Configurational control of low-symmetry heteroleptic metal-organic cages with asymmetric ligands.

Low-symmetry metal-organic cages (MOCs) can better mimic the structure of biological enzymes compared to high-symmetry MOCs, due to their unique internal cavities that resemble the specialized and irregular active sites of enzymes. In this study, two low-symmetry heteroleptic MOCs with six Pd(ii) centers, PdL L and PdL L , were successfully constructed by combining two strategies: asymmetric ligand assembly and multi-ligand co-assembly. Crystallographic characterization and analysis revealed that PdL L is a mixture of potentially 16 isomers.

NIR-II Emissive Persistent Neutral π-Radical with Rapid Doublet Internal Conversion for Efficient Cancer Photothermal Theranostics.

Organic radicals are considered prospective materials for near-infrared (NIR) photothermal applications, however, sustainability remains the major obstacle of recently reported ionic radical photothermal agents. This work achieved robust sustainability on a series of neutral π-radicals through rational design donor (D)-acceptor (A). With efficient doublet internal conversion, 10H-spiro(acridine-9,9'-fluorene) (SFA)-BTM presented strong NIR absorption extended to 1000 nm and efficient non-radiative relaxation.

Pathway Engineering in Pd-Based Supramolecular Cage Synthesis via Inner-Outer Steric Synergy.

For artificial supramolecular architectures designed to mimic biological systems, achieving different pathway synthesis is challenging due to the requirement of multiple stable and interconvertible intermediates. Here, we propose a novel "inner-outer steric synergy" strategy and investigate controllable pathway engineering for the synthesis of specific structures. Firstly, three structures (Ring-PdL , Bowl-PdL and Cage-PdL ) with interconversion properties were selectively formed by assembling externally modified ligand L with Pd(II).

Characterization of subcutaneous and visceral de-differentiated fat cells.

Objective: The capacity of mature adipocytes to de-differentiate into fibroblast-like cells has been demonstrated in vitro and a few, rather specific in vivo conditions. A detailed comparison between de-differentiated fat (DFAT) cells and adipose stem and progenitor cells (ASPCs) from different adipose depots is yet to be conducted. Moreover, whether de-differentiation of mature adipocytes from classical subcutaneous and visceral depots occurs under physiological conditions remains unknown.

Ultra-High Metal-Ion Selectivity Induced by Intramolecular Cation-π Interactions for the One-Pot Synthesis of Precise Heterometallic Architectures.

Heterometallic supramolecules, known for their unique synergistic effects, have shown broad applications in photochemistry, host-guest chemistry, and catalysis. However, there are great challenges to precisely construct heterometallic supramolecules rather than a statistical mixture, due to the limited metal-ion selectivity of coordination units. In particular, heterometallic architectures precisely encoded with different metal ions usually fail to form in a one-pot method when only one type of coordinated motif exists due to its poor metal-ion selectivity.

Highly Efficient Near-Infrared Luminescent Radicals with Emission Peaks over 750 nm.

Purely organic molecules exhibiting near-infrared (NIR) emission possess considerable potential for applications in both biological and optoelectronic technological domains, owing to their inherent advantages such as cost-effectiveness, biocompatibility, and facile chemical modifiability. However, the repertoire of such molecules with emission peaks exceeding 750 nm and concurrently demonstrating high photoluminescence quantum efficiency (PLQE) remains relatively scarce due to the energy gap law. Herein, we report two open-shell NIR radical emitters, denoted as DMNA-Cz-BTM and DMNA-PyID-BTM, achieved through the strategic integration of a donor group (DMNA) onto the Cz-BTM and PyID-BTM frameworks, respectively.

Sphingomyelin is involved in regulating UCP1-mediated nonshivering thermogenesis.

Adipogenesis is one of the major mechanisms for adipose tissue expansion, during which spindle-shaped mesenchymal stem cells commit to the fate of adipocyte precursors and differentiate into round-shaped fat-laden adipocytes. Here, we investigated the lipidomic profile dynamics of ex vivo-differentiated brown and white adipocytes derived from the stromal vascular fractions of interscapular brown (iBAT) and inguinal white adipose tissues. We showed that sphingomyelin was specifically enriched in terminally differentiated brown adipocytes, but not white adipocytes.

Perirenal adipose tissue contains a subpopulation of cold-inducible adipocytes derived from brown-to-white conversion.

Perirenal adipose tissue (PRAT) is a unique visceral depot that contains a mixture of brown and white adipocytes. The origin and plasticity of such cellular heterogeneity remains unknown. Here, we combine single-nucleus RNA sequencing with genetic lineage tracing to reveal the existence of a distinct subpopulation of & adipocytes that arises from brown-to-white conversion during postnatal life in the periureter region of mouse PRAT.

