Planar Tetracoordinate Silicon in Si3Cu3- Cluster.

Photoelectron spectroscopy and theoretical calculations have identified the global minimum structure of the 16-valence electron Si3Cu3- cluster, which features a planar tetracoordinate silicon (ptSi) in a rhombic arrangement. The Si3 and Cu3 triangles are interconnected by an Si2/Cu2 edge, forming an ordered chain-like structure. Besides the conventional 2c-2e σ-bond connecting Si3 and Cu3, the stability of this cluster is reinforced by a delocalized 3c-2e σ-bond in Cu3 and a π-bond in Si3. Our study provides rare experimental confirmation of a planar hypercoordinate heavier Group 14 element, opening possibilities for exploring similar structures in two-dimensional materials.

Associations between sensory impairment and functional limitations among older Chinese adults: mediating roles of social isolation and cognition.

BACKGROUND: The high prevalence of sensory impairment and functional limitations in older adults is a significant concern, yet there is limited understanding of the relationship between these two conditions. Therefore, the objective of this study was to investigate the pathways connecting sensory impairment and functional limitations by examining serial multiple mediating effects of social isolation and cognition in older adults. METHODS: Using the China Health and Retirement Longitudinal Study dataset, a sample of 4871 older adults was selected. The study variables included sensory impairment, functional limitations, social isolation and cognition, and other covariates. A hierarchical multiple linear regression model was used to assess the association between sensory impairment and functional limitations. Mediation analysis was conducted to explore the sequential multiple mediating effects of social isolation and cognitive function in the relationship between sensory impairment and functional limitations. RESULTS: Our findings revealed a significant and positive association between sensory impairment and functional limitations (B = 0.615, 95% CI: 0.397, 0.834). After adjusting for social isolation and cognitive function, the impact of sensory impairment on functional limitations accounted for 87.19% of the total effect. Additionally, approximately 12.81% of the significant relationship between dual sensory impairment and functional limitations was mediated by social isolation and cognitive function. A serial multiple mediating pathway (sensory impairment → social isolation → cognition → functional limitations) was identified, with a coefficient of 0.013 (95% CI: 0.006, 0.020). CONCLUSIONS: Our study provides evidence for the mediating effects of social isolation and cognition in the relationship between sensory impairment and functional limitations. Given the prevalence of functional limitations among older adults with sensory impairment, it is crucial to consider social isolation and cognitive function in efforts to reduce the burden of disability care. Future validation of these findings through longitudinal studies is necessary.

The prophylactic application of low-dose rabbit antithymocyte globulin in matched siblings HSCT with high-risk factors for graft-versus-host disease.

Relapse and graft-versus-host disease (GVHD) are currently the predominant causes of mortality post allogeneic hematopoietic stem cell transplantation (allo-HSCT). The contentious use of antithymocyte globulin (ATG) for preventing GVHD in matched sibling HSCT scenarios has been a topic of significant debate. A retrospective analysis was conducted on matched sibling HSCT cases with high-risk factors for GVHD in our center from January 2018 to June 2023. Our assessment revealed that the group administered with ATG exhibited a 30 % incidence of acute GVHD (aGVHD), in contrast to 81.8 % in the non-ATG cohort (P = 0.037) among matched sibling HSCT cases with high GVHD risk factors. Furthermore, chronic GVHD (cGVHD) occurred in 20 % of the ATG group and 72.7 % of the non-ATG group (P = 0.03). Notably, the administration of ATG did not significantly impact disease relapse (p = 0.149), infection rates (p = 0.64), granulocyte recovery time (p = 0.15), platelet recovery time (p = 0.12), overall survival (p = 0.889), or disease-free survival time (p = 0.787). The use of rabbit antithymocyte globulin (r-ATG) at a 5 mg/kg dosage demonstrated a notable reduction in aGVHD and cGVHD incidences within sibling matched HSCT cases with high-risk factors for GVHD, without increasing rates of disease recurrence or infections. These findings highlight the potential benefit of using low-dose r-ATG in high-risk of GVHD sibling matched allogeneic HSCTs, although further validation with a larger cohort is necessary.

[Spatiotemporal Variation Characteristics of Ozone and Identification of Key Influencing Factors Based on Random Forest Model： A Case Study of Chuzhou City].

