ChromEvol v.3: modeling rate heterogeneity in chromosome number evolution.

Changes in chromosome numbers are a prominent driver of plant evolution, impacting ecological diversification, stress tolerance, and phenotypes. ChromEvol is a widely used software tool for deciphering patterns of chromosome-number change along a phylogeny of interest. It evaluates the fit of alternative models to the data, estimates transition rates of different types of events, and infers the expected number of events along each branch of the phylogeny.

From propenolysis to enyne metathesis: tools for expedited assembly of 4,8-azaboranaphthalene and extended polycycles with embedded BN.

The synthesis of BN-containing molecules, which have an interesting isosteric relationship to their parent all-C cores, has drawn a great deal of attention as an avenue to alter and tune molecular function. Nevertheless, many cores with embedded BN are still hard to synthesize, and thus, further effort is required in this direction. Herein, we present an integrated approach to BN-containing polycycles rooted in an exceptionally clean B-N condensation of amines with a tri-allylborane.

Using ChromEvol to Determine the Mode of Chromosomal Evolution.

The ChromEvol software was the first to implement a likelihood-based approach, using probabilistic models that depict the pattern of chromosome number change along a specified phylogeny. The initial models have been completed and expanded during the last years. New parameters that model polyploid chromosome evolution have been implemented in ChromEvol v.

Cyclic Homo- and Heterohalogen Di-λ-diarylhalonium Structures.

In the context of the ever-growing interest in the cyclic diaryliodonium salts, this work presents synthetic design principles for a new family of structures with two hypervalent halogens in the ring. The smallest bis-phenylene derivative, [(CH)I], was prepared through oxidative dimerization of a precursor bearing the -disposed iodine and trifluoroborate groups. We also report, for the first time, the formation of cycles containing two different halogen atoms.

Multi-Knock-a multi-targeted genome-scale CRISPR toolbox to overcome functional redundancy in plants.

Plant genomes are characterized by large and complex gene families that often result in similar and partially overlapping functions. This genetic redundancy severely hampers current efforts to uncover novel phenotypes, delaying basic genetic research and breeding programmes. Here we describe the development and validation of Multi-Knock, a genome-scale clustered regularly interspaced short palindromic repeat toolbox that overcomes functional redundancy in Arabidopsis by simultaneously targeting multiple gene-family members, thus identifying genetically hidden components.

A non-homogeneous model of chromosome-number evolution to reveal shifts in the transition patterns across the phylogeny.

Changes in chromosome numbers, including polyploidy and dysploidy events, play a key role in eukaryote evolution as they could expediate reproductive isolation and have the potential to foster phenotypic diversification. Deciphering the pattern of chromosome-number change within a phylogeny currently relies on probabilistic evolutionary models. All currently available models assume time homogeneity, such that the transition rates are identical throughout the phylogeny.

"Captive by the Uncertainty"-Experiences with Anticipatory Guidance for People Living with Dementia and Their Caregivers at a Specialty Dementia Clinic.

Background: After a diagnosis of Alzheimer's disease and related disorders, people living with dementia (PWD) and caregivers wonder what disease trajectory to expect and how to plan for functional and cognitive decline. This qualitative study aimed to identify patient and caregiver experiences receiving anticipatory guidance about dementia from a specialty dementia clinic.

Objective: To examine PWD and caregiver perspectives on receiving anticipatory guidance from a specialty dementia clinic.

Bee flowers drive macroevolutionary diversification in long-horned bees.

The role of plant-pollinator interactions in the rapid radiation of the angiosperms have long fascinated evolutionary biologists. Studies have brought evidence for pollinator-driven diversification of various plant lineages, particularly plants with specialized flowers and concealed rewards. By contrast, little is known about how this crucial interaction has shaped macroevolutionary patterns of floral visitors.

Exploring benzylic -C(sp)-boron-silicon and boron-tin centers as a synthetic platform.

