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. In line with this, freshly isolated adipocytes of iBAT showed higher sphingomyelin content than those of inguinal white adipose tissue. Upon cold exposure, sphingomyelin abundance in iBAT gradually decreased in parallel with reduced sphingomyelin synthase 1 protein levels. Cold-exposed animals treated with an inhibitor of sphingomyelin hydrolases failed to maintain core body temperature and showed reduced oxygen consumption and iBAT UCP1 levels. Conversely, blockade of sphingomyelin synthetic enzymes resulted in enhanced nonshivering thermogenesis, reflected by elevated body temperature and UCP1 levels. Taken together, our results uncovered a relation between sphingomyelin abundance and fine-tuning of UCP1-mediated nonshivering thermogenesis.

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. The NCoN is constructed by multiplying the H-bonding sites and tuning the conformation/geometry of the H-bonding segment to optimize the multivalence cooperativity of H-bonds. The rationally designed H-bonding segment with high conformational compliance favors the formation of tightly packed H-bond arrays comprising higher-density and stronger H-bonds. Consequently, the H-bonded crosslinks in the NCoN display a covalent crosslinking effect but retain on-demand dynamics and reversibility. The resultant ultrastable SPN not only displays remarkable resistance to heat up to 120 °C, water soaking, and a broad spectrum of solvents, but also possesses a superhigh true stress at break (1.1 GPa) and an ultrahigh toughness (406 MJ m-3 ). Despite the covalent-network-like stability, the SPN is recyclable through activating its reversibility in a high-polarity solvent heated to a threshold temperature.

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. Herein, we report a highly luminescent metallo-supramolecular radical cage (LMRC) constructed by the assembly of a tritopic terpyridinyl ligand RL with tris(2,4,6-trichlorophenyl)methyl (TTM) radical and Zn2+. Electrospray ionization-mass spectrometry (ESI-MS), traveling-wave ion mobility-mass spectrometry (TWIM-MS), X-ray crystallography, electron paramagnetic resonance (EPR) spectroscopy, and superconducting quantum interference device (SQUID) confirm the formation of a prism-like supramolecular radical cage. LMRC exhibits a remarkable photoluminescence quantum yield (PLQY) of 65%, which is 5 times that of RL; meanwhile, LMRC also shows high photostability. Notably, significant magnetoluminescence can be observed for the high-concentration LMRC (15 wt % doped in PMMA film); however, the magnetoluminescence of 0.1 wt % doped LMRC film vanishes, revealing negligible spin-spin interactions between two radical centers in LMRC.

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

Three structurally similar gold(III) complexes with C∧N∧C tridentate ligands, [1; C∧N∧C = 2,6-diphenylpyridine], [2; C∧N∧C = 2,6-diphenylpyrazine], and [3; C∧N∧C = 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 ΔET1-T1' between the lowest-energy triplet state (T1) and the second lowest-energy triplet state (T1') of complexes 2 and 3, suggesting that the excitons in the T1 state can reach the emissive higher-energy T1' through the RIC process. In addition, the non-emissive T1 states of gold(III) complexes in solution can be ascribed to the easily accessible metal-centered (3MC) state or possibly tunneling into high-energy vibrationally excited singlet states for nonradiative decay. The low efficiency of 3 is attributed to the deactivation pathway via the 3MC state. The present study elucidates the relationship between structure and property of gold(III) complexes featuring C∧N∧C ligands and providing a comprehensive understanding of the significant differences in their luminescence behaviors.

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, SA and SB, through coordination-driven self-assemblies of the triphenylamine (TPA)-based donor L with different diplatinum(II) acceptors LA and LB, respectively. These metallo-cages take advantage of their steric nature and curved conformation to more effectively limit the free rotation of the benzene ring and hinder π-π stacking in the solid state, which successfully inhibited fluorescence quenching and realizing highly efficient luminescent properties. Therefore, this work offers a new design strategy for preparing materials with excellent luminescent properties.

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. The spatial configurations of these assemblies (one double-decker and three "S-shaped" or "X-shaped" triple-decker structures) depend on the angles of these TPE-derived ligands. Notably, the three triple-decker structures are geometric isomers. Furthermore, photophysical studies show that these complexes exhibit different ratios of radiative (kr ) and non-radiative (knr ) rate constant due to the different spatial arrangements of TPE moieties. This study provides not only a unique strategy for the construction of multi-stacks with specific spatial arrangement, but also a promising platform for investigating the aggregation behavior of fluorescent chromophores.

