Compression of Organic Molecules Coupled with Hydrogen Bonding Extends the Charge Carrier Lifetime in BA2SnI4.

Two-dimensional (2D) metal halide perovskites, such as BA2SnI4 (BA═CH3(CH2)3NH3), exhibit an enhanced charge carrier lifetime in experiments under strain. Experiments suggest that significant compression of the BA molecule, rather than of the inorganic lattice, contributes to this enhancement. To elucidate the underlying physical mechanism, we apply a moderate compressive strain to the entire system and subsequently introduce significant compression to the BA molecules. We then perform ab initio nonadiabatic molecular dynamics simulations of nonradiative electron-hole recombination. We observe that the overall lattice compression reduces atomic motions and decreases nonadiabatic coupling, thereby delaying electron-hole recombination. Additionally, compression of the BA molecules enhances hydrogen bonding between the BA molecules and iodine atoms, which lengthens the Sn-I bonds, distorts the [SnI6]4- octahedra, and suppresses atomic motions further, thus reducing nonadiabatic coupling. Also, the elongated Sn-I bonds and weakened antibonding interactions increase the band gap. Altogether, the compression delays the nonradiative electron-hole recombination by more than a factor of 3. Our simulations provide new and valuable physical insights into how compressive strain, accommodated primarily by the organic ligands, positively influences the optoelectronic properties of 2D layered halide perovskites, offering a promising pathway for further performance improvements.

Self-passivation of Halide Interstitial Defects by Organic Cations in Hybrid Lead-Halide Perovskites: Ab Initio Quantum Dynamics.

Halide interstitial defects severely hinder the optoelectronic performance of metal halide perovskites, making research on their passivation crucial. We demonstrate, using ab initio nonadiabatic molecular dynamics simulations, that hydrogen vacancies (Hv) at both N and C atoms of the methylammonium (MA) cation in MAPbI3 efficiently passivate iodine interstitials (Ii), providing a self-passivation strategy for dealing with the Hv and Ii defects simultaneously. Hv at the N site (Hv-N) introduces a defect state into the valence band, while the state contributed by Hv at the C site (Hv-C) evolves from a shallow level at 0 K to a deep midgap state at ambient temperature, exhibiting a high environmental activity. Both Hv-N and Hv-C are strong Lewis bases, capable of capturing and passivating Ii defects. Hv-C is a stronger Lewis base, bonds with Ii better, and exhibits a more pronounced passivation effect. The charge carrier lifetimes in the passivated systems are significantly longer than in those containing either Hv or Ii, and even in pristine MAPbI3. Our demonstration of the Hv and Ii defect self-passivation in MAPbI3 suggests that systematic control of the relative concentrations of Hv and Ii can simultaneously eliminate both types of defects, thereby minimizing charge and energy losses. The demonstrated defect self-passivation strategy provides a promising means for defect control in organic-inorganic halide perovskites and related materials and deepens our atomistic understanding of defect chemistry and charge carrier dynamics in solar energy and optoelectronic materials.

Defect Engineering of Bi2WO6 for Enhanced Photocatalytic Degradation of Antibiotic Pollutants.

Infiltration of excessive antibiotics into aquatic ecosystems plays a significant role in antibiotic resistance, a major global health challenge. It is therefore critical to develop effective technologies for their removal. Herein, defect-rich Bi2WO6 nanoparticles are solvothermally prepared via epitaxial growth on pristine Bi2WO6 seed nanocrystals, and the efficiency of the photocatalytic degradation of ciprofloxacin, a common antibiotic, is found to increase markedly from 62.51% to 98.27% under visible photoirradiation for 60 min. This is due to the formation of a large number of structural defects, where the synergistic interactions between grain boundaries and adjacent dislocations and oxygen vacancies lead to an improved separation and migration efficiency of photogenerated carriers and facilitate the adsorption and degradation of ciprofloxacin, as confirmed in experimental and theoretical studies. Results from this work demonstrate the unique potential of defect engineering for enhanced photocatalytic performance, a critical step in removing antibiotic contaminants in aquatic ecosystems.

