Regulatory mechanism of Sarmentosin and Quercetin on lipid accumulation in primary hepatocyte of GIFT tilapia (Oreochromis niloticus) with fatty liver.

Sarmentosin (SA) and Quercetin (QC) are two active components of Sedum Sarmentosum Bunge, which is a traditional Chinese herbal medicine. This study aimed to investigate the role and regulatory mechanism of SA and QC in fatty liver of Genetic Improvement of Farmed Tilapia (GIFT) tilapia. GIFT tilapia were randomly divided into two groups with three replicates per treatment (30 fish in each replicate): normal diet group (average weight 3.51±0.31 g) and high-fat diet group (average weight 3.44±0.09 g). After 8 weeks feeding trial, growth index, lipid deposition, and biochemical indexes were measured. Lipid deposition, and lipid and inflammation-related gene expression were detected in a primary hepatocyte model of fatty liver of GIFT tilapia treated with SA or QC. Our results showed that high-fat diet caused lipid deposition and peroxidative damage in the liver of GIFT tilapia. The cell counting kit-8 assay results indicated that 10 µM SA and 10 µM of QC both had the least effect on hepatocyte proliferation. Moreover, both 10 µM of SA and 10 µM of QC showed lipolytic effects and inhibited the expression of lipid-related genes (FAS, Leptin, SREBP-1c, and SREBP2) in fatty liver cells. Interestingly, QC induced autophagosome-like subcellular structure and increased the expression of IL-8 in fatty liver cells. In conclusion, this study confirmed that SA and QC improved fatty liver caused by high-fat diet, providing a novel therapeutic approach for fatty liver of GIFT tilapia.

Syntheses, Structural Analyses, and Properties of Condensed Arenes with Multihelicity.

A C1-symmetric hexapole helicene (HH) and a C3-symmetric dodecapole helicene (DH) were prepared, and their three-dimensional structures were verified by X-ray crystallography and density functional theory calculations. The molecular geometries and local helical configurations of their most stable diastereomers were correctly predicted by arranging suitable conformations of the peripheral aryl rings. Importantly, the outermost three [5]helicenes with a consistent configuration in DH were observed to increase the thermostability, enantiomerization barrier (ΔH⧧ = 40.5 kcal/mol), specific rotation ([α]24D = -4228°) and absorption dissymmetry factor (gabs = 1.35 × 10-3 at 453 nm).

exo-6b2-Methyl-Substituted Pentabenzocorannulene: Synthesis, Structural Analysis, and Properties.

exo-6b2-Methyl-substituted pentabenzocorannulene (exo-PBC-Me) was synthesized by the palladium-catalyzed cyclization of 1,2,3-triaryl-1H-cyclopenta[l]phenanthrene. Its bowl-shaped geometry with an sp3 carbon atom in the backbone and a methyl group located at the convex (exo) face was verified by X-ray crystallography. According to DFT calculations, the observed conformer is energetically more favorable than the endo one by 39.9 kcal/mol. Compared to the nitrogen-doped analogs with intact π-conjugated backbones (see the main text), exo-PBC-Me displayed a deeper bowl depth (avg. 1.93 Å), redshifted and broader absorption (250-620 nm) and emission (from 585 to more than 850 nm) bands and a smaller optical HOMO-LUMO gap (2.01 eV). exo-PBC-Me formed polar crystals where all bowl-in-bowl stacking with close π ⋅ ⋅ ⋅ π contacts is arranged unidirectionally, providing the potential for applications as organic semiconductors and pyroelectric materials. This unusual structural feature, molecular packing, and properties are most likely associated with the assistance of the methyl group and the sp3 carbon atom in the backbone.

Overcrowded 14,14'-Bidibenzo[a,j]anthracenes: Challenges in Syntheses and Atypical Property of Lacking Symmetry-Breaking Charge Transfer (SBCT).

14,14'-Bidibenzo[a,j]anthracenes (BDBAs) were prepared by iridium-catalyzed annulation of 5,5'-biterphenylene with alkynes. The molecular geometries of overcrowded BDBAs were verified by X-ray crystallography. The two dibenzo[a,j]anthryl moieties are connected through the sterically hindered 14 positions, resulting in highly distorted molecular halves. The conformation with a small twist angle between two molecular halves can minimize steric conflicts between the substituents at 1 and 13 positions and the carbon atoms of the central axis, as well as steric clashes between those substituents. One such example is octafluoro-substituted BDBA, where the interplanar angle between two anthryl moieties is approximately 31° (currently the lowest reported value, cf. 81° in 9,9'-bianthracene). The intramolecular interactions and electronic couplings between two molecular halves resulted in upfield 1H NMR signals, redshifted absorption and emission bands, and a reduced HOMO-LUMO gap. Photodynamic investigations on BDBAs indicated that the formation of the conventional symmetry-breaking charge transfer (SBCT) state was suspended by restricted rocking around the central C-C bond. Such a mechanism associated with this highly constrained conformation was examined for the first time.