A stepwise build-up of multi-substituted C carbon centers is an attractive, conceptually simple, but often synthetically challenging type of disconnection. To this end, this report describes how -α,α-dimetalloid-substituted benzylic reagents bearing boron/silicon or boron/tin substituent sets are an excellent stepping stone towards diverse substitution patterns. These -dimetalloids were readily accessed, either by known carbenoid insertion into C-B bonds or by the newly developed scalable deprotonation/metallation approach.

Preparation and Synthetic Applicability of Imidazole-Containing Cyclic Iodonium Salts.

A novel approach to the preparation of imidazole-substituted cyclic iodonium salts has been developed via the oxidative cyclization of 1-phenyl-5-iodoimidazole using a cheap and available Oxone/HSO oxidative system. The structure of the new polycyclic heteroarenes has been confirmed by single-crystal X-ray diffractometry, revealing the characteristic structure features for cyclic iodonium salts. The newly produced imidazole-flanked cyclic iodonium compounds were found to readily engage in a heterocyclization reaction with elemental sulfur, affording benzo[5,1-]imidazothiazoles in good yields.

Iodane-Guided ortho C-H Allylation.

A metal-free C-H allylation strategy is described to access diverse functionalized ortho-allyl-iodoarenes. The method employs hypervalent (diacetoxy)iodoarenes and proceeds through the iodane-guided "iodonio-Claisen" allyl transfer. The use of allylsilanes bearing electron-withdrawing functional groups unlocks the functionalization of a broad range of substrates, including electron-neutral and electron-poor rings.

Heterogeneity in the rate of molecular sequence evolution substantially impacts the accuracy of detecting shifts in diversification rates.

As species richness varies along the tree of life, there is a great interest in identifying factors that affect the rates by which lineages speciate or go extinct. To this end, theoretical biologists have developed a suite of phylogenetic comparative methods that aim to identify where shifts in diversification rates had occurred along a phylogeny and whether they are associated with some traits. Using these methods, numerous studies have predicted that speciation and extinction rates vary across the tree of life.

Crystal-to-Crystal Synthesis of Photocatalytic Metal-Organic Frameworks for Visible-Light Reductive Coupling and Mechanistic Investigations.

Postmodification of reticular materials with well-defined catalysts is an appealing approach to produce new catalytic functional materials with improved stability and recyclability, but also to study catalysis in confined spaces. A promising strategy to this end is the postfunctionalization of crystalline and robust metal-organic frameworks (MOFs) to exploit the potential of crystal-to-crystal transformations for further characterization of the catalysts. In this regard, two new photocatalytic materials, MOF-520-PC1 and MOF-520-PC2, are straightforwardly obtained by the postfunctionalization of MOF-520 with perylene-3-carboxylic acid (PC1) and perylene-3-butyric acid (PC2).

Stepwise Mechanism for the Bromination of Arenes by a Hypervalent Iodine Reagent.

A mild, metal-free bromination method of arenes has been developed using the combination of bis(trifluoroacetoxy)iodobencene and trimethylsilyl bromide. In situ-formed dibromo(phenyl)-λ3-iodane (PhIBr) is proposed as the reactive intermediate. This methodology using PIFA/TMSBr has been applied with success to a great number of substrates (25 examples).

Cobalt Amide Imidate Imidazolate Frameworks as Highly Active Oxygen Evolution Model Materials.

Two imidazolate-based Co-MOFs, IFP-5 and IFP-8 (imidazolate framework Potsdam), with a different peripheral group -R (-Me and -OMe, respectively) have been synthesized by a solvothermal method and tested toward the oxygen evolution reaction (OER). Remarkably, IFP-8 presents much lower overpotentials (319 mV at 10 mA/cm and 490 mV at 500 mA/cm) than IFP-5 toward OER, as confirmed by online gas chromatography measurements (Faradaic yield of O > 99%). Moreover, the system is extraordinarily stable during 120 h, even when used as a catalyst toward the overall water splitting reaction without any sign of fatigue.

The Power of Iodane-Guided C-H Coupling: A Group-Transfer Strategy in Which a Halogen Works for Its Money.