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)). Such switching of two types of emissions could be attributable to the modulation of the intramolecular charge transfer (ICT) and twist between donor and acceptor units. In the theoretical framework of the state hybridization, the excited-state properties are analyzed to reveal the intrinsic structure-property relationships for the donor-based HLCT and TADF molecules. This work not only offers an in-depth understanding of the excited-state properties of HLCT/TADF molecules, but also provides theoretical guidelines for the designing and screening of highly efficient electroluminescent materials.

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. With the aid of ultra-high-vacuum, low-temperature scanning tunneling microscopy (UHV-LT-STM), we were able to investigate four isomeric structures corresponding to four types of binding modes of ligand LA with two major conformations complexes A. The distribution of isomers measured by STM and total binding energy of each isomer obtained by density functional theory (DFT) calculations suggested that the most abundant isomer could be the most stable one with highest total binding energy. Finally, through shortening the linker between inner and outer layers and the length of arms, the arrangement of dissymmetrical ligand LB could be controlled within one binding mode corresponding to the single conformation for complexes B.

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. Four dissymmetrical ditopic ligands were designed and synthesized. By increasing the dissymmetry of length or angle, conformations of assemblies were precisely controlled to form discrete cis-Pdn L2n molecular cages.

Fluorescence Regulation and Photoresponsivity in AIEE Supramolecular Gels Based on a Cyanostilbene Modified Benzene-1,3,5-Tricarboxamide Derivative.

Supramolecular interactions play an important role in regulating the optical properties of molecular materials. Different arrangements of identical molecules can afford a more straightforward insight into the contributions of supramolecular interactions. Herein, a novel gelator, BTTPA, composed of a benzene-1,3,5-tricarboxamide (BTA) central unit functionalized with three cyanostilbenes is designed, which forms two kinds of gels in DMSO/water mixtures. Depending on the water volume content, the gels exhibit quite different aggregation-induced emission enhancement (AIEE) properties, with one emitting a green emission (G-gel), and the second emitting a blue emission (B-gel). The main reason for this difference is that water affects H-bonding and π-π interactions, further resulting in disparate packing modes of gelators. In addition, only the G-gel displays gel-to-sol transition accompanied with fluorescence switching according to the trans-cis photoisomerization of cyanostilbene under UV light irradiation. The B-gel does not exhibit any change because of its tight hexagonal packing arrangement. Such packing modes restricted the space in which molecules were located and inhibited the transformation of configuration of cyanostilbene. These phenomena underline the incomparable status of packing modes and molecular configuration in regulating fluorescence properties and photoresponse behavior in organic solid-state luminescent materials.

Rigidified and expanded N-annulated perylenes as efficient donors in organic sensitizers for application in solar cells.

A class of N-annulated perylene (NP)-based organic dyes used in dye-sensitized solar cells has been investigated by means of quantum chemical calculations. The NPs are rigidified with thiophene or benzene rings in both a one-sided and two-sided manner on a 5- or 6-member ring and are considered as electron donors in dyes. To gain a better understanding of the effect of such modulation of NP moieties on the dye performance, the geometrical and electronic structures, the optical absorption and intramolecular charge transfer properties of the dyes and dye-TiO2 complexes are analyzed in detail to establish the structure-property relationship. The calculated results indicate that the rigidified NP moieties could improve light-harvesting capacities, modulate the energy levels of frontier orbitals, accelerate intramolecular charge transfer by decreasing the aromaticity of the π-system, decreasing the reorganization energy and avoiding electon trapping in the possible multiple electron transfer pathways, and facilitate charge separation with a lower coulombic attractive energy. In particular, the bilateral dyes via a 6-member immobilization would be promising candidates with excellent performance. We hope that our calculations could give a more in-depth physical insight on the structure-property relationship and provide guidance for the exploration of high-performance NP-based dyes.

Quantum-Chemical Insights into the Phosphorescence Efficiencies of Blue-Emitting Platinum Complexes with Phenylene-Bridged Pincer Ligands.

