Cell type specific differences in transcriptome profiles of adipose derived stem cells and vaginal fibroblasts in patients with pelvic organ prolapse.

This study examined the molecular phenotypes of adipose-derived stem cells (ASCs) and vaginal fibroblasts (VFBs) and assessed whether pelvic organ prolapse (POP) affects their biological properties. We performed RNA sequencing of paired ASCs and VFBs from six patients with POP and six controls (CTRL). The transcriptomes of POP and CTRL in either ASCs or VFBs were compared (DESeq2, false discovery rate (FDR) < 0.

A trimetallic bismuth(I)-based allyl cation.

The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis and unique electronic structure fundamentals. In this work, we describe the synthesis and characterization of a highly reduced bismuth salt featuring a cationic core based on three contiguous Bi(I) centres. The triatomic bismuth-based core exhibits an electronic configuration that mimics the canonical description of the archetypical carbon-based π-allyl cation.

3D-Printed Polymeric Biomaterials for Health Applications.

3D printing, also known as additive manufacturing, holds immense potential for rapid prototyping and customized production of functional health-related devices. With advancements in polymer chemistry and biomedical engineering, polymeric biomaterials have become integral to 3D-printed biomedical applications. However, there still exists a bottleneck in the compatibility of polymeric biomaterials with different 3D printing methods, as well as intrinsic challenges such as limited printing resolution and rates.

Synthesis and Characterization of Monomeric Triarylbismuthine Oxide.

The synthesis and isolation of a bismuth-based analogue of the venerable triphenylphosphine oxide (PhPO) has remained a chimera to synthetic chemists for many years, due to its predicted high reactivity and instability. Through the hydrolysis of a cationic fluorotriarylbismuthonium(V) salt, we report here the isolation of unique hydroxytriarylbismuth(V) complexes, which served as precursor for the formation of the elusive monomeric triarylbismuthine oxide DippBi=O. Combined spectroscopic, crystallographic and computational studies provided insight into the bonding situation of the first monomeric triorganobismuth oxide complex.

Activation and C-C Coupling of Aryl Iodides via Bismuth Photocatalysis.

Within the emerging field of bismuth redox catalysis, the catalytic formation of C-C bonds using aryl halides would be highly desirable; yet such a process remains a synthetic challenge. Herein, we present a chemoselective bismuth-photocatalyzed activation and subsequent coupling of (hetero)aryl iodides with pyrrole derivatives to access C(sp)-C(sp) linkages through C-H functionalization. This unique reactivity is the result of the bismuth complex featuring two redox state-dependent interactions with light, which 1) activates the Bi(I) complex for oxidative addition via MLCT, and 2) promotes the homolytic cleavage of aryl Bi(III) intermediates through a LLCT process.

Synthesis and characterization of chlorotriarylbismuthonium salts.

This work reports the synthesis and structural study of a family of chlorotriarylbismuthonium salts. The abstraction of a chlorine atom with NaBAr from triarylbismuth dichloride species leads to monomeric and dimeric chlorotriarylbismuthonium species, which show a distinct behavior in solution and solid-state in comparison to their fluorotriarylbismuthonium analogues.

Activation and Catalytic Degradation of SF and PhSF at a Bismuth Center.

In this work, we report the catalytic degradation of SF and PhSF using ,, pincer bismuthinidene complexes ( and ). Exposure of SF and PhSF to results in the reduction of the S(VI) substrates and concomitant formation of Bi(III) and Bi(II) compounds, which were isolated and characterized. The oxidized bismuth-based products were demonstrated to undergo reduction with PMe, recovering the starting complex .

Reductive Cyclopropanation through Bismuth Photocatalysis.

We present here a catalytic method based on a low-valent Bi complex capable of cyclopropanation of double bonds under blue LED irradiation. The catalysis features various unusual Bi-based organometallic steps, namely, (1) two-electron inner sphere oxidative addition of Bi(I) complex to CHI, (2) light-induced homolysis of the Bi(III)-CHI bond, (3) subsequent iodine abstraction-ring-closing, and (4) reduction of Bi(III) to Bi(I) with an external reducing agent to close the cycle. Stoichiometric organometallic experiments support the proposed mechanism.

"Naked Nickel"-Catalyzed Amination of Heteroaryl Bromides.

In this Letter, we report that the air-stable "naked nickel" [Ni(stb)] is a competent catalyst in thermal C-N bond formation between (hetero)aryl bromides and -based nucleophiles. The catalytic system is characterized by a "naked nickel" complex and Zn and by the absence of external light sources, photocatalysts, exogenous ligands, and electrical setups. Upon application of this method, various heteroaryls bearing Lewis-basic heteroatoms can be accommodated and directly aminated with a set of primary and secondary amines.

Bismuth in Radical Chemistry and Catalysis.

Whereas indications of radical reactivity in bismuth compounds can be traced back to the 19 century, the preparation and characterization of both transient and persistent bismuth-radical species has only been established in recent decades. These advancements led to the emergence of the field of bismuth radical chemistry, mirroring the progress seen for other main-group elements. The seminal and fundamental studies in this area have ultimately paved the way for the development of catalytic methodologies involving bismuth-radical intermediates, a promising approach that remains largely untapped in the broad landscape of synthetic organic chemistry.

Bi-Catalyzed Trifluoromethylation of C(sp)-H Bonds under Light.

We disclose a Bi-catalyzed C-H trifluoromethylation of (hetero)arenes using CFSOCl under light irradiation. The catalytic method permits the direct functionalization of various heterocycles bearing distinct functional groups. The structural and computational studies suggest that the process occurs through an open-shell redox manifold at bismuth, comprising three unusual elementary steps for a main group element.

