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The activity and cholesterol-binding behavior of the steroidogenic acute regulatory protein (StAR) 1 and StARD3-D7 are assessed, indicating that StARD6 has activity equal to StARD1, whereas StARD, D5, and D7 has little or no activity with adrenal mitochondria in vitro. StARD6 is expressed only in male germ-line cells and it has displayed biological and biophysical properties that have implied a role in steroidogenesis.

Research has been conducted on the asymmetric hydrosilylation of aromatic alkenes. Results indicate that the reaction gives access to the optically pure benzylic alcohols after Tamao oxidation.

We study laser-driven isomerization reactions through an excited electronic state using the recently developed Geometrical Optimization procedure. Our goal is to analyze whether an initial wave packet in the ground state, with optimized amplitudes and phases, can be used to enhance the yield of the reaction at faster rates, driven by a single picosecond pulse or a pair of femtosecond pulses resonant with the electronic transition. We show that the symmetry of the system imposes limitations in the optimization procedure, such that the method rediscovers the pump-dump mechanism. [ABSTRACT FROM AUTHOR]

We have recently proposed a laser control scheme for ultrafast absorption in multilevel systems by parallel transfer. In this work we develop an analytical model that better takes into account the main features of electronic absorption in molecules. We show that the initial vibrational coherence in the ground electronic state can be used to greatly enhance the rate and yield of absorption when ultrashort pulses are used, provided that the phases of the coherences are taken into account. On the contrary, the initial coherence plays no role in the opposite limit, when a single long pulse drives the optical transition. The theory is tested by numerical simulations in the first absorption band of Na2. [ABSTRACT FROM AUTHOR]

Recently, control over the bond length of a diatomic molecule with the use of parabolic chirped pulses was predicted on the basis of numerical calculations [Chang; et al. Phys. Rev. A2010, 82, 063414]. To achieve the required bond elongation, a laser scheme was proposed that implies population inversion and vibrational trapping in a dissociative state. In this work we identify two regimes where the scheme works, called the strong and the weak adiabatic regimes. We define appropriate parameters to identify the thresholds where the different regimes operate. The strong adiabatic regime is characterized by a quasi-static process that requires longer pulses. The molecule is stabilized at a bond distance and at a time directly controlled by the pulse in a time-symmetrical way. In this work we analyze the degree of control over the period and elongation of the bond as a function of the pulse bandwidth. The weak adiabatic regime implies dynamic deformation of the bond, which allows for larger bond stretch and the use of shorter pulses. The dynamics is anharmonic and not time-symmetrical and the final state is a wave packet in the ground potential. We show how the vibrational energy of the wave packet can be controlled by changing the pulse duration. [ABSTRACT FROM AUTHOR]

Membrane-bound phosphodiesterase 6 (PDE6) plays an important role in visual signal transduction by regulating cGMP levels in rod photoreceptor cells. Our understanding of PDE6 catalysis and structure suffers from inadequate characterization of the α and β subunit catalytic core, interactions of the core with two intrinsically disordered, proteolysis-prone inhibitory PDE? (P?) subunits, and binding of two types of isoprenyl-binding protein δ, called PrBP/δ, to the isoprenylated C-termini of the catalytic core. Structural studies of native PDE6 have been also been hampered by the lack of a heterologous expression system for the holoenzyme. In this work, we purified PDE6 in the presence of PrBP/δ and screened for additives and detergents that selectively suppress PDE6 basal activity while sparing that of the trypsin-activated enzyme. Some detergents removed PrBP/δ from the PDE complex, separating it from the holoenzyme after PDE6 purification. Additionally, selected detergents also significantly reduced the level of dissociation of PDE6 subunits, increasing their homogeneity and stabilizing the holoenzyme by substituting for its native membrane environment. [ABSTRACT FROM AUTHOR]

Fluorescence imaging of cell membrane glycoproteins based on metabolic labeling faces challenges including the sensitivity and spatial specificity and the use of a high concentration of unnatural sugars. To overcome these limitations, we developed a method for in situ imaging of cell membrane glycoproteins by operating Cas12a activity, and employing the ultrabright DNA nanostructure, FluoroCube (FC), as a signal reporter. Following Cas12a activation, we observed stable and intense fluorescence signals within 15 min. The combination of bright FC and Cas12a's amplification capability allows for effective imaging with only 5 μM of unnatural sugars and a brief 24-h incubation. Computational modeling demonstrates that Cas12a specifically cleaves FC in the 11-17 nm range of the glycosylation site, enabling spatially precise imaging. This approach successfully enabled fluorescence imaging of glycoproteins across various cell lines and the detection of changes in glycoprotein levels induced by drugs.