Blue phosphorescent platinum complexes with phenylene-bridged pincer ligands, [Pt(dmib)Cl] [1; dmib = m-bis(methylimidazolyl)benzene], [Pt(mizb)Cl] [2; mizb = bis( N-methylimidazolium)benzene], and [Pt(dpzb)Cl] [3; dpzb = m-bis(3,5-dimethylpyrazolyl)benzene], have been investigated theoretically to rationalize the marked differences of their phosphorescence efficiencies. On the basis of density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations, the geometrical and electronic structures, absorption and emission properties, and radiative and nonradiative processes are analyzed in detail. The emission from the emissive lowest triplet state (T1) originates from a mixture of metal-to-ligand charge-transfer (3MLCT) and intraligand charge-transfer (3ILCT) states. The calculated radiative decay rate constants of T1 of the complexes are comparable and in the same order of magnitude with the experimental measurements. Therefore, the potential energy profiles for the deactivation processes from T1 via temperature-independent and -dependent pathways are explored to reveal the effect of nonradiative decay on phosphorescence. The calculated results indicate that the very weak emission of 3 could be ascribed to the deactivation process via the metal-centered (3MC) state, which can be readily accessible via a spontaneous process from the T1 state. This work provides more in-depth insight into the nature of the emissive excited state, shielding light on a better understanding of the excited-state behavior of phosphorescent platinum complexes.

2-(2-Hydroxyphenyl)benzimidazole-based four-coordinate boron-containing materials with highly efficient deep-blue photoluminescence and electroluminescence.

Two novel four-coordinate boron-containing emitters 1 and 2 with deep-blue emissions were synthesized by refluxing a 2-(2-hydroxyphenyl)benzimidazole ligand with triphenylborane or bromodibenzoborole. The boron chelation produced a new π-conjugated skeleton, which rendered the synthesized boron materials with intense fluorescence, good thermal stability, and high carrier mobility. Both compounds displayed deep-blue emissions in solutions with very high fluorescence quantum yields (over 0.70). More importantly, the samples showed identical fluorescence in the solution and solid states, and the efficiency was maintained at a high level (approximately 0.50) because of the bulky substituents between the boron atom and the benzimidazole unit, which can effectively separate the flat luminescent units. In addition, neat thin films composed of 1 or 2 exhibited high electron and hole mobility in the same order of magnitude 10(-4), as determined by time-of-flight. The fabricated electroluminescent devices that employed 1 or 2 as emitting materials showed high-performance deep-blue emissions with Commission Internationale de L'Eclairage (CIE) coordinates of (X = 0.15, Y = 0.09) and (X = 0.16, Y = 0.08), respectively. Thus, the synthesized boron-containing materials are ideal candidates for fabricating high-performance deep-blue organic light-emitting diodes.

Reversible Piezofluorochromic Property and Intrinsic Structure Changes of Tetra(4-methoxyphenyl)ethylene under High Pressure.

During the past decade, luminescent mechanochromism has received much attention. Despite the garnered attention, only a few studies have reported the effect of internal molecular structure change on the performance of mechanochromic fluorescence. Here, we chose tetra(4-methoxyphenyl)ethylene (TMOE) as a model molecule to study the correlation between structure and fluorescence property under a hydrostatic pressure produced by a diamond anvil cell (DAC). TMOE is a methoxy-substituted tetraphenylethylene (TPE) derivative and has a nearly centrosymmetric structure and a natural propeller shape. Ultraviolet-visible absorption and fluorescence spectra of TMOE and TPE in solution proved that the presence of methoxy groups in TMOE is responsible for the difference in fluorescence emissions of TMOE and TPE. Under a hydrostatic pressure, the in situ fluorescence spectra of TMOE at different concentrations show that the fluorescence intensity gradually weakens, accompanied by an obvious redshift. The Raman peak intensities decrease gradually, and the peaks disappear eventually with the pressure increasing. These spectral changes are attributed to the changes in the intramolecular conformation, that is, the strengthening of the weak C-H···O hydrogen bonds in TMOE molecules, which is caused by the twisted dihedral angle between the benzene ring and the carbon rigid plane of ethylene. Density functional theory simulation further confirms that the decreased dihedral angle could weaken Raman peak intensity, which is consistent with our experimental results.

Organic Crystals with Near-Infrared Amplified Spontaneous Emissions Based on 2'-Hydroxychalcone Derivatives: Subtle Structure Modification but Great Property Change.

A series of highly efficient deep red to near-infrared (NIR) emissive organic crystals 1-3 based on the structurally simple 2'-hydroxychalcone derivatives were synthesized through a simple one-step condensation reaction. Crystal 1 displays the highest quantum yield (Φf) of 0.32 among the reported organic single crystals with an emission maximum (λem) over 710 nm. Comparison between the bright emissive crystals 1-3 and the nearly nonluminous compounds 4-7 clearly gives evidence that a subtle structure modification can arouse great property changes, which is instructive in designing new high-efficiency organic luminescent materials. Notably, crystals 1-3 exhibit amplified spontaneous emissions (ASE) with extremely low thresholds. Thus, organic deep red to NIR emissive crystals with very high Φf have been obtained and are found to display the first example of NIR fluorescent crystal ASE.