Development of Solid Waste-Based Composite Calcium Ferrite Flux and Its Application in Hot Metal Pre-Dephosphorization.

To enhance the slagging efficiency of the lime-based slag system during the pre-treatment stage of hot metal, a composite calcium ferrite flux based on aluminum industry solid waste was developed in this study. The melting characteristics of the flux and its application in the pre-treatment of hot metal were investigated. The results indicated that the main phases of the composite calcium ferrite were CaFe2O4, Ca2Fe2O5, and Ca2(Fe,Al)2O4. It exhibited high oxidation, high alkalinity, and a low melting point, thereby achieving excellent melting performance. Simulations of various dephosphorization fluxes in the pre-treatment of high-phosphorus hot metal, ordinary hot metal, and kilogram-scale dephosphorization experiment processes were conducted. Under the same experimental conditions, the composite calcium ferrite flux was able to achieve a dephosphorization rate of over 90% and a final phosphorus content of less than 0.02 wt% under high carbon content ([%C] = 3.2 wt%). In the application of hot metal pre-dephosphorization, this flux was able to achieve efficient melting and rapid slagging of lime at a lower temperature, and its slagging time was 50% faster than that of calcium ferrite flux. In addition, this flux enhanced the utilization efficiency of lime during the steelmaking process, effectively prevented the agglomeration of slag, and achieved efficient slag-metal separation. These characteristics were significantly better than the application effect of calcium ferrite flux. This flux has significant implications for the industrial application of deep dephosphorization in the pre-treatment stage of hot metal or the early stage of converter steelmaking.

A New Series of Sandwich-Type 5,5'-Biterphenylenes: Synthetic Challenge, Structural Uniqueness and Photodynamics.

A new series of biaryls, bi-linear-terphenylenes (BLTPs), were prepared using the tert-butyllithium-mediated cyclization as the key synthetic step. The three-dimensional structures of the studied compounds were verified using X-ray crystallography and DFT calculations. Tetraaryl(ethynyl)-substituted BLTPs are highly crowded molecules, and the internal rotation around the central C-C bond is restricted due to a high barrier (>50 kcal/mol). These structures contain several aryl/terphenylenyl/aryl sandwiches, where the through-space π-π (TSPP) interactions are strongly reflected in the shielding of 1 H NMR chemical shifts, reduction of oxidation potentials, increasing aromaticity of the central six-membered ring and decreasing antiaromaticity of the four-membered rings in a terphenylenyl moiety based on NICS(0) and iso-chemical shielding surfaces. Despite the restricted C-C bond associated intramolecular TSPP interactions for BLTPs in the ground state, to our surprise, the electronic coupling between two linear terphenylenes (LTPs) in BLTPs in the excited state is weak, so that the excited-state behavior is dominated by the corresponding monomeric LTPs. In other words, all BLTPs undergo ultrafast relaxation dynamics via strong exciton-vibration coupling, acting as a blue-light absorber with essentially no emission.

Synthesis, structural analysis, and properties of highly twisted alkenes 13,13'-bis(dibenzo[a,i]fluorenylidene) and its derivatives.

The rotation of a C = C bond in an alkene can be efficiently accelerated by creating the high-strain ground state and stabilizing the transition state of the process. Herein, the synthesis, structures, and properties of several highly twisted alkenes are comprehensively explored. A facile and practical synthetic approach to target molecules is developed. The twist angles and lengths of the central C = C bonds in these molecules are 36-58° and 1.40-1.43 Å, respectively, and confirmed by X-ray crystallography and DFT calculations. A quasi-planar molecular half with the π-extended substituents delivers a shallow rotational barrier (down to 2.35 kcal/mol), indicating that the rotation of the C = C bond is as facile as that of the aryl-aryl bond in 2-flourobiphenyl. Other versatile and unique properties of the studied compounds include a broad photoabsorption range (from 250 up to 1100 nm), a reduced HOMO-LUMO gap (1.26-1.68 eV), and a small singlet-triplet energy gap (3.65-5.68 kcal/mol).