Sirtuin 3-activated superoxide dismutase 2 mediates fluoride-induced osteoblastic differentiation in vitro and in vivo by down-regulating reactive oxygen species.

Skeletal fluorosis is a chronic metabolic bone disease caused by long-term excessive fluoride intake. Abnormal differentiation of osteoblasts plays an important role in disease progression. Research on the mechanism of fluoride-mediated bone differentiation is necessary for the prevention and treatment of skeletal fluorosis. In the present study, a rat model of fluorosis was established by exposing it to drinking water containing 50 mg/L F-. We found that fluoride promoted Runt-related transcription factor 2 (RUNX2) as well as superoxide dismutase 2 (SOD2) and sirtuin 3 (SIRT3) expression in osteoblasts of rat bone tissue. In vitro, we also found that 4 mg/L sodium fluoride promoted osteogenesis-related indicators as well as SOD2 and SIRT3 expression in MG-63 and Saos-2 cells. In addition, we unexpectedly discovered that fluoride suppressed the levels of reactive oxygen species (ROS) and mitochondrial reactive oxygen species (mtROS) in osteoblasts. When SOD2 or SIRT3 was inhibited in MG-63 cells, fluoride-decreased ROS and mtROS were alleviated, which in turn inhibited fluoride-promoted osteogenic differentiation. In conclusion, our results suggest that SIRT3/SOD2 mediates fluoride-promoted osteoblastic differentiation by down-regulating reactive oxygen species.

Intrinsic defects in B-site columnar-ordered halide double perovskites Cs2AgPdBr5.

Cs2AgPdBr5 is a new type of double perovskite with one-dimensional electronic dimensionality, which is expected to be a promising candidate of photovoltaic materials. Considering that defects usually exist in real materials, in this study, we investigate the intrinsic defect properties of Cs2AgPdBr5 from first principles. First, the phase diagram of Cs2AgPdBr5 is calculated. It turns out that its thermodynamic stable region is small, suggesting that the growth conditions should be carefully controlled to obtain high-quality samples. By systematically investigating the Fermi-level pinning behavior, we find that p-type Cs2AgPdBr5 can be obtained at an Ag-poor condition. At the same time, Pd2+i and Pd1+Ag are the only two deep-level recombination centers at 300 K. Therefore, if possible, the amount of palladium should be relatively small in the synthesis process. Our study provides guidance to obtain high-performance Cs2AgPdBr5 materials for photovoltaic applications.

Single Molecular Reaction of Water on a ZnO Surface.

The dissociation of a single water molecule on a ZnO(101̅0) surface has been investigated at the atomic level by low temperature STM manipulation combined with DFT calculations. The positive pulses applied from the tip inject electrons into the system and break the bonding between water and the ZnO surface, thus leading to the hopping of water molecules. Negative pulses inject holes wherein the lower energy ones split the free O-H bond pointing out of the surface whereas the higher energy ones split the second O-H bond that is directed to the surface through hydrogen bonding. Moreover, the yielded proton and hydroxyl species present distinctly charged status through different reaction pathways, manifesting their unique impacts on tailoring the surface properties of the metal oxide.

Half-filled intermediate bands in doped inorganic perovskites for solar cells.

Efficiency of solar cells can be improved by introducing intermediate bands. However, width and occupation requirements on the intermediate bands bring challenges for materials design. In this study, we systematically investigate the electronic structure of doped CsPbX3 (X = Cl, Br, or I). A screening in transition metals suggests that Cr and Mo doped perovskites have dispersive and half-filled intermediate bands, which is desirable for building solar cells. However, intermediate bands originated from degenerated d orbitals are easily split when the octahedral symmetry of the local chemical environment around the dopant is broken. To avoid this problem, we further perform a screening of non-transition metals aiming to generate sp orbital-based intermediate bands. It turns out that In and Ga can generate a half-filled intermediate band, which is not sensitive to the local symmetry. The estimated efficiency of In and Ga doped CsPbCl3 at a doping concentration of 8.3% is 57.97% and 54.21%, notably higher than the Shockley-Queisser limit (40.7%). Results presented here demonstrate the potential of intermediate band engineering in photovoltaic applications.