The cause of ozone pollution is a complex scientific problem. Studying the spatiotemporal variation characteristics of O3 at different time scales and analyzing the key influencing factors of O3 concentration is of great significance for the precise formulation of urban air pollution control measures and the improvement of urban air quality. Based on the analysis of the spatiotemporal variation characteristics of O3 concentration in Chuzhou City, we studied the 12 ozone-influencing factors of meteorology and pollutants at multiple time scales using Spearman correlation analysis and a random forest model. The results showed that： ① The O3 pollution level of Chuzhou City showed an aggravating trend, and the O3 concentration distribution showed a spatial pattern of "high in the southeast and low in the northwest." ② From February to May, SO2 concentration had a strong impact on the increase in O3 concentration. From June to September, PM2.5 and PM10 were significantly positively correlated with ozone and had a greater impact. ③ Relative humidity, temperature, and wind speed had a significant impact on O3, whereas barometric pressure and hourly rainfall had a weak impact. ④ The O3 pollution mechanism in Chuzhou City changed from "pollutant-controlled" to "meteorology-controlled." ⑤ Among meteorological and pollutant factors, the three influencing factors that had the greatest influence on O3 concentration were temperature, wind speed, and relative humidity, with PM10 concentration, PM2.5 concentration, and SO2 concentration also contributing. All of the above six influencing factors had a significant nonlinear relationship with the O3 concentration.

[Impact and Mechanism of Medium and Small Flood Regulation in the Three Gorges Reservoir on the Phytoplankton in Tributary Bays].

The regulation of small- and medium-sized floods （RSMF） has become the main mode of regulation in the flood season of the Three Gorges Reservoir （TGR）. To study the response of phytoplankton in the tributary bays of the TGR to the RSMF, a typical eutrophic tributary of the TGR, Xiangxi River, was investigated for the spatiotemporal distribution characteristics of phytoplankton and nutrients in the main and tributary streams from 2020 to 2021. The response characteristics of phytoplankton in the tributary bays to the RSMF were analyzed. The results indicated that during the RSMF, the chlorophyll a （Chl-a） in the water body of the Xiangxi River decreased with the increase in the water level in front of the dam, whereas during the reservoir impounding at the end of flood season, the concentration of Chl-a increased again. During the RSMF, the Chlorophyta and Diatoma were the main communities of planktonic algae in the Xiangxi River. The phytoplankton community changed with the RSMF. When the water level fluctuation increased, diatoms were the main species, whereas when the water level fluctuation was small, blue and green algae were the main species. The concentration of Chl-a was more sensitive to changes in TN concentration. When the flow velocity was >0.25 m·s-1 or the suspended sediment content was >10 mg·L-1, the concentration of Chl-a in the water was inhibited. After 2010, the typical outbreak time of algal blooms in the Xiangxi River Reservoir Bay shifted to the flood season, with only two non-flood season algal blooms. Further attention needs to be paid to the response of algal blooms in the reservoir to small- and medium-sized flood control during the flood season.

Engineering PTS-based glucose metabolism for efficient biosynthesis of bacterial cellulose by Komagataeibacter xylinus.

Bacterial cellulose (BC) is a renewable biomaterial that has attracted significant attention due to its excellent properties and wide applications. Komagataeibacter xylinus CGMCC 2955 is an important BC-producing strain. It primarily produces BC from glucose while simultaneously generating gluconic acid as a by-product, which acidifies the medium and inhibits BC synthesis. To enhance glucose uptake and BC synthesis, we reconstructed the phosphoenolpyruvate-dependent glucose phosphotransferase system (PTSGlc) and strengthened glycolysis by introducing heterologous genes, resulting in a recombinant strain (GX08PTS03; Δgcd::ptsHIcrrE. coli::ptsGE. coli::pfkAE. coli). Strain GX08PTS03 efficiently utilized glucose for BC production without accumulating gluconic acid. Subsequently, the fermentation process was systematically optimized. Under optimal conditions, strain GX08PTS03 produced 7.74 g/L of BC after 6 days of static fermentation, with a BC yield of 0.39 g/g glucose, which were 87.41 % and 77.27 % higher than those of the wild-type strain, respectively. The BC produced by strain GX08PTS03 exhibited a longer fiber diameter along with a lower porosity, significantly higher solid content, crystallinity, tensile strength, and Young's modulus. This study is novel in reporting that the engineered PTSGlc-based glucose metabolism could effectively enhance the production and properties of BC, providing a future outlook for the biopolymer industry.