Recently, polyurethane elastomer (TPU) has attracted more and more attention depending on its excellent optical, mechanical, and retreatment properties. The high strength of polyurethane has always been pursued, which can enable its application in more fields. In this work, an aliphatic polyurethane elastomer membrane (HRPU6) was successfully synthesized, and its strength was obviously improved by solvent annealing technology. The tensile strength and adhesion strength can reach 64.56 and 2.58 MPa, but 36.55 and 1.57 MPa only before solvent annealing, respectively. The impact strength of laminated glass based on HRPU has also been significantly improved after solvent annealing, confirmed through drop ball impact testing. It has been confirmed that the increase in strength of HRPU6 is attributed to the enhancement of hydrogen bonding and the improvement of the phase separation degree.

Metal-organic frameworks (MOFs) are potential candidates for gas-selective adsorbents for the separation of an ethylene/ethane mixture. To accelerate material discovery, high-throughput computational screening is a viable solution. However, classical force fields, which were widely employed in recent studies of MOF adsorbents, have been criticized for their failure to cover complicated interactions such as those involving π electrons. Herein, we demonstrate that machine learning force fields (MLFFs) trained on quantum-chemical reference data can overcome this difficulty. We have constructed a MLFF to accurately predict the adsorption energies of ethylene and ethane on the organic linkers of MOFs and discovered that the π electrons from both the ethylene molecule and the aromatic rings in the linkers could substantially influence the selectivity for gas adsorption. Four kinds of MOF linkers are identified as having promise for the separation of ethylene and ethane, and our results could also offer a new perspective on the design of MOF building blocks for diverse applications.

The synthesis and characterization of platinum(II) and palladium(II) complexes bearing two (dimers Pt(L pc ) 2 Cl 2 and Pd(L pc ) 2 Cl 2 ), one (monomers Pt(L pc )(L ref )Cl 2 and Pd(L pc )(L ref )Cl 2 ), or no (reference compounds Pt(L ref ) 2 Cl 2 and Pd(L ref ) 2 Cl 2 ) pentacene-based pyridyl ligands are presented. Photophysical properties of the dimers are probed by means of steady-state and time-resolved transient absorption measurements in comparison to the monomer and model compounds. Our results document that despite enhanced spin-orbit coupling from the presence of heavy atoms, intramolecular singlet fission (iSF) is not challenged by intersystem crossing. iSF thus yields correlated triplet pairs and even uncorrelated triplet excited states upon decoherence. Importantly, significant separation of the two pentacenyl groups facilitates decoupling of the two chromophores. Furthermore, the mechanism of iSF is altered depending on the respective metal center, that is, Pt(II) versus Pd(II). The dimer based on Pt(II), Pt(L pc ) 2 Cl 2 , exhibits a direct pathway for the iSF and forms a correlated triplet pair with singlet-quintet spin-mixing within 10 ns in variable solvents. On the other hand, the dimer based on Pd(II), Pd(L pc ) 2 Cl 2 , leads to charge transfer mixing during the population of the correlated triplet pair that is dependent on solvent polarity. Moreover, Pd(L pc ) 2 Cl 2 gives rise to a stable equilibrium between singlet and quintet correlated triplet pairs with lifetimes of up to 170 ns. Inherent differences in the size and polarizability, when contrasting platinum(II) with palladium(II), are the most likely rationale for the underlying trends., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Co-published by University of Science and Technology of China and American Chemical Society.)

Photon energy conversion can be accomplished in many different ways, including the two opposing manners, down-conversion (i.e., singlet fission, SF) and up-conversion (i.e., triplet-triplet annihilation up-conversion, TTA-UC). Both processes have the potential to help overcome the detailed balance limit of single-junction solar cells. Tetracene, in which the energies of the lowest singlet excited state and twice the triplet excited state are comparable, exhibits both down- and up-conversion. Here, we have designed meta -diethynylphenylene- and 1,3-diethynyladamantyl-linked tetracene dimers, which feature different electronic coupling, to characterize the interplay between intramolecular SF (intra-SF) and intramolecular TTA-UC (intra-TTA-UC) via steady-state and time-resolved absorption and fluorescence spectroscopy. Furthermore, we have used Pd-phthalocyanine as a sensitizer to enable intra-TTA-UC in the two dimers via indirect photoexcitation in the near-infrared part of the solar spectrum. The work is rounded off by temperature-dependent measurements, which outline key aspects of how thermal effects impact intra-SF and intra-TTA-UC in different dimers.