Homocysteine induces vascular inflammatory response via SMAD7 hypermethylation in human umbilical vein smooth muscle cells.

Homocysteine (Hcy) can induce atherosclerosis through the inflammatory response and DNA methylation disorder. Our recent study has reported a novel epigenetic modified gene related to atherosclerosis -SMAD7. To further understand the pathogenesis of atherosclerosis, the current study was designed to investigate an inflammatory role of Hcy in human umbilical vein smooth muscle cells (HUVSMCs) through interfering with SMAD7 methylation. Using MALDI-TOF MS, we found that Hcy increased DNA methylation levels of SMAD7 promoter in a dose and time-dependent manner in HUVSMCs. Meanwhile, both SMAD7 mRNA and protein levels were decreased along with the increase of Hcy concentrations and treating time. Decreased SMAD7 levels led to up regulation of pro-inflammatory cytokines (TNF-α and IL-1ß) expression in HUVSMCs. Furthermore, we found that activation of NF-κB pathway was the mechanism by which reduced Smad7 levels enhanced vascular inflammation. Thus, Hcy is able to activate NF-κB-mediated vascular inflammatory response via inducing hypermethylation of SMAD7 promoter in HUVSMCs. The in vitro findings supplement our recent clinical study that SMAD7 methylation as a novel marker in atherosclerosis and further elucidate the role of Hcy in atherogenesis.

Multi-Objective Sliding Mode Control on Vehicle Cornering Stability with Variable Gear Ratio Actuator-Based Active Front Steering Systems.

Active front steering (AFS) is an emerging technology to improve the vehicle cornering stability by introducing an additional small steering angle to the driver's input. This paper proposes an AFS system with a variable gear ratio steering (VGRS) actuator which is controlled by using the sliding mode control (SMC) strategy to improve the cornering stability of vehicles. In the design of an AFS system, different sensors are considered to measure the vehicle state, and the mechanism of the AFS system is also modelled in detail. Moreover, in order to improve the cornering stability of vehicles, two dependent objectives, namely sideslip angle and yaw rate, are considered together in the design of SMC strategy. By evaluating the cornering performance, Sine with Dwell and accident avoidance tests are conducted, and the simulation results indicate that the proposed SMC strategy is capable of improving the cornering stability of vehicles in practice.

Signalling pathways underlying pulsed electromagnetic fields in bone repair.

Pulsed electromagnetic field (PEMF) stimulation is a prospective non-invasive and safe physical therapy strategy for accelerating bone repair. PEMFs can activate signalling pathways, modulate ion channels, and regulate the expression of bone-related genes to enhance osteoblast activity and promote the regeneration of neural and vascular tissues, thereby accelerating bone formation during bone repair. Although their mechanisms of action remain unclear, recent studies provide ample evidence of the effects of PEMF on bone repair. In this review, we present the progress of research exploring the effects of PEMF on bone repair and systematically elucidate the mechanisms involved in PEMF-induced bone repair. Additionally, the potential clinical significance of PEMF therapy in fracture healing is underscored. Thus, this review seeks to provide a sufficient theoretical basis for the application of PEMFs in bone repair.

Anthocyanins from blueberry ameliorated arsenic-induced memory impairment, oxidative stress, and mitochondrial-biosynthesis imbalance in rat hippocampal neurons.