Highly Distorted Multiple Helicenes: Syntheses, Structural Analyses, and Properties.

A series of hexapole helicenes (HHs) and nonuple helicenes (NHs) were prepared from 1,3,5-tris[2-(arylethynyl)phenyl]benzene through two steps, namely, iodocyclization and subsequent palladium-catalyzed annulation with ortho-bromoaryl carboxylic acids. The crucial advantages of this synthetic method are the facile introduction of substituents, high regioselectivity, and efficient backbone extension. Three-dimensional structures of three C1-symmetric HHs and one C3-symmetric NH were elucidated using X-ray crystallography. Unlike most conventional multiple helicenes, the HHs and NHs investigated herein possess a unique structural feature where some double helical moieties share a terminal naphthalene unit. Chiral resolution of a HH and an NH was successfully achieved, and the enantiomerization barrier (ΔH‡) of the HH was experimentally determined to be 31.2 kcal/mol. A straightforward method for predicting the most stable diastereomer was developed based on density functional theory calculations and structural considerations. It was found that the relative potential energies (ΔHrs) of all diastereomers for two HHs and one NH can be obtained using minimal computational effort to analyze the types, helical configurations, numbers, and ΔH(MP-MM)s [= H(M,P/P,M) - H(M,M/P,P)] of the double helicenyl fragments.

Highly Substituted Acephenanthrylenes and Their π-Extended Derivatives: Syntheses, Structural Analyses, and Properties.

This investigation demonstrates that a series of (highly) substituted acephenanthrylenes (APs) 2, benzo[l]acephenanthrylene 3, and dicyclopenta[cd,mn]pyrene 4 are easily prepared by palladium-catalyzed cycloaromatization of 2,3-diethynylbiphenyls 1. The first nonpyrolysis synthesis of 4 by two-fold cycloaromatization was achieved in a high yield. This synthetic protocol has two crucial advantages: facile introduction of various substituents and efficient extension of the AP backbone.

Diindeno[2,1-b:2',1'-h]biphenylenes: Syntheses, Structural Analyses, and Properties.

A series of diindeno[2,1-b:2',1'-h]biphenylenes with open-shell singlet ground states and interesting properties were prepared. The studied compounds consist of p-quinodimethane moieties, which suffer from geometric perturbation with bond angles of around 90°. The substituent effects on structural parameters, local aromaticity, and properties were systematically explored.

Quantitative 3D real-space analysis of Laves phase supraparticles.

Assembling binary mixtures of nanoparticles into crystals, gives rise to collective properties depending on the crystal structure and the individual properties of both species. However, quantitative 3D real-space analysis of binary colloidal crystals with a thickness of more than 10 layers of particles has rarely been performed. Here we demonstrate that an excess of one species in the binary nanoparticle mixture suppresses the formation of icosahedral order in the self-assembly in droplets, allowing the study of bulk-like binary crystal structures with a spherical morphology also called supraparticles. As example of the approach, we show single-particle level analysis of over 50 layers of Laves phase binary crystals of hard-sphere-like nanoparticles using electron tomography. We observe a crystalline lattice composed of a random mixture of the Laves phases. The number ratio of the binary species in the crystal lattice matches that of a perfect Laves crystal. Our methodology can be applied to study the structure of a broad range of binary crystals, giving insights into the structure formation mechanisms and structure-property relations of nanomaterials.

New [2,2]Fluorenophanes Give Insights into Asymmetric Charge Transfer-Mediated Exciton Delocalization along the π-π Packing Direction.

A series of new [2,2]fluorenophanes has been synthesized and characterized; among them, molecules of crystallographically asymmetric anti-[2.2](1,4)(4,1)fluorenophane (K2C-2) aggregate to form one-dimensional supramolecular chain structures through effective intermolecular π-π overlapping. This, in combination with the synergistic intramolecular π-π interaction, leads to prominent dual emission mediated by charge transfer (CT) exciton delocalization. Support of this new insight is given by mapping the transition density along the π-π packing direction where the intramolecular excitation and intermolecular CT coexist in K2C-2.

[2,2](5,8)Picenophanedienes: Syntheses, Structural Analyses, Molecular Dynamics, and Reversible Intramolecular Structure Conversion.

