Single-Carbon Insertion into Single C-C Bonds with Diazirines.

A novel platform for the skeletal editing of single C-C bonds via a single-carbon insertion has been developed using diazirines. This strategy involves the photogeneration of arylchlorocarbenes as carbynoid species that undergo site-selective carbene insertion into tertiary C-H bonds and a subsequent Wagner-Meerwein rearrangement promoted by a silver salt. Our skeletal editing strategy based on a formal selective carbyne C-C bond insertion has been demonstrated in six core-to-core conversions, including linear and cyclic benzylic substrates, alkanes and late-stage functionalizations.

Rh-Catalyzed Enantioselective Single-Carbon Insertion of Alkenes.

The interest in the discovery and development of skeletal editing processes that selectively insert, exchange, or delete an atom in organic molecules has significantly increased over the last few years. However, processes of this class that proceed through the creation of a chiral center with high asymmetric induction have been largely unexplored. Herein, we report an enantioselective single-carbon insertion in aryl- and alkyl-substituted alkenes mediated by a catalytically generated chiral Rh-carbynoid and phosphate nucleophiles that produce enantioenriched allylic phosphates (enantiomeric ratio (e.

Correction: Investing in entropy: the strategy of cucurbit[]urils to accelerate the intramolecular Diels-Alder cycloaddition reaction of tertiary furfuryl amines.

[This corrects the article DOI: 10.1039/D4SC01816H.].

Investing in entropy: the strategy of cucurbit[]urils to accelerate the intramolecular Diels-Alder cycloaddition reaction of tertiary furfuryl amines.

Cucurbit[]urils, renowned for their host-guest chemistry, are becoming versatile biomimetic receptors. Herein, we report that cucurbit[7]uril (CB[7]) accelerates the intramolecular Diels-Alder (IMDA) reaction for previously elusive and unreactive tertiary -methyl--(homo)allyl-2-furfurylamines by up to 4 orders of magnitude under mild conditions. Using H NMR titrations and ITC experiments, we characterize the dissimilar thermodynamic and kinetic properties of the complexes.

Urinalysis and culture results of free-catch urine samples in dogs: a randomised controlled trial.

Objectives: To evaluate the prevalence of bacterial presence in free-catch urine samples preceded by either a standardised prepped ("clean-catch") protocol versus unprepped (non-cleaned) voiding.

Materials And Methods: The study was a single-centre prospective single-blinded randomised controlled trial. Urine samples were obtained from 100 client-owned dogs presenting for routine evaluation.

Benefits of multinomial processing tree models with discrete and continuous variables in memory research: an alternative modeling proposal to Juola et al. (2019).

Signal detection theory (SDT) and two-high threshold models (2HT) are often used to analyze accuracy data in recognition memory paradigms. However, when reaction times (RTs) and/or confidence levels (CLs) are also measured, they usually are analyzed separately or not at all as dependent variables (DVs). We propose a new approach to include these variables based on multinomial processing tree models for discrete and continuous variables (MPT-DC) with the aim to compare fits of SDT and 2HT models.

Late-Stage Aryl C-H Bond Cyclopropenylation with Cyclopropenium Cations.

Herein, we disclose the first regio-, site- and chemoselective late-stage (hetero)aryl C-H bond cyclopropenylation with cyclopropenium cations (CPCs). The process is fast, operationally simple and shows an excellent functional group tolerance in densely-functionalized drug molecules, natural products, agrochemicals and fluorescent dyes. Moreover, we discovered that the installation of the cyclopropene ring in drug molecules could not only be used to shield against metabolic instability but also as a synthetic tool to reach medicinally-relevant sp -rich scaffolds exploiting the highly-strained nature of the cyclopropene ring with known transformations.

Generating Fischer-Type Rh-Carbenes with Rh-Carbynoids.