In this study, blueberry anthocyanins extract (BAE) was used to investigate its protective effect on arsenic-induced rat hippocampal neurons damage. Arsenic exposure resulted in elevated levels of oxidative stress, decreased antioxidant capacity and increased apoptosis in rat hippocampal brain tissue and mitochondria. Immunohistochemical results showed that arsenic exposure also significantly decreased the expression of mitochondrial biosynthesis-related factors PGC-1α and TFAM. Treatment with BAE alleviated the decrease in antioxidant capacity, mitochondrial biogenesis related protein PGC-1α/NRF2/TFAM expression, and ATP production of arsenic induced hippocampal neurons in rats, and improved cognitive function in arsenic damaged rats. This study provides new insights into the detoxification effect of anthocyanins on the nervous system toxicity caused by metal exposure in the environment, indicating that anthocyanins may be a natural antioxidant against the nervous system toxicity caused by environmental metal exposure.

Piezoelectrically-activated antibacterial catheter for prevention of urinary tract infections in an on-demand manner.

Catheter-associated urinary tract infection (CAUTI) is a common clinical problem, especially during long-term catheterization, causing additional pain to patients. The development of novel antimicrobial coatings is needed to prolong the service life of catheters and reduce the incidence of CAUTIs. Herein, we designed an antimicrobial catheter coated with a piezoelectric zinc oxide nanoparticles (ZnO NPs)-incorporated polyvinylidene difluoride-hexafluoropropylene (ZnO-PVDF-HFP) membrane. ZnO-PVDF-HFP could be stably coated onto silicone catheters simply by a one-step solution film-forming method, very convenient for industrial production. In vitro, it was demonstrated that ZnO-PVDF-HFP coating could significantly inhibit bacterial growth and the formation of bacterial biofilm under ultrasound-mediated mechanical stimulation even after 4 weeks. Importantly, the on and off of antimicrobial activity as well as the strenth of antibacterial property could be controlled in an adaptive manner via ultrasound. In a rabbit model, the ZnO-PVDF-HFP-coated catheter significantly reduced the incidence CAUTIs compared with clinically-commonly used catheters under assistance of ultrasonication, and no side effect was detected. Collectively, the study provided a novel antibacterial catheter to prevent the occurrence of CAUTIs, whose antibacterial activity could be controlled in on-demand manner, adaptive to infection situation and promising in clinical application.

The sp3 Defect Decreases Charge Carrier Lifetime in (8,3) Single-Walled Carbon Nanotubes.

A recent experimental approach introduces sp3 defects into single-walled carbon nanotubes (SWNTs) through controlled functionalization with guanine, resulting in a decrease in charge carrier lifetime. However, the physical mechanism behind this phenomenon remains unclear. We employ nonadiabatic molecular dynamics to systematically model the nonradiative recombination process of electron-hole pairs in SWNTs with sp3 defects generated by a guanine molecule. We demonstrate that the introduction of sp3 defects creates an overlapping channel between the highest occupied (HOMO) and lowest unoccupied molecular orbital (LUMO), significantly enhancing the nonadiabatic (NA) coupling and leading to a 4.7-fold acceleration in charge carrier recombination compared to defect-free SWNTs. The charge carrier recombination slows significantly at a lower temperature (50 K) due to the weakening of the NA coupling. Our results rationalize the accelerated recombination of charge carriers in SWNTs with sp3 defects in experiments and contribute to a deeper understanding of the carrier dynamics in SWNTs.

Increasing the Efficiency of Photocatalytic Water Splitting via Introducing Intermediate Bands.

Photocatalytic water splitting is a potential way to utilize solar energy. To be practically useful, it is important to have a high solar-to-hydrogen (STH) efficiency. In this study, we propose a conceptually new photocatalytic water splitting model based on intermediate bands (IBs). In this new model, introducing IBs within the band gap can significantly increase the STH efficiency limit (from 30.7% to 48.1% without an overpotential and from 13.4% to 36.2% with overpotentials) compared to that in conventional single-band gap photocatalytic water splitting. First-principles calculations indicate that N-doped TiO2, Bi-doped TiO2, and P-doped ZnO have suitable IBs that can be used to construct IB photocatalytic water splitting systems. The STH efficiency limits of these three doped systems are 10.0%, 12.0%, and 19.0%, respectively, while those of pristine TiO2 and ZnO without IB are only 0.9% and 1.6%, respectively. The IB photocatalytic water splitting model proposed in this study opens a new avenue for photocatalytic water splitting design.