Change of Flavonoid Content in Wheatgrass in a Historic Collection of Wheat Cultivars.

Wheatgrass is recognized for its nutritional and medicinal properties, partly attributed to its flavonoid content. The objective of this study was to assess the flavonoid content and antioxidant properties of wheatgrass obtained from a wide range of 145 wheat cultivars, which included Chinese landraces (CL), modern Chinese cultivars (MCC), and introduced modern cultivars (IMC). The flavonoids were extracted using a solution of 80% methanol, and their content was evaluated using ultra-high-performance liquid chromatography-mass spectrometry (UHPLC-MS). The results revealed the assessed cultivars showed significant variation in their total flavonoid content (TFC), with MCCs generally having higher amounts compared to CLs. PCA analysis demonstrated clear variations in flavonoid profiles between different cultivar groups, emphasizing the evolutionary inconsistencies in wheat breeding. The antioxidant assays, ABTS, DPPH, and FRAP, exhibited robust abilities for eliminating radicals, which were found to be directly associated with the amounts of flavonoids. In addition, this study investigated the correlation between the content of flavonoids and the ability to resist powdery mildew in a collection of mutated wheat plants. Mutants exhibiting heightened flavonoid accumulation demonstrated a decreased severity of powdery mildew, suggesting that flavonoids play a protective role against fungal infections. The results highlight the potential of wheatgrass as a valuable source of flavonoids that have antioxidant and protective effects. This potential is influenced by the genetic diversity and breeding history of wheatgrass. Gaining insight into these connections can guide future wheat breeding endeavors aimed at improving nutritional value and in strengthening disease resistance. The current finding provides critical information for developing wheatgrass with high flavonoid content and antioxidant activity.

Cognitive impairment in patients with bipolar disorder alone versus those with bipolar disorder comorbid with borderline personality disorder.

BACKGROUND: Bipolar disorder (BD) is a severe mental illness. BD often coexists with borderline personality disorders, making the condition more complex. AIM: To explore the differences in cognitive impairment between patients with BD and those with BD comorbid with borderline personality disorder. METHODS: Eighty patients with BD and comorbid borderline personality disorder and 80 patients with BD alone were included in groups A and B, respectively, and 80 healthy volunteers were included as controls. Cognitive function in each group was evaluated using the Chinese version of the repeatable battery for the assessment of neuropsychological status (RBANS), the Stroop color-word test, and the Wechsler intelligence scale-revised (WAIS-RC). RESULTS: The indices of the RBANS, Stroop color-word test, and WAIS-RC in groups A and B were significantly lower than those of the control group (P < 0.05). Group A had significantly longer Stroop color-word test times for single-character, single-color, double-character, and double-color, lower scores of immediate memory, visual breadth, verbal function dimensions and total score of the RBANS, as well as lower scores of verbal IQ, performance IQ, and overall IQ of the WAIS-RC compared with group B (P < 0.05). Compared to group B, group A exhibited significantly longer single-character time, single-color time, double-character time, and double-color time in the Stroop color-word test (P < 0.05). CONCLUSION: The cognitive function of patients with BD complicated with borderline personality disorder is lower than that of patients with BD.

InnTl4-nH+ (n = 0∼4): Tetracoordinate Hydrogen in a Planar Fashion?

The recent report of planar tetracoordinate hydrogen (ptH) in In4H+ is very intriguing in planar hypercoordinate chemistry. Our high-level CCSD(T) calculations revealed that the proposed D4h-symmetric ptH In4H+ is a first-order saddle point with an imaginary frequency in the out-of-plane mode of the hydrogen atom. In fact, at the CCSD(T)/aug-cc-pV5Z/aug-cc-pV5Z-PP level, the C4v isomer, with the H atom located 0.70 Å above the In4 plane, is 0.5 kcal/mol more stable than the D4h isomer. However, given the small perturbation from planarity and essentially barrierless C4v ↔ D4h ↔ C4v transition, the vibrationally averaged structure can still be considered as a planar. Extending our exploration to the InnTl4-nH+ (n = 0-3) systems, we found all these ptH structures, except for In2Tl2H+, to be the putative global minimum. The single σ-delocalized interaction between the central hydrogen atom and InnTl4-n ligand rings proves pivotal in establishing planarity and aromaticity and conferring substantial stability upon these rule-breaking ptH species.