This study presents an important and efficient synthetic approach to 5,8-dibromo-2,11-di-tert-butylpicene (3), with multigram scale, which was then converted to a new series of picenophanes (6-10). The tub-shaped [2,2](5,8)picenophanediene 8 with two cis-ethylene linkers was explored using X-ray crystallography. The tub-to-tub inversion proceed through the successive bending of the linkers and the barrier for isopropyl-substituted derivative 10 was experimentally estimated to be 18.7 kcal/mol. Picenophanes with a large π-system and semi-rigid structure exhibited anomalous photophysical properties. The ethano-bridged picenophane shows the weak exciton delocalization while the cis-ethylene-bridged picenophane exhibits dual emission rendered by the weakly delocalized exciton and excimer. With the aid of the ultrafast time-resolved emission spectroscopy, the mechanism of the excimer formation is resolved, showing a unique behavior of two-state reversible reaction with fast structural deformation whose lifetime is around 20 ps at 298 K. This work demonstrates that the slight difference in the bridge of tub-shaped picenophanes renders distinct photophysical behavior, revealing the potential of harnessing inter-moiety reaction in the picenophane systems.

Influence of humor expression on suicidal ideation among adolescents: mediating effects of depressive emotion and positive emotion.

BACKGROUND: The occurrence and degree of suicidal ideation during the past month in adolescents should be regarded seriously. Several studies have noted that humor expression style and depressive emotion may influence adolescents' suicidal ideation. However, there is insufficient evidence concerning whether positive emotion reduces such suicidal ideation in adolescents. In addition, the relationships among humor expression, depressive emotion, positive emotion and suicidal ideation remain to be confirmed. Therefore, in this study, we aimed to test the mediating roles of depressive emotion and positive emotion in the relationship between humor expression and recent adolescent's suicidal ideation. METHODS: A total of 1551 students in junior high school completed questionnaires. The collected data were analyzed using structural equation modeling (SEM) with LISREL 8.80 and Monte Carlo resampling with R. RESULTS: The results indicate that suicidal ideation in adolescents during the past month was related not only to humor expression but also to depressive emotion and positive emotion. The stronger the depressive emotion felt, the stronger the suicidal ideation; in contrast, the stronger the positive emotion, the weaker the suicidal ideation. Moreover, depressive emotion and positive emotion were found to mediate the relationship between humor expression and suicidal ideation; additionally, positive emotion was found to mediate the relationship between depressive emotion and suicidal ideation. CONCLUSION: These results highlight that depressive emotion and positive emotion may mediate the influence of humor expression on suicidal ideation among adolescents, and positive emotion may mediate the influence of depressive emotion on suicidal ideation. More attention should be paid to decreasing adolescents' self-deprecating humor expression and depressive emotion, whereas more witty response humor expression and positive emotion should be encouraged to prevent their suicidal ideation.

Coupling of electricity generation and denitrification in three-phase single-chamber MFCs in high-salt conditions.

High-salt conditions reduce the efficiency of electricity generation and nitrogen removal in microbial fuel cells (MFCs). In this work, we propose a three-phase single-chamber MFC (TP-MFC) by setting up a phase with immobilized cells in a conventional bipolar single-chamber MFC (common MFC). Cells from Halomonas were used as the immobilized phase, because these cells secrete the compatible solute ectoine and exhibit simultaneous nitrification and denitrification (SND). This enhanced the efficiency of SND and subsequent electricity generation under high-salt conditions. The average voltage of TP-MFC generated during the stable period in the presence of 30 g/L NaCl was 439.3 mV, which was 55.2% higher than that generated in common MFC. In addition, the N-removal rate of TP-MFC at 72 h was 63.4%, which was 38.4% higher than that of common MFC. The 16S rRNA diversity analysis showed an improved abundance of Pseudomonas, Acinetobacter, Alcaligenes, and Halomonas in TP-MFC, indicating that the ectoine secreted by immobilized Halomonas conferred substantial salt-tolerance on the electrogenic bacteria growing in a high-salt environment. This paper establishes an efficient and convenient method for improving the salt tolerance of microbial flora in MFCs, which is of great significance for the application of MFCs in high-strength wastewater treatment.

The complete chloroplast genome of Musa beccarii.