Mechanistic Studies on the Bismuth-Catalyzed Transfer Hydrogenation of Azoarenes.

Organobismuth-catalyzed transfer hydrogenation has recently been disclosed as an example of low-valent Bi redox catalysis. However, its mechanistic details have remained speculative. Herein, we report experimental and computational studies that provide mechanistic insights into a Bi-catalyzed transfer hydrogenation of azoarenes using p-trifluoromethylphenol (4) and pinacolborane (5) as hydrogen sources.

Oxidative Addition of Aryl Electrophiles into a Red-Light-Active Bismuthinidene.

The oxidative addition of aryl electrophiles is a fundamental organometallic reaction widely applied in the field of transition metal chemistry and catalysis. However, the analogous version based on main group elements still remains largely underexplored. Here, we report the ability of a well-defined organobismuth(I) complex to undergo formal oxidative addition with a wide range of aryl electrophiles.

Bismuth-Catalyzed Amide Reduction.

In this article we report that a cationic version of Akiba's Bi complex catalyzes the reduction of amides to amines using silane as hydride donor. The catalytic system features low catalyst loadings and mild conditions, en route to secondary and tertiary aryl- and alkylamines. The system tolerates functional groups such as alkene, ester, nitrile, furan and thiophene.

Dihydrogen and Ethylene Activation by a Sterically Distorted Distibene.

Herein, we report the synthesis of a sterically distorted distibene ([4] ) and its transition-metal-like reactivity towards two fundamental feedstock chemicals: H and ethylene. Although [4] exhibits an unusually long Sb=Sb distance and noticeable backbone distortion in the solid state, NMR data suggest that [4] remains predominantly as a dimer in solution, even at high temperatures. However, it was proposed that the elusive reactivity of [4] toward H and ethylene results from reversible dissociation of [4] into the transient stibinidene ([4]), which could be observed by NMR spectroscopic techniques.

Bismuth radical catalysis in the activation and coupling of redox-active electrophiles.

Radical cross-coupling reactions represent a revolutionary tool to make C(sp)-C and C(sp)-heteroatom bonds by means of transition metals and photoredox or electrochemical approaches. However, the use of main-group elements to harness this type of reactivity has been little explored. Here we show how a low-valency bismuth complex is able to undergo one-electron oxidative addition with redox-active alkyl-radical precursors, mimicking the behaviour of first-row transition metals.

Synthesis and isolation of a triplet bismuthinidene with a quenched magnetic response.

Large spin-orbit coupling (SOC) is an intrinsic property of the heavy elements that directly affects the electronic structures of the compounds. In this work, we report the synthesis and characterization of a monocoordinate bismuthinidene that features a rigid and bulky ligand. All magnetic measurements [superconducting quantum interference device (SQUID), nuclear magnetic resonance (NMR)] point to a diamagnetic compound.

Nickel Meets Aryl Thianthrenium Salts: Ni(I)-Catalyzed Halogenation of Arenes.

Herein, a regioselective, late-stage two-step arene halogenation method is reported. We propose how unusual Ni(I)/(III) catalysis is enabled by a combination of aryl thianthrenium and Ni redox properties that is hitherto unachieved with other (pseudo)halides. The catalyst is accessed in situ from inexpensive NiCl·6(HO) and zinc without the need of supporting ligands.

Synthesis, Isolation, and Characterization of Two Cationic Organobismuth(II) Pincer Complexes Relevant in Radical Redox Chemistry.

Herein, we report the synthesis, isolation, and characterization of two cationic organobismuth(II) compounds bearing N,C,N pincer frameworks, which model crucial intermediates in bismuth radical processes. X-ray crystallography uncovered a monomeric Bi(II) structure, while SQUID magnetometry in combination with NMR and EPR spectroscopy provides evidence for a paramagnetic = 1/2 state. High-resolution multifrequency EPR at the X-, Q-, and W-band enable the precise assignment of the full - and Bi -tensors.

Bio-Inspired Deaminative Hydroxylation of Aminoheterocycles and Electron-Deficient Anilines.

Among the tools available to chemists for drug design of bioactive compounds, the bioisosteric replacement of atoms or groups of atoms is the cornerstone of modern strategies. Despite the undeniable interest in amino-to-hydroxyl interchange, enzymatic deaminative hydroxylation remains unmatched. Herein, we report a user friendly and safe procedure to selectively convert aminoheterocycles to their hydroxylated analogues by means of a simple pyrylium tetrafluoroborate salt.

Ni-Catalyzed Oxygen Transfer from NO onto sp-Hybridized Carbons.

Herein we disclose a catalytic synthesis of cycloalkanols that harnesses the potential of NO as an oxygen transfer agent onto sp-hybridized carbons. The protocol is distinguished by its mild conditions and wide substrate scope, thus offering an opportunity to access carbocyclic compounds from simple precursors even in an enantioselective manner. Preliminary mechanistic studies suggest that the oxygen insertion event occurs at an alkylnickel species and that NO is the O transfer reagent.

Synthesis and Structure of Mono-, Di-, and Trinuclear Fluorotriarylbismuthonium Cations.

A series of cationic fluorotriarylbismuthonium salts bearing differently substituted aryl groups (Ar = 9,9-Me-9H-xanthene, Ph, Mes, and 3,5-Bu-CH) have been synthesized and characterized. While the presence of simple phenyl substituents around the Bi center results in a polymeric structure with three Bi centers in the repeating monomer, substituents at the - and -positions lead to cationic mono- and dinuclear fluorobismuthonium complexes, respectively. Preparation of all compounds is accomplished by fluoride abstraction from the parent triaryl Bi(V) difluorides using NaBAr (BAr = B[CH-3,5-(CF)] ).