[Extraction process optimization and link evaluation of Reyanning Mixture based on quality by design idea].

Reyanning Mixture is one of the superior Chinese patent medicine varieties of "Qin medicine". Based on the idea of quality by design(QbD), the extraction process of the Reyanning Mixture was optimized. The caffeic acid, polydatin, resveratrol, and emodin were used as critical quality attributes(CQAs). The material-liquid ratio, extraction temperature, and extraction time were taken as critical process parameters(CPPs) by the Plackett-Burman test. The mathematical model was established by the star design-effect surface method, and the design space was constructed and verified. The optimal extraction process of the Reyanning Mixture was obtained as follows: material-liquid ratio of 11.84 g·mL~(-1), extraction temperature at 81 ℃, and two extractions. A partial least-square(PLS) quantitative model for CQAs was established by using near-infrared spectroscopy(NIRS) combined with high-performance liquid chromatography(HPLC) under the optimal extraction process. The results showed that the correlation coefficients of the correction set(R_c) and validation set(R_p) of the quantitative models of four CQAs were more than 0.9. The root mean square error of the correction set(RMSEC) were 0.744, 6.71, 3.95, and 1.53 µg·mL~(-1), respectively, and the root mean square error of the validation set(RMSEP) were 0.709, 5.88, 2.92, and 1.59 µg·mL~(-1), respectively. Therefore, the optimized extraction process of the Reyanning Mixture is reasonable, feasible, stable, and reliable. The NIRS quantitative model has a good prediction, which can be used for the rapid content determination of CQAs during extraction. They can provide an experimental basis for the process research and quality control of Reyanning Mixture.

Stable Lithium Oxygen Batteries Enabled by Solvent-diluent Interaction in N,N-dimethylacetamide-based Electrolytes.

In the pursuit of next-generation ultrahigh-energy-density Li-O2 batteries, it is imperative to develop an electrolyte with stability against the strong oxidation environments. N,N-dimethylacetamide (DMA) is a recognized solvent known for its robust resistance to the highly reactive reduced oxygen species, yet its application in Li-O2 batteries has been constrained due to its poor compatibility with the Li metal anode. In this study, a rationally selected hydrofluoroether diluent, methyl nonafluorobutyl ether (M3), has been introduced into the DMA-based electrolyte to construct a localized high concentration electrolyte. The stable -CH3 and C-F bonds within the M3 structure could not only augment the fundamental properties of the electrolyte but also fortify its resilience against attacks from O2 - and 1O2. Additionally, the strong electron-withdrawing groups (-F) presented in the M3 diluent could facilitate coordination with the electron-donating groups (-CH3) in the DMA solvent. This intermolecular interaction promotes more alignments of Li+-anions with a small amount of M3 addition, leading to the construction of an anion-derived inorganic-rich SEI that enhances the stability of the Li anode. As a result, the Li-O2 batteries with the DMA/M3 electrolyte exhibit superior cycling performance at both 30 °C (359th) and -10 °C (120th).

Efficacy and risk of donor-derived CAR-T treatment of relapsed B-cell acute lymphoblastic leukemia after hematopoietic stem cell transplantation.

The one-year survival rate for patients experiencing a relapse of B-cell acute lymphocytic leukemia (B-ALL) following hematopoietic stem cell transplantation (HSCT) is approximately 30%. Patients experiencing a relapse after allogeneic HSCT frequently encounter difficulties in obtaining autologous CAR-T products. We conducted a study involving 14 patients who received donor-derived CAR-T therapy for relapsed B-ALL following HSCT between August 2019 and May 2023 in our center. The results revealed a CR/CRi rate of 78.6% (11/14), a GVHD rate of 21.4% (3/14), and a 1-year overall survival (OS) rate of 56%. Decreased bone marrow donor cell chimerism in 9 patients recovered after CAR-T therapy. The main causes of death were disease progression and infection. Further analysis showed that GVHD (HR 7.224, 95% CI 1.42-36.82, P = 0.017) and platelet recovery at 30 days (HR 6.807, 95% CI 1.61-28.83, P = 0.009) are significantly associated with OS after CAR-T therapy. Based on the findings, we conclude that donor-derived CAR-T cells are effective in treating relapsed B-ALL patients following HSCT. Additionally, GVHD and poor platelet recovery impact OS, but further verification with a larger sample size is needed.