Arsenic-Induced, Mitochondria-Mediated Apoptosis Is Associated with Decreased Peroxisome Proliferator-Activated Receptor γ Coactivator α in Rat Brains.

Chronic exposure to arsenic in drinking water damages cognitive function, and nerve cell apoptosis is one of the primary characteristics. The damage to mitochondrial structure and/or function is one of the main characteristics of apoptosis. Peroxisome proliferator-activated receptor γ coactivator α (PGC-1α) is involved in the regulation of mitochondrial biogenesis, energy metabolism, and apoptosis. In this study, we aimed to study the role of PGC-1α in sodium arsenite (NaAsO2)-induced mitochondrial apoptosis in rat hippocampal cells. We discovered that increased arsenic-induced apoptosis in rat hippocampus increased with NaAsO2 (0, 2, 10, and 50 mg/L, orally via drinking water for 12 weeks) exposure by TUNEL assay, and the structure of mitochondria was incomplete and swollen and had increased lysosomes, lipofuscins, and nuclear membrane shrinkage observed via transmission electron microscopy. Furthermore, NaAsO2 reduced the levels of Bcl-2 and PGC-1α and increased the levels of Bax and cytochrome C expression. Moreover, correlation analysis showed that brain arsenic content was negatively correlated with PGC-1α levels and brain ATP content; PGC-1α levels were negatively correlated with apoptosis rate; and brain ATP content was positively correlated with PGC-1α levels, but no significant correlation between ATP content and apoptosis has been observed in this study. Taken together, the results of this study indicate that NaAsO2-induced mitochondrial pathway apoptosis is related to the reduction of PGC-1α, accompanied by ATP depletion.

The disruption of blood-brain barrier induced by long-term arsenic exposure is associated with the increase of MMP-9 and MMP-2: The characteristics are similar to those caused by senescence.

Accumulating evidence suggests that Matrix metalloproteinase-9 (MMP-9) and -2 (MMP-2) are involved in the neuropathological processes by contributing to breaking the extracellular matrix and the tight junctions that constitute the blood-brain barrier (BBB). However, the influences of arsenic (As) on these two MMPs were inconsistent. In the cross-sectional study of 500 adults, serum MMP-2 and MMP-9 positively correlated with urine arsenic. And the positive correlation between urine tAs and serum MMP-9/2 was found in people older than 59 years. In vivo studies, we found that arsenic exposure or senescence might decrease number of neurons and neuritic density and increase serum and cortical MMP-9/2 levels. Furthermore, arsenic exposure or senescence could disrupt the tight junction of BBB and elevate MMP-9 and MMP-2 expression in the cerebral microvascular endothelium. The MMP-9 and MMP-2 are of particular interest when researching the link between arsenic exposure and nerve damage.

The Important Role of Optical Absorption in Determining the Efficiency of Intermediate Band Solar Cells and a Design Principle for Perovskite Doping.

The efficiency of solar cells can be increased by introducing an intermediate band (IB) in the band gap. Considering that absorption within the band gap is typically weak, the efficiency of IB solar cells was overestimated previously, with a strong enough optical absorption assumed. Here, we propose a new formulism to calculate the limit of the efficiency of IB solar cells with the ideal absorption assumption removed, which can be used to evaluate the effect of absorption. New IB materials are designed via doping double perovskite, which has a relatively strong absorption within the band gap with both d-p and s-p transitions. The limit of the efficiency of a 2 µm thick Sn-doped Cs2AgBiBr6 is 38.6% under the AM1.5G spectrum, which is only ∼6% smaller than the ideal-absorption estimation. Results presented here provide a new dimension in the rational design of IB solar cell materials.