We describe the first catalytic generation of Fischer-type acyloxy Rh(II)-carbenes from carboxylic acids and Rh(II)-carbynoids. This novel class of transient donor/acceptor Rh(II)-carbenes evolved through a cyclopropanation process providing access to densely functionalized cyclopropyl-fused lactones with excellent diastereoselectivity. DFT calculations allowed the analysis of the properties of Rh(II)-carbynoids and acyloxy Rh(II)-carbenes as well as the characterization of the mechanism.

Heterogeneity estimation in meta-analysis of standardized mean differences when the distribution of random effects departs from normal: A Monte Carlo simulation study.

Background: Advantages of meta-analysis depend on the assumptions underlying the statistical procedures used being met. One of the main assumptions that is usually taken for granted is the normality underlying the population of true effects in a random-effects model, even though the available evidence suggests that this assumption is often not met. This paper examines how 21 frequentist and 24 Bayesian methods, including several novel procedures, for computing a point estimate of the heterogeneity parameter ([Formula: see text]) perform when the distribution of random effects departs from normality compared to normal scenarios in meta-analysis of standardized mean differences.

Catalytic Synthesis of Cyclopropenium Cations with Rh-Carbynoids.

Herein, we report the first catalytic one-step synthesis of cyclopropenium cations (CPCs) with readily available alkynes and hypervalent iodine reagents as carbyne sources. Key to the process is the catalytic generation of a novel Rh-carbynoid that formally transfers monovalent cationic carbynes (:C-R) to alkynes via an oxidative [2+1] cycloaddition. Our process is able to synthesize a new type of CPC substituted with an ester group that underpins the regioselective attack of a broad range of carbon and heteroatomic nucleophiles, thus providing a new platform for the synthesis of valuable cyclopropenes difficult or not possible to make by current methodologies.

A Generalizable Evaluated Approach, Applying Advanced Geospatial Statistical Methods, to Identify High Lead Exposure Locations at Census Tract Scale: Michigan Case Study.

Background: Despite great progress in reducing environmental lead (Pb) levels, many children in the United States are still being exposed.

Objective: Our aim was to develop a generalizable approach for systematically identifying, verifying, and analyzing locations with high prevalence of children's elevated blood Pb levels (EBLLs) and to assess available Pb models/indices as surrogates, using a Michigan case study.

Methods: We obtained BLL test results of children of age in Michigan from 2006-2016; we then evaluated them for data representativeness by comparing two percentage EBLL (%EBLL) rates (number of children tested with EBLL divided by both number of children tested and total population).

Catalytic alkene skeletal modification for the construction of fluorinated tertiary stereocenters.

Herein we describe the first construction of fluorinated tertiary stereocenters based on an alkene C(sp)-C(sp) bond cleavage. The new process, that takes advantage of a Rh-catalyzed carbyne transfer, relies on a branched-selective fluorination of tertiary allyl cations and is distinguished by a wide scope including natural products and drug molecule derivatives as well as adaptability to radiofluorination.

Methods for estimating the sampling variance of the standardized mean difference.

One of the most widely used effect size indices for meta-analysis in psychology is the (SMD). The most common way to synthesize a set of estimates of the SMD is to weight them by the inverse of their variances. For this, it is necessary to estimate the corresponding sampling variances.

Apixaban and Dalteparin for the Treatment of Venous Thromboembolism in Patients with Different Sites of Cancer.

Efficacy and safety of anticoagulant treatment for venous thromboembolism (VTE) may vary in patients with different cancer sites. We evaluated the rates of VTE recurrence and major bleeding and the relative efficacy and safety of 6-month treatment with oral apixaban or subcutaneous dalteparin in patients with different cancer sites randomized in the Caravaggio study. Primary cancer was located at gastrointestinal sites in 375 patients (32.

Does "Open" Rhyme with "Special"? Comparing Personality, Sexual Satisfaction, Dominance and Jealousy of Monogamous and Non-monogamous Practitioners.