[Knockdown of motility-related genes of Komagataeibacter xylinus and its effect on bacterial cellulose synthesis].

Bacterial cellulose (BC) is a biopolymer synthesized by bacteria, which possess excellent characteristics such as high water holding capacity, high crystallinity, and high purity. It is widely used in food, medical, cosmetics, and functional films. Komagataeibacter xylinus is a model strain used in BC synthesis research. In bacteria, motility-related genes are associated with BC synthesis, whereas in Komagataeibacter xylinus CGMCC 2955, the functions of motility-related genes and their effects on BC synthesis are not known. To address this gap, we used the λ Red recombinant system to individually knock out motA, motB, and mot2A respectively, and constructed the knockout strains K. x-ΔmotA, K. x-ΔmotB, and K. x-Δmot2A. Additionally, both motA and motB were disrupted to construct the K. x-ΔmotAB mutant. The results demonstrated that knockout strain K. x-ΔmotAB exhibited the highest BC yield, reaching (5.05±0.26) g/L, which represented an increase of approximately 24% compared to wild-type strains. Furthermore, the BC synthesized by this strain exhibited the lowest porosity, 54.35%, and displayed superior mechanical properties with a Young's modulus of up to 5.21 GPa. As knocking out motA and motB genes in K. xylinus CGMCC 2955 did not reduce BC yield; instead, it promoted BC synthesis. Consequently, this research further deepened our understanding of the relationship between motility and BC synthesis in acetic acid bacteria. The knockouts of motA and motB genes resulted in reduced BC porosity and improved mechanical properties, provides a reference for BC synthesis and membrane structure regulation modification.

Exploring the Use of "Honorary Transition Metals" To Push the Boundaries of Planar Hypercoordinate Alkaline-Earth Metals.

The quest for planar hypercoordinate atoms (phA) beyond six has predominantly focused on transition metals, with dodecacoordination being the highest reported thus far. Extending this bonding scenario to main-group elements, which typically lack d orbitals despite their larger atomic radius, has posed significant challenges. Intrigued by the potentiality of covalent bonding formation using the d orbitals of the heavier alkaline-earth metals (Ae = Ca, Sr, Ba), the so-called "honorary transition metals", we aim to push the boundaries of planar hypercoordination. By including rings formed by 12-15 atoms of boron-carbon and Ae centers, we propose a design scheme of 180 candidates with a phA. Further systematic screening, structural examination, and stability assessments identified 10 potential clusters with a planar hypercoordinate alkaline-earth metal (phAe) as the lowest-energy form. These unconventional structures embody planar dodeca-, trideca-, tetradeca-, and pentadecacoordinate atoms. Chemical bonding analyses reveal the important role of Ae d orbitals in facilitating covalent interactions between the central Ae atom and the surrounding boron-carbon rings, thereby establishing a new record for coordination numbers in the two-dimensional realm.

Physochlainae Radix: A Review of Ethnobotany, Phytochemistry, Pharmacology, Q-marker Prediction, and Future Directions.

BACKGROUND: Upon the release of the selection results of "Qin Medicine," numerous Chinese herbal medicines and proprietary Chinese medicines have regained attention. Physochlainae Radix (Huashanshen), a herbal medicine named after Mount Hua, the prominent peak in the Qinling Mountains, has garnered particular interest. Despite this, the impact of Physochlainae Radix and Qin medicines as a whole remains significantly overshadowed by the renown of Mount Hua. METHODS: Search on Using "Physochlainae Radix" as the keyword; searches were conducted across China National Knowledge Infrastructure (CNKI), Wanfang Data, WIP Database, PubMed, Web of Science, and the National Library of China databases. RESULTS: This study presents an overview of Physochlainae Radix by reviewing its history, chemical composition, preparation methods, planting and cultivation practices, concoctions, alkaloid detection, contraindications for use, resource recycling, and predicting quality markers. CONCLUSION: To facilitate the further application and development of Physochlainae Radix, this study also addresses the challenges in the development of Qin medicines and proposes potential solutions.