Musa becccarii N.W. Simmonds is one of the most important wild banana species native to Borneo. The chromosome number, 2n = 18, is new to the genus Musa. Wild populations of M. beccarii have been reduced enormously due to massive land clearing for oil palm plantations. In this study, we report the complete chloroplast genome of Musa beccarii by next-generation sequencing (NGS). The total length of the complete chloroplast genome was 168,457 bp, and the overall GC content of the whole genome is 36.8%. The cp genome of Musa beccarii contained a pair of inverted repeat regions of 34,819 bp, which were separated by the large single copy of 88,166bp and the small single copy of 11,059 bp. It encoded 114 genes, including 79 protein-coding genes, 31 tRNA genes, and 4 rRNA ribosomal genes. The most genes occur as a single copy, while 21 gene species occur in double copies. The phylogenetic analysis demonstrateds Musa becccarii formed a single branch among genus Musa. This complete chloroplast genome will provide important information for conservation and identification of species of Musa spp.

The complete chloroplast genome of Musa acuminata var. chinensis.

Musa acuminata var. chinensis is one of the most important wild banana species native to China which has huge potential breeding value by its cold tolerance and disease resistance. In this study, we first reported the complete chloroplast genome of M. acuminata var. chinensis and explore its phylogenetic position using a maximum likelihood phylogenetic tree. The chloroplast genome of M. acuminata var. chinensis is 170,402 bp in length and the overall GC content of the whole genome is 36.8%. It consisting of a pair of inverted repeat (IR, 35,320 bp) regions, a large single-copy (LSC, 88,870 bp) and a small single-copy (SSC, 10,900 bp). The chloroplast genome contained 112 genes, including 79 protein-coding genes, 29 tRNA genes, and 4 rRNA ribosomal genes. The most genes occur as a single copy, while 23 gene species occur in double copies. Phylogenetic analysis of 7 selected chloroplast genomes revealed that M. acuminata var. chinensis was closely related to M. acuminata ssp. malaccensis. The complete chloroplast genome of M. acuminata var. chinensis will greatly enhance precious gene resources for banana breeding programs in the future.

Indeno[1,2-b]fluorene-Based [2,2]Cyclophanes with 4n/4n and 4n/[4n+2] π†Electrons: Syntheses, Structural Analyses, and Excitonic Coupling Properties.

Indeno[1,2-b]fluorene-based [2,2]cyclophanes with 4n/4n and 4n/[4n+2] π-electron systems were prepared, and their structures were identified by X-ray crystallography. With short π-π distances around 3.0 Å, [2.2](5,11)indeno[1,2-b]fluorenophane and its precursor [2.2](5,11)indeno[1,2-b]fluorene-6,12-dionophane exhibit remarkable transannular interactions, leading to their unusual electrochemical and photophysical properties. With the aid of femtosecond transient absorption spectroscopy, the transition from the monomeric excited state to the redshifted H-type dimeric state was first observed, correlating to the calculated excitonic energy splitting and the steady-state absorption spectra induced by charge-transfer-mediated superexchange interaction.

Designing Strong Optical Absorbers via Continuous Tuning of Interparticle Interaction in Colloidal Gold Nanocrystal Assemblies.

We program the optical properties of colloidal Au nanocrystal (NC) assemblies via an unconventional ligand hybridization (LH) strategy to precisely engineer interparticle interactions and design materials with optical properties difficult or impossible to achieve in bulk form. Long-chain hydrocarbon ligands used in NC synthesis are partially exchanged, from 0% to 100%, with compact thiocyanate ligands by controlling the reaction time for exchange. The resulting NC assemblies show transmittance, reflectance, optical permittivity, and direct-current (DC) resistivity that continuously traverse a dielectric-metal transition, providing analog tuning of their physical properties, unlike the digital control realized by complete exchange with ligands of varying length. Exploiting this LH strategy, we create Au NC assemblies that are strong, ultrathin film optical absorbers, as seen by a 6× increase in the extinction of infrared light compared to that in bulk Au thin films and by a temperature rise of 20 °C upon illumination with 808 nm light. Our LH strategy may be applied to the design of materials constructed from NCs of different size, shape, and composition for specific applications.

Nanocrystal Core Size and Shape Substitutional Doping and Underlying Crystalline Order in Nanocrystal Superlattices.

Substitutional doping is a potentially powerful technique to control the properties of nanocrystal (NC) superlattices (SLs). However, not every NC can be substituted into any lattice, as the NCs have to be close in size and shape, limiting the application of substitutional doping. Here we show that this limitation can be overcome by employing ligands of various size. We show that small NCs with long ligands can be substituted into SLs of big NCs with short ligands. Furthermore, we show that shape differences can also be overcome and that cubes can substitute spheres when both are coated with long ligands. Finally, we use the NC effective ligand size, softness, and effective overall size ratio to explain observed doping behaviors.