Several dumbbell conjugates featuring M 3 N@ I h (M = Sc, Y) and C 80 (M = Sc, Y) and C 60 were prepared to systematically investigate interfullerene electronic interactions and excited state dynamics. From electrochemical investigations, we concluded that the redox potentials of our M 3 N@ I (M = Sc, Y) dumbbells depend largely on the interfullerene electronic interactions. Assisted by DFT calculation, the unique role of metal atoms was highlighted. Most importantly, ultrafast spectroscopy experiments revealed symmetry-breaking charge separation in Sc h -C 80 (M = Sc, Y) dumbbells depend largely on the interfullerene electronic interactions. Assisted by DFT calculation, the unique role of metal atoms was highlighted. Most importantly, ultrafast spectroscopy experiments revealed symmetry-breaking charge separation in Sc 3 N@C 80 -dumbbell to yield an unprecedented (Sc 3 N@C 80 ) •+ -(Sc 3 N@C 80 ) •- charge separated state. This is, to the best of our knowledge, the first time that symmetry-breaking charge separation following photoexcitation is corroborated in a fullerene system. As such, our work shed light on the significance of interfullerene electronic interactions and their uniqueness for modulating excited state properties.

Despite the significant number of studies that have recently focused on plant invasion and invasive plants' success, many uncertainties still exist on the effects of invasive plant identity and diversity on the native plant response under different levels of diversity. A mixed planting experiment was conducted using the native Lactuca indica ( L. indica ) and four invasive plants. The treatments consisted of 1, 2, 3, and 4 levels of invasive plants richness in different combinations in competition with the native L. indica . Here, the results showed that native plant response depends on the invasive plant identity and invasive plant diversity, which increases the native plant total biomass under 2-3 levels of invasive plant richness and decreases under high invasive plant density. This plant diversity effect was more significant in the native plant relative interaction index, which shows negative values except under a single invasion with Solidago canadensis and Pilosa bidens . The native plant leaf nitrogen level increased under four levels of invasive plant richness, which means more affected by invasive plant identity than invasive plant diversity. Finally, this study demonstrated that native plant response under invasion depends on the identity and diversity of invasive plants., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

A growing number of studies reported that obesity is one of the major inducements for osteoporosis by promoting excessive adipogenic differentiation of bone marrow mesenchymal stem cells (BMSCs). Marine-derived DHA-enriched phosphatidylcholine (DHA-PC) exhibited activities to improve ovariectomized-induced osteoporosis and kidney damage. However, the potential effect of DHA-PC and efficacy differences between DHA-PC and traditional DHA (DHA-triglyceride, DHA-TG) on BMSCs differentiation in obesity-induced osteoporosis were not clear. In the present study, obesity-induced osteoporotic mice were supplemented with DHA-TG and DHA-PC for 120 days. Results showed that supplementing with DHA-PC improved the bone mineral density and biomechanical properties, increased the new bone formation rate by 55.2%, and reduced the amount of bone marrow fat to a greater extent than DHA-TG. Further in vitro results showed that DHA-PC significantly promoted the osteogenic differentiation and inhibited the adipogenic differentiation of BMSCs. Mechanistically, DHA-PC supplement up-regulated Wnt/β-catenin pathway in BMSCs and up-regulated the expression of osteogenic transcription factors, thereby promoting osteogenic differentiation. In summary, DHA-PC exerted a superior effect to DHA-TG in improving obesity-induced osteoporosis. The results provided new evidence for the application of different molecular forms of DHA in treatment of osteoporosis.

The sea cucumber intestine is a major by-product of sea cucumber processing and contains high levels of protein. In this study, we isolated and identified 28 novel osteogenic peptides from sea cucumber intestinal hydrolysis by the activity-tracking method for the first time. In vitro experimental results showed that compared with high molecular weight, the peptides from sea cucumber intestine (SCIP) with molecular weight <3 kDa more significantly promoted the proliferation and mineralized nodules of MC3T3-E1 cell and exhibited potential integrin binding capacity. In vivo experimental results showed that the SCIP supplement significantly increased the longitudinal bone length and elevated the height of the growth plate (especially the hypertrophic zone, 37.2%, p < 0.01) in adolescent mice. Further, immunofluorescence labeling results indicated that the SCIP supplement increased chondrocyte transdifferentiate to osteoblast in the growth plate close to the diaphysis. Mechanistically, transcriptome analysis revealed that the SCIP supplement induced the dedifferentiation of chondrocyte to osteoprogenitor cell via integrin-mediated histone acetylation and then redifferentiated to osteoblast via integrin-mediated Wnt/β-catenin signaling. These results reported for the first time that sea cucumber intestine had the potential to develop into a dietary supplement for promoting osteogenic, and provide new evidence for the mechanism of dietary promotes chondrocyte to osteoblast transdifferentiation.