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 Ucp1-&Cidea+ adipocytes that arises from brown-to-white conversion during postnatal life in the periureter region of mouse PRAT. Cold exposure restores Ucp1 expression and a thermogenic phenotype in this subpopulation. These cells have a transcriptome that is distinct from subcutaneous beige adipocytes and may represent a unique type of cold-recruitable adipocytes. These results pave the way for studies of PRAT physiology and mechanisms controlling the plasticity of brown/white adipocyte phenotypes.

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-ß 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. Mice with the I482V variant displayed an intermediate phenotype, with partial resistance to HFD-induced obesity, reduction in subcutaneous, but not visceral, fat mass, decreased systemic lipolysis and reduced ALK7 signaling. Surprisingly, mice carrying the N150H variant were metabolically indistinguishable from wild type under HFD, although ALK7 signaling was reduced at low ligand concentrations. CONCLUSION: Together, these results validate ALK7 as an attractive drug target in human obesity and suggest a lower threshold for ALK7 function in humans compared to mice.

Theoretical investigation of electronic structure and charge transport property of 9,10-distyrylanthracene (DSA) derivatives with high solid-state luminescent efficiency.

The electronic structure and charge transport property of 9,10-distyrylanthracene (DSA) and its derivatives with high solid-state luminescent efficiency were investigated by using density functional theory (DFT). The impact of substituents on the optimized structure, reorganization energy, ionization potential (IP) and electronic affinity (EA), frontier orbitals, crystal packing, transfer integrals and charge mobility were explored based on Marcus theory. It was found that the hole mobility of DSA was 0.21 cm(2) V(-1) s(-1) while the electron mobility was 0.026 cm(2) V(-1) s(-1), which were relatively high due to the low reorganization energies and high transfer integrals. The calculated results showed that the charge transport property of these compounds can be significantly tuned via introducing different substituents to DSA. When one electron-withdrawing group (cyano group) was introduced into DSA, DSA-CN exhibited hole mobility of 0.14 cm(2) V(-1) s(-1) which was on the same order of that of DSA. However, the electron mobility of DSA-CN decreased to 8.14 × 10(-4) cm(2) V(-1) s(-1) due to the relatively large reorganization energy and disadvantageous transfer integral. The effect of electron-donating substituents was investigated by introducing methoxy group and tertiary butyl into DSA. DSA-OCH(3) and DSA-TBU showed much lower charge mobility than DSA resulting from the steric hindrance of substituents. On the other hand, both of them exhibited balanced transport properties (for DSA-OCH(3), the hole and electron mobility was 0.0026 and 0.0027 cm(2) V(-1) s(-1); for DSA-TBU, the hole and electron mobility was 0.045 and 0.012 cm(2) V(-1) s(-1)) because of their similar transfer integrals for both hole and electron. DSA and its derivatives were supposed to be one of the most excellent emissive materials for organic electroluminescent applications because of their high charge mobility and high solid-state luminescent efficiency.

Exchange narrowing and exciton delocalization in disordered J aggregates: simulated peak shapes in the two dimensional spectra.

Delocalized excitons in elementary linear J aggregates of two-level molecules absorb a photon into the low-energy edge of an exciton band. Absorption of a second photon is blue-shifted as the lowest energy state is occupied. This setup of states leads to a double-peak feature in a set of two dimensional photon echo spectra for excitonic bands. The delocalization properties of excitons, thus, strongly affect the peak lineshapes and their relative amplitudes. Simulations of various two dimensional spectra of a linear J aggregate are presented and possible schemes to quantitatively characterize the peak profiles are suggested. This allows to relate observable peak lineshapes to the exciton delocalization.

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.k.a. large graph corpora) and then fine-tuning the model on different related downstream applications with different graph schemas. To address this problem, we propose a framework of graph-aware language model pre-training (GaLM) on a large graph corpus, which incorporates large language models and graph neural networks, and a variety of fine-tuning methods on downstream applications. We conduct extensive experiments on Amazon's real internal datasets and large public datasets. Comprehensive empirical results and in-depth analysis demonstrate the effectiveness of our proposed methods along with lessons learned.