Romantic relationships are changing in Western culture. The recent rise of alternative relationship models called consensual non-monogamies (CNMs) has drawn attention toward them. Western cultures largely stereotype and stigmatize CNMs, portraying their practitioners (among other aspects) as psychologically distinct from monogamous practitioners.

β-Diazocarbonyl Compounds: Synthesis and their Rh(II)-Catalyzed 1,3 C-H Insertions.

Herein, we describe the first electrophilic diazomethylation of ketone silyl enol ethers with diazomethyl-substituted hypervalent iodine reagents that gives access to unusual β-diazocarbonyl compounds. The potential of this unexplored class of diazo compounds for the development of new reactions was demonstrated by the discovery of a rare Rh-catalyzed intramolecular 1,3 C-H carbene insertion that led to complex cyclopropanes with excellent stereocontrol.

Spectral Color Management in Virtual Reality Scenes.

Virtual reality has reached a great maturity in recent years. However, the quality of its visual appearance still leaves room for improvement. One of the most difficult features to represent in real-time 3D rendered virtual scenes is color fidelity, since there are many factors influencing the faithful reproduction of color.

A transition-metal-free & diazo-free styrene cyclopropanation.

An operationally simple and broadly applicable novel cyclopropanation of styrenes using -diiodomethyl carbonyl reagents has been developed. Visible-light triggered the photoinduced generation of iodomethyl carbonyl radicals, able to cyclopropanate a wide array of styrenes with excellent chemoselectivity and functional group tolerance. To highlight the utility of our photocyclopropanation, we demonstrated the late-stage functionalization of biomolecule derivatives.

Catalytic Cleavage of C()-C() Bonds with Rh-Carbynoids.

We report a catalytic strategy that generates rhodium-carbynoids by selective diazo activation of designed carbyne sources. We found that rhodium-carbynoid species provoke C()-C() bond scission in alkenes by inserting a monovalent carbon unit between both -hybridized carbons. This skeletal remodeling process accesses synthetically useful allyl cation intermediates that conduct to valuable allylic building blocks upon nucleophile attack.

Familiarity, recollection, and receiver-operating characteristic (ROC) curves in recognition memory.

The Atkinson-Shiffrin theory describes and explains some of the processes involved in storing and retrieving information in human memory. Here we examine predictions of related models for search and decision processes in recognizing information in long-term memory. In some models, recognition is presumably based on a test item's familiarity judgment, and subsequent decisions follow from the sensitivity and decision parameters of signal detection theory.

Recovering the variance of d' from hit and false alarm statistics.

Sometimes the reports of primary studies that are potentially analyzable within the signal detection theory framework do not report sample statistics for its main indexes, especially the sample variance of d'. We describe a procedure for estimating the variance of d' from other sample statistics (specifically, the mean and variance of the observed rates of hit and false alarm). The procedure acknowledges that individuals can be heterogeneous in their sensitivity and/or decision criteria, and it does not adopt unjustifiable or needlessly complex assumptions.

Group analyses can hide heterogeneity effects when searching for a general model: Evidence based on a conflict monitoring task.

In experimental psychology, a unique model of general processing is often sought to represent the behaviors of all individuals. We address the question of whether seeking this objective - a unique model - is the most fruitful scientific strategy by studying a specific case example. In order to approach an answer to such a question, we compared the conventional approach in experimental psychology with analyses at the individual level by applying a specific mathematical modeling approach.

A protein functionalization platform based on selective reactions at methionine residues.

Nature has a remarkable ability to carry out site-selective post-translational modification of proteins, therefore enabling a marked increase in their functional diversity. Inspired by this, chemical tools have been developed for the synthetic manipulation of protein structure and function, and have become essential to the continued advancement of chemical biology, molecular biology and medicine. However, the number of chemical transformations that are suitable for effective protein functionalization is limited, because the stringent demands inherent to biological systems preclude the applicability of many potential processes.