The development of electrolytes with high safety, high ionic conductivity, and the ability to inhibit lithium dendrites growth is crucial for the fabrication of high-energy-density lithium metal batteries. In this study, a ternary eutectic electrolyte is designed with LiTFSI (TFSI = bis(trifluoromethanesulfonyl)imide), butyrolactam (BL), and succinonitrile (SN). This electrolyte exhibits a high ion conductivity, nonflammability, and a wide electrochemical window. The competitive solvation effect among SN, BL, and Li + reduces the viscosity and improves the stability of the eutectic electrolyte. The preferential coordination of BL toward Li + facilitates the formation of stable solid electrolyte interphase films, leading to homogeneous and dendrite-free Li plating. As expected, the LiFePO 4 /Li cell with this ternary eutectic electrolyte delivers a high capacity retention of 90% after 500 cycles at 2 C and an average Coulombic efficiency of 99.8%. Moreover, Ni-rich LiNi 0.8 Co 0.1 Al 0.1 O 2 /Li and LiNi 0.8 Co 0.1 Mn 0.1 O 2 /Li cells based on the modified ternary eutectic electrolyte achieve an outstanding cycling performance. This study provides insights for understanding and designing better electrolytes for lithium metal batteries and analogous sodium/potassium metal batteries.

Hydrogels with inherent antibacterial ability are a focus in soft tissue repair. Herein, a series of antibacterial hydrogels were fabricated by quaternized N -[3-(dimethylamino)propyl] methacrylamide (quaternized P(DMAPMA-DMA-DAA)) bearing copolymers with dithiodipropionic acid dihydrazide (DTDPH) as cross-linker. The hydrogels presented efficient self-healing capability as well as a pH and redox-triggered gel-sol-gel transition property that is based on the dynamic acylhydrazone bond and disulfide linkage. Furthermore, the hydrogels showed good antibacterial activity, biocompatibility, degradability, and sustained release ability. More importantly, the in vivo experiments demonstrated that the hydrogels loaded with mouse epidermal growth factor (mEGF) significantly accelerated wound closure by preventing bacterial infection and promoting cutaneous regeneration in the wound model. The antibacterial hydrogels with self-healing behavior hold great potential in wound treatment.

Reaching the goal of developing an insensitive high-energy molecule ( IHEM ) is a major challenge. In this study, 3,5-diamino-6-hydroxy-2-oxide-4-nitropyrimidone ( IHEM-1 ) was synthesized in one step from 2,4,6-triamino-5-nitropyrimidine-1,3-dioxide hydrate (ICM-102 hydrate). The density of compound IHEM-1 is 1.95 g cm -3 with a decomposition temperature of 271 °C. Its detonation velocity and pressure are 8660 m s -1 and 33.64 GPa, respectively, which are far superior to the detonation performance of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), while its sensitivity is identical with that of TATB. In addition, four derivatives ( 1a , chloride; 1b , nitrate; 1c , perchlorate; and 1d , dinitramide) were prepared on the basis of the weak base site (N-O group) and show excellent energetic properties. By combining a series of advantages, including simple preparation, high yield, high density, very low solubility in aqueous solution, high thermostability, insensitivity, and excellent detonation performance, IHEM-1 approaches an ideal insensitive high-energy molecule. Compounds 1b - 1d are also competitive as new high-energy-density materials.

Many countries have dedicated to the mitigation of air pollution in the past several decades. However, evidence of beneficial effects of air quality improvement on chronic kidney disease (CKD) remains limited. We thus investigated the effects of dynamic changes (including deterioration and improvement) in air quality on the incidence of CKD in a longitudinal study in Taiwan. During 2001-2016, this study recruited a total of 163,197 Taiwanese residents who received at least two standard physical examinations. The level of fine particle matter (PM 2.5 ) was estimated using a high-resolution (1 km 2 ) satellite-based spatio-temporal model. We defined changes of PM 2.5 concentrations (ΔPM 2.5 ) as the difference between the two-year average measurements during follow-up and during the immediately preceding visit. The time-dependent Cox regression model was adopted to evaluate the relationships between ΔPM 2.5 and the incidence of CKD after adjusting for a series of covariates. The concentrations of PM 2.5 in Taiwan peaked around 2004 and began to decrease since 2005. We observed an approximate linear concentration-response relationship of ΔPM 2.5 with CKD incidence. Every 5 μg/m 3 decrease in the ambient concentration of PM 2.5 was associated with a 25% reduced risk of CKD development [hazard ratio (HR): 0.75; 95% CI: 0.73, 0.78]. In conclusion, this study demonstrated that the improvement of PM 2.5 air quality might be associated with a lower risk of CKD development. Our findings indicate that reducing air pollution may effectively prevent the development of CKD.