Graph-Aware Language Model Pre-Training on a Large Graph Corpus Can Help Multiple Graph Applications.

Model pre-training on large text corpora has been demonstrated effective for various downstream applications in the NLP domain. In the graph mining domain, a similar analogy can be drawn for pre-training graph models on large graphs in the hope of benefiting downstream graph applications, which has also been explored by several recent studies. However, no existing study has ever investigated the pre-training of text plus graph models on large heterogeneous graphs with abundant textual information (a.

Human ACVR1C missense variants that correlate with altered body fat distribution produce metabolic alterations of graded severity in knock-in mutant mice.

Background & Aims: Genome-wide studies have identified three missense variants in the human gene ACVR1C, encoding the TGF-β superfamily receptor ALK7, that correlate with altered waist-to-hip ratio adjusted for body mass index (WHR/BMI), a measure of body fat distribution.

Methods: To move from correlation to causation and understand the effects of these variants on fat accumulation and adipose tissue function, we introduced each of the variants in the mouse Acvr1c locus and investigated metabolic phenotypes in comparison with a null mutation.

Results: Mice carrying the I195T variant showed resistance to high fat diet (HFD)-induced obesity, increased catecholamine-induced adipose tissue lipolysis and impaired ALK7 signaling, phenocopying the null mutants.

Ultrastable, Superrobust, and Recyclable Supramolecular Polymer Networks.

Supramolecular polymer networks (SPNs), crosslinked by noncovalent bonds, have emerged as reorganizable and recyclable polymeric materials with unique functionality. However, poor stability is an imperative challenge faced by SPNs, because SPNs are susceptible to heat, water, and/or solvents due to the dynamic and reversible nature of noncovalent bonds. Herein, the design of a noncovalent cooperative network (NCoN) to simultaneously stabilize and reinforce SPNs is reported, resulting in an ultrastable, superrobust, and recyclable SPN.

Coordination-Induced Conformational Control Enables Highly Luminescent Metallo-Cages.

In recent years, luminescent materials have received a great deal of attention due to their wide range of applications. However, exploring a simple solution to overcome the fluorescence quenching resulting from the aggregation of conventional organic fluorophores remains a valuable area of investigation. In this study, we successfully constructed two metallo-cages, namely, and , through coordination-driven self-assemblies of the triphenylamine (TPA)-based donor with different diplatinum(II) acceptors and , respectively.

A Highly Luminescent Metallo-Supramolecular Radical Cage.

Luminescent metal-radicals have recently received increasing attention due to their unique properties and promising applications in materials science. However, the luminescence of metal-radicals tends to be quenched after formation of metallo-complexes. It is challenging to construct metal-radicals with highly luminescent properties.

Unraveling the Marked Differences of the Excited-State Properties of Arylgold(III) Complexes with CNC Tridentate Ligands.

Three structurally similar gold(III) complexes with CNC tridentate ligands, [; CNC = 2,6-diphenylpyridine], [; CNC = 2,6-diphenylpyrazine], and [; CNC = 2,6-diphenyltriazine], have been investigated theoretically to rationalize the marked difference in emission behaviors. The geometrical and electronic structures, spectra properties, radiative and nonradiative decay processes, as well as reverse intersystem crossing and reverse internal conversion (RIC) processes were thoroughly analyzed using density functional theory (DFT) and time-dependent DFT calculations. The computed results indicate that there is a small energy difference between the lowest-energy triplet state (T) and the second lowest-energy triplet state (T) of complexes and , suggesting that the excitons in the T state can reach the emissive higher-energy T through the RIC process.

Rational designs of structurally similar TADF and HLCT emitters with benzo- or naphtho-carbazole units as electron donors.

Thermally activated delayed fluorescence (TADF) and hybridized local and charge transfer (HLCT) emitters are two types of highly efficient electroluminescent materials which could improve their internal quantum efficiency (IQE) by converting triplet excitons to singlet ones. However, the molecular designs of TADF and HLCT materials are usually carried out separately because of their distinct emission mechanisms. In this work, we report a rational design strategy for the realization of switching between HLCT and TADF emissions in structurally similar donor-acceptor (D-A) type molecules, which are constructed with the same electron donors (benzo- or naphtho-carbazole) and acceptors with tunable electron-withdrawing abilities (benzonitrile (BN) and benzene-1,2,3,4,5-pentacarbonitrile (BPN)).

Multi-Decker Emissive Supramolecular Architectures Based on Shape-Complementary Ligands Pair.