Biodegradable Silk Fibroin Nanocarriers to Modulate Hypoxia Tumor Microenvironment Favoring Enhanced Chemotherapy.

Biopolymer silk fibroin (SF) is a great candidate for drug carriers characterized by its tunable biodegradability, and excellent biocompatibility properties. Recently, we have constructed SF-based nano-enabled drug delivery carriers, in which doxorubicin (Dox) and atovaquone (Ato) were encapsulated with Arg-Gly-Asp-SF-Polylactic Acid (RSA) to form micellar-like nanoparticles (RSA-Dox-Ato NPs). The RGD peptide was decorated on micellar-like nanoparticles, promoting tumor accumulation of the drug. Meanwhile, Ato, as a mitochondrial complex III inhibitor inhibiting mitochondrial respiration, would reverse the hypoxia microenvironment and enhance chemotherapy in the tumor. In vitro, the biopolymer alone showed extremely low cytotoxicity to 4T1 cell lines, while the RSA-Dox-Ato demonstrated a higher inhibition rate than other groups. Most significantly, the ROS levels in cells were obviously improved after being treated with RSA-Dox-Ato, indicating that the hypoxic microenvironment was alleviated. Eventually, SF-based targeted drug carrier provides biocompatibility to reverse hypoxia microenvironment in vivo for enhancing chemotherapy, strikingly suppressing tumor development, and thereby suggesting a promising candidate for drug delivery system.

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The wood used for funeral utensil in ancient tomb is a kind of valuable materials and important for understanding vegetation, climate and society conditions in the history. Here, we identified the tree species and dated the time of wooden utensils for funeral excavated from tombs in Shuijia Village, Shenyang, using wood anatomy methods and dendrochronological techniques. The results showed that 7 out of the 16 wood samples were identified as Pinus tabuliformis from Pinaceae, 8 were Larix sp. from Pinaceae and most likely Larix olgensis, and the rest one was Acer sp. from Aceraceae. Currently, these tree species are still widely distributed in Liaoning Province, indicating that forest structure (tree species composition) is relatively stable and that the climate at that time was quite similar to that at present. The timbers used for wooden utensils of funeral for civilian tombs had regional biogeographic characteristics and reflected regional social productivity development level in Mukden (now Shenyang) in Qing Dynasty: most of them were native tree species with low cost and high availability; the main timber trees were conifer species, and a few of them were broadleaved trees. These timbers were likely from the forest in Shenyang or mountainous areas in Eastern Liaoning, with Hunhe River waterway being an important transport way for timbers to Shenyang. Some P. tabuliformis and Larix sp. timbers could be cross-dated well, and the growth period of the trees was determined to be 1680s-1770s (early to mid-Qing Dynasty). The variations of tree-ring width of these timbers had good consistency and high climate sensitivity, reflecting the consistency of regional climate and environment. These timbers have the potential to indicate the climate condition of the early to mid-Qing Dynasty.

Recent advances in CD8+ regulatory T cell research.

Various subgroups of CD8+ T lymphocytes do not only demonstrate cytotoxic effects, but also serve important regulatory roles in the body's immune response. In particular, CD8+ regulatory T cells (CD8+ Tregs), which possess important immunosuppressive functions, are able to effectively block the overreacting immune response and maintain the body's immune homeostasis. In recent years, studies have identified a small set of special CD8+ Tregs that can recognize major histocompatibility complex class Ib molecules, more specifically Qa-1 in mice and HLA-E in humans, and target the self-reactive CD4+ T ce lls. These findings have generated broad implications in the scientific community and attracted general interest to CD8+ Tregs. The present study reviews the recent research progress on CD8+ Tregs, including their origin, functional classification, molecular markers and underlying mechanisms of action.