Thermoelectric (TE) technology provides a new way to directly harvest and convert the heat continuously released from the human body. The greatest challenge for TE materials applied in wearable TE generators is compatible with the constantly changing morphology of the human body while offering a continuous and stable power output. Here, a stretchable carboxylic single-walled carbon nanotube (SWNT)-based TE fiber is prepared by an improved wet-spinning method. The stable Seebeck coefficient of the annealed carboxylic SWNT-based TE fiber is 44 μV/K even under the tensile strain of ∼30%. Experimental results show that the fiber can continue to generate constant TE potential when it is changed to various shapes. The new stretchable TE fiber has a larger Seebeck coefficient and more stretchability than existing TE fibers based on the Seebeck effect, opening a path to using the technology for a variety of practical applications.

Recent years have witnessed various in-depth research efforts on self-reconstruction behavior toward electrocatalysis. Tracking the phase transformation and evolution of true active sites is of great significance for the development of self-reconstructed electrocatalysts. Here, the optimized atomic sulfur-doped bismuth nanobelt (S-Bi) is fabricated via an electrochemical self-reconstruction evolved from Bi 2 S 3 . Advanced technologies have demonstrated that the nonmetallic S atoms have been doped into the lattice Bi frame, leading to the reconstruction of local electronic structure of Bi. The as-prepared S-Bi nanobelt exhibits a remarkable NH 3 generation rate of 10.28 μg h -1 mg -1 and Faradaic efficiency of 10.48%. Density functional theory calculations prove that the S doping can significantly lower the energy barrier of the rate-determining step and enlarge the N≡N bond for further dissociation toward N 2 fixation. This work not only establishes insights into the evolution process of electrochemically derived self-reconstruction but also unravels the root of the N 2 reduction reaction mechanism associated with the atomic nonmetal dopants.

Elevated atmospheric nitrogen (N) deposition has significantly influenced aquatic ecosystems, especially with regard to their N budgets and phytoplankton growth potentials. Compared to a considerable number of studies on oligotrophic lakes and oceanic waters, little evidence for the importance of N deposition has been generated for eutrophic lakes, even though emphasis has been placed on reducing external N inputs to control eutrophication in these lakes. Our high-resolution observations of atmospheric depositions and riverine inputs of biologically reactive N species into eutrophic Lake Dianchi (the sixth largest freshwater lake in China) shed new light onto the contribution of N deposition to total N loads. Annual N deposition accounted for 15.7% to 16.6% of total N loads under variable precipitation conditions, 2-fold higher than previous estimates (7.6%) for the Lake Dianchi. The proportion of N deposition to total N loads further increased to 27-48% in May and June when toxic blooms of the ubiquitous non-N 2 fixing cyanobacteria Microcystis spp. are initiated and proliferate. Our observations reveal that reduced N (59%) contributes a greater amount than oxidized N to total N deposition, reaching 56-83% from late spring to summer. Progress toward mitigating eutrophication in Lake Dianchi and other bloom-impacted eutrophic lakes will be difficult without reductions in ammonia emissions and subsequent N deposition.

A particular bispyrene fluorophore (1) with two pyrene moieties covalently linked via a hydrophilic spacer was synthesized. Fluorescence measurements reveal that the fluorescence emission of 1 could be well modulated by a cationic surfactant, dodecyltrimethylammonium bromide (DTAB). Protein sensing studies illustrate that the selected ensemble based on 1/DTAB assemblies exhibits ratiometric responses to nonmetalloproteins and turn-off responses to metalloproteins, which can be used to differentiate the two types of proteins. Moreover, negatively charged nonmetalloproteins can be discriminated from the positively charged ones according to the difference in ratiometric responses. Fluorescence sensing studies with control bispyrenes indicate that the polarity of the spacer connecting two pyrene moieties plays an important role in locating bispyrene fluorophore in DTAB assemblies, which further influences its sensing behaviors to noncovalent interacting proteins. This study sheds light on the influence of the probe structure on the sensing performance of a fluorescent ensemble based on probe and surfactant assemblies.