Dye aggregates have attracted a great deal of attention due to their widespread applications in organic light-emitting devices, light-harvesting systems, etc. However, the strategies to precisely control chromophores with specific spatial arrangements still remain a great challenge. In this work, a series of double- and triple-decker supramolecular complexes are successfully constructed by coordination-driven self-assembly of carefully designed shape-complementary ligands, one claw-like tetraphenylethylene (TPE)-based host ligand and three tetratopic or ditopic guest ligands.

Programmable photoresponsive materials based on a single molecule distinct topochemical reactions.

Engineering the preorganization of photoactive units remains a big challenge in solid-state photochemistry research. It is of not only theoretical importance in the construction of topochemical reactions but also technological significance in the fabrication of advanced materials. Here, a cyanostilbene derivative, ()-2-(3,5-bis(trifluoromethyl)phenyl)-3-(naphthalen-2-yl) acrylonitrile (BNA), was crystallized into two polymorphs under different conditions.

Quantifiable stretching-induced fluorescence shifts of an elastically bendable and plastically twistable organic crystal.

Organic crystals with mechanical stimulus-response properties are being developed increasingly nowadays. However, the studies involving tensile-responsive crystals are still lacking due to the strict requirement of crystals with good flexibility. In this work, an organic crystal with the ability of elastic bending and plastic twisting upon loading stress and shearing force, respectively, is reported.

Conformational Control of a Metallo-Supramolecular Cage via the Dissymmetrical Modulation of Ligands.

In nature as well as life systems, the presence of asymmetrical and dissymmetrical structures with specific functions is extremely common. However, the construction of metallo-supramolecular assemblies based on dissymmetrical ligands still remains a considerable challenge for avoiding the generation of unexpected isomers with similar thermodynamic stabilities, especially for three-dimensional supramolecular structures. In this study, a strategy for the conformational control of metallo-supramolecular cages via the enhancement of ligand dissymmetry was proposed.

Comprehensive understanding of Tn5 insertion preference improves transcription regulatory element identification.

Tn5 transposase, which can efficiently tagment the genome, has been widely adopted as a molecular tool in next-generation sequencing, from short-read sequencing to more complex methods such as assay for transposase-accessible chromatin using sequencing (ATAC-seq). Here, we systematically map Tn5 insertion characteristics across several model organisms, finding critical parameters that affect its insertion. On naked genomic DNA, we found that Tn5 insertion is not uniformly distributed or random.

Prognostic Prediction of Cytogenetically Normal Acute Myeloid Leukemia Based on a Gene Expression Model.

Acute myeloid leukemia (AML) refers to a heterogeneous group of hematopoietic malignancies. The well-known European Leukemia Network (ELN) stratifies AML patients into three risk groups, based primarily on the detection of cytogenetic abnormalities. However, the prognosis of cytogenetically normal AML (CN-AML), which is the largest AML subset, can be hard to define.

Self-Assembly of Metallo-Supramolecules with Dissymmetrical Ligands and Characterization by Scanning Tunneling Microscopy.

Asymmetrical and dissymmetrical structures are widespread and play a critical role in nature and life systems. In the field of metallo-supramolecular assemblies, it is still in its infancy for constructing artificial architectures using dissymmetrical building blocks. Herein, we report the self-assembly of supramolecular systems based on two dissymmetrical double-layered ligands.

Crystal Engineering of a Hydrazone Molecule toward High Elasticity and Bright Luminescence.

Flexible luminescent crystals have attracted increasing attention on account of the potential application value in optical material fields. How to design crystals with high elasticity and bright luminescence is an urgent duty that material researchers want to effectuate. Crystal engineering could achieve different crystal materials with various functions based on one molecular structure.

Targeting of apoptosis gene loci by reprogramming factors leads to selective eradication of leukemia cells.

Applying somatic cell reprogramming strategies in cancer cell biology is a powerful approach to analyze mechanisms of malignancy and develop new therapeutics. Here, we test whether leukemia cells can be reprogrammed in vivo using the canonical reprogramming transcription factors-Oct4, Sox2, Klf4, and c-Myc (termed as OSKM). Unexpectedly, we discover that OSKM can eradicate leukemia cells and dramatically improve survival of leukemia-bearing mice.

Helical supramolecular polymer nanotubes with wide lumen for glucose transport: towards the development of functional membrane-spanning channels.

The manipulation of strong noncovalent interactions provides a concise and versatile strategy for constructing highly ordered supramolecular structures. By using a shape-persistent building block consisting of phenanthroline derivatives and two quadruply hydrogen-bonding AADD moieties, a type of precise helical supramolecular polymer (HSP) nanotube has been developed. The helical conformation of the supramolecular polymers has been proved various techniques, showing significantly expanded topologies of supramolecular polymers.