Mass Transfer Analysis for Achieving High-Rate Lithium-Air Batteries.

Lithium-air batteries (LABs) have aroused worldwide interest due to their high energy density as a promising next-generation battery technology. From a practical standpoint, one of the most pressing issues currently in LABs is their poor rate performance. Accelerating the mass transfer rate within LABs is a crucial aspect for enhancing their rate capability. In this Perspective, we have meticulously analyzed the ion and oxygen transport processes to provide readers with a comprehensive understanding of the mass transfer within LABs. Following this, we have discussed potential misconceptions in the existing literature and propose our recommendations for improving the rate performance of LABs. This Perspective provides a deep insight into the mass transfer process in LABs and offers promising strategies for developing other high-rate metal-O2 batteries.

BCKDK modification enhances the anticancer efficacy of CAR-T cells by reprogramming branched chain amino acid metabolism.

Altered branched chain amino acids (BCAAs), including leucine, isoleucine, and valine, are frequently observed in patients with advanced cancer. We evaluated the efficacy of chimeric antigen receptor (CAR) T cell-mediated cancer cell lysis potential in the immune microenvironment of BCAA supplementation and deletion. BCAA supplementation increased cancer cell killing percentage, while accelerating BCAA catabolism and decreasing BCAA transporter decreased cancer cell lysis efficacy. We thus designed BCKDK engineering CAR T cells for the reprogramming of BCAA metabolism in the tumor microenvironment based on the genotype and phenotype modification. BCKDK overexpression (OE) in CAR-T cells significantly improved cancer cell lysis, while BCKDK knockout (KO) resulted in inferior lysis potential. In an in vivo experiment, BCKDK-OE CAR-T cell treatment significantly prolonged the survival of mice bearing NALM6-GL cancer cells, with the differentiation of central memory cells and an increasing proportion of CAR-T cells in the peripheral circulation. BCKDK-KO CAR-T cell treatment resulted in shorter survival and a decreasing percentage of CAR-T cells in the peripheral circulation. In conclusion, BCKDK-engineered CAR-T cells exert a distinct phenotype for superior anticancer efficiency.

Revealing Hydrogen Bond Effect in Rechargeable Aqueous Zinc-Organic Batteries.

The surrounding hydrogen bond (H-bond) interaction around the active sites plays indispensable functions in enabling the organic electrode materials (OEMs) to fulfill their roles as ion reservoirs in aqueous zinc-organic batteries (ZOBs). Despite important, there are still no works could fully shed its real effects light on. Herein, quinone-based small molecules with a H-bond evolution model has been rationally selected to disclose the regulation and equilibration of H-bond interaction between OEMs, and OEM and the electrolyte. It has been found that only a suitable H-bond interaction could make the OEMs fully liberate their potential performance. Accordingly, the 2,5-diaminocyclohexa-2,5-diene-1,4-dione (DABQ) with elaborately designed H-bond structure exhibits a capacity of 193.3 mAh g-1 at a record-high mass loading of 66.2 mg cm-2 and 100 % capacity retention after 1500 cycles at 5 A g-1. In addition, the DABQ//Zn battery also possesses air-rechargeable ability by utilizing the chemistry redox of proton. Our results put forward a specific pathway to precise utilization of H-bond to liberate the performance of OEMs.

Reconfiguring the Hydrogen Networks of Aqueous Electrolyte to Stabilize Iron Hexacyanoferrate for High-Voltage pH-Decoupled Cell.

Prussian blue analogs (PBAs) are promising insertion-type cathode materials for different types of aqueous batteries, capable of accommodating metal or non-metal ions. However, their practical application is hindered by their susceptibility to dissolution, which leads to a shortened lifespan. Herein, we have revealed that the dissolution of PBAs primarily originates from the locally elevated pH of electrolytes, which is caused by the proton co-insertion during discharge. To address this issue, the water-locking strategy has been implemented, which interrupts the generation and Grotthuss diffusion of protons by breaking the well-connected hydrogen bonding network in aqueous electrolytes. As a result, the hybrid electrolyte enables the iron hexacyanoferrate to endure over 1000 cycles at a 1 C rate and supports a high-voltage pH-decoupled cell with an average voltage of 1.95 V. These findings provide insights for mitigating the dissolution of electrode materials, thereby enhancing the viability and performance of aqueous batteries.