Hypervalent organoiodane reagents are ubiquitous in organic synthesis, both as oxidants and as electrophilic group-transfer agents. In addition to these hallmark applications, a complementary strategy is gaining momentum that exploits the ability of λ -iodanes to undergo iodine-to-arene group transfer, for example, via iodonio-Claisen-type rearrangement processes. This Minireview discusses recent advances in the use of this method to access a variety of the C-H-functionalized iodoarenes.

Screening and Preliminary Biochemical and Biological Studies of [RuCl(-cymene)(,-bis(diphenylphosphino)-isopropylamine)][BF] in Breast Cancer Models.

Breast cancer is the second leading cause of cancer death worldwide. Despite progress in drug discovery, identification of the correct population is the limiting factor to develop new compounds in the clinical setting. Therefore, the aim of this study is to evaluate the effects of a new metallodrug, [RuCl(-cymene)(,-bis(diphenylphosphino)-isopropylamine)][BF] (), as a lead pnp-Ru compound by screening and preliminary biochemical and biological studies in different breast cancer subtypes.

Synthesis of Polysubstituted Iodoarenes Enabled by Iterative Iodine-Directed para and ortho C-H Functionalization.

Among halogenated aromatics, iodoarenes are unique in their ability to produce the bench-stable halogen(III) form. Earlier, such iodine(III) centers were shown to enable C-H functionalization ortho to iodine via halogen-centered rearrangement. The broader implications of this phenomenon are explored by testing the extent of an unusual iodane-directed para C-H benzylation, as well as by developing an efficient C-H coupling with sulfonyl-substituted allylic silanes.

Synthesis of Five-Membered Iodine-Nitrogen Heterocycles from Benzimidazole-Based Iodonium Salts.

Pseudocyclic 2-benzimidazolyl-substituted diaryliodonium salts were obtained by the reaction of the corresponding [hydroxy(tosyloxy)iodo]arenes with arenes in the presence of trifluoromethanesulfonic acid. X-ray structural analysis of these iodonium salts confirmed their pseudocyclic structure with a short (2.57-2.

The Coming of Age in Iodane-Guided ortho-C-H Propargylation: From Insight to Synthetic Potential.

As early as 1991 Ochiai et al. reported that an acid-activated form of phenyliodine diacetate, PhI(OAc) , undergoes a reaction with propargyl-silanes, germanes and stannanes to give the ortho-propargyl iodobenzene. This formal C-H alkylation was proposed to take place through an unusual (even to date) iodonio-based [3,3] rearrangement of an intermediate allenylsilane.

Aminophosphine ligands as a privileged platform for development of antitumoral ruthenium(ii) arene complexes.

The rapid and modular synthesis of the aminophosphine core has been exploited as a tool for rapid development of antitumoral metallodrug candidates. Starting with a series of structurally diverse aminophosphines, all obtained in a single step from commercial amines, a family of Ru(ii)-cymene complexes have been generated and tested in vitro for anti-tumoral activity in a series of cell lines, including the platinum-resistant A2780R. Through this approach, Ru(ii)-aminophosphine complexes have been identified with the IC value range as low as 10-0.

Triarylmethane Dyes for Artificial Repellent Cotton Fibers.

Families of new hydrophobic and/or oleophobic triarylmethane dyes possessing long hydrocarbon or polyfluorinated chains have been prepared. When covalently grafted on to cotton fabric, these dyes give rise to a new type of colored superhydrophobic fibers.

Predictors of Patterns of Alcohol-Related Blackouts Over Time in Youth From the Collaborative Study of the Genetics of Alcoholism: The Roles of Genetics and Cannabis.

Objective: Alcohol-related blackouts (ARBs) are anterograde amnesias related to heavy alcohol intake seen in about 50% of drinkers. Although a major determinant of ARBs relates to blood alcohol concentrations, additional contributions come from genetic vulnerabilities and possible impacts of cannabis use disorders (CUDs). We evaluated relationships of genetics and cannabis use to latent class trajectories of ARBs in 829 subjects from the Collaborative Study of the Genetics of Alcoholism (COGA).