and piriform cortices by odor landmark-based navigation.

Olfactory navigation is universal across the animal kingdom. Humans, however, have rarely been considered in this context. Here, we combined olfactometry techniques, virtual reality (VR) software, and neuroimaging methods to investigate whether humans can navigate an olfactory landscape by learning the spatial relationships among discrete odor cues and integrating this knowledge into a spatial map.

Non-randomized evaluation of hospitalization after a prescription for nirmatrelvir/ritonavir versus molnupiravir in high-risk COVID-19 outpatients.

Objectives: To assess and compare subsequent hospital admissions within 30 days for patients after receiving a prescription for either oral nirmatrelvir/ritonavir or oral molnupiravir.

Methods: We conducted a retrospective review of 3207 high-risk, non-hospitalized adult COVID-19 patients who received a prescription for molnupiravir (n = 209) or nirmatrelvir/ritonavir (n = 2998) at an academic medical centre in New York City from April to December 2022. Variables including age, vaccination status, high-risk conditions and demographic factors were pulled from the electronic medical record.