Tuning the circularly polarized phosphorescence of platinum(II) complexes through a chiral cation strategy.

Circularly polarized phosphorescent (CPP) materials, especially chiral platinum(II) complexes, which combine the advantages of both circularly polarized luminescence (CPL) and phosphorescence, show broad potential applications in chiral optoelectronic devices. Developing CPP emitters with both excellent chiroptical properties and high yield is urgently needed. Here, a chiral cation strategy is employed to construct the CPP Pt(II) complexes R/S-ABA·[Pt(ppy)Cl2] and R/S-MBA·[Pt(ppy)Cl2] through a simple one-step reaction with almost 100% yield. The circular dichroism and CPL spectra confirm that the chirality was successfully transferred to the [Pt(ppy)Cl2]- anion. The luminescence asymmetry factors (glum) are +1.4/-1.8 × 10-3 for R/S-ABA·[Pt(ppy)Cl2] and +4.4/-2.8 × 10-3 for R/S-MBA·[Pt(ppy)Cl2]. The stronger chiroptical property of R/S-MBA·[Pt(ppy)Cl2] is attributed to the enhanced chiral structural deformation and better matched electric and magnetic transition dipole moments. This chiral cation strategy is confirmed to efficiently construct CPP Pt(II) complexes, which will accelerate the development of CPP emitters towards commercialization.

Study of Aging Temperature on the Thermal Compression Behaviors and Microstructure of a Novel Ni-Cr-Co-Based Superalloy.

Nickel-based superalloys have been widely used in the aerospace industry, and regulating the reinforcing phases is the key to improving the high-temperature strength of the alloy. In this study, a series of aging treatments (650 °C, 750 °C, 850 °C and 950 °C for 8 h) were designed to study different thermal deformation behaviors and microstructure evolutions for a novel nickel-based superalloy. Among the aged samples, the 950 °C aged sample achieved the peak stress of ~323 MPa during the thermal deformation and the highest microhardness of ~315 HV after thermal compression, which were the greatest differences compared to before deformation. In addition, the grains of the 950 °C sample exhibit deformed fibrous shapes, and the grain orientation is isotropic, while the other samples exhibited isotropy. In the 850 °C and 950 °C high-temperature aging samples, the γ' precipitate (about 20 nm in size) is gradually precipitated, which inhibits the movement of dislocation in the grain during compression, thus inhibiting the occurrence of dynamic recrystallization and improving the high-temperature mechanical properties of the alloy.

Wafer-Scale Patterning Integration of Chiral 3D Perovskite Single Crystals toward High-Performance Full-Stokes Polarimeter.

Chiral three-dimensional (3D) perovskites exhibit exceptional optoelectronic characteristics and inherent chiroptical activity, which may overcome the limitations of low-dimensional chiral optoelectronic devices and achieve superior performance. The integrated chip of high-performance arbitrary polarized light detection is one of the aims of chiral optoelectronic devices and may be achieved by chiral 3D perovskites. Herein, we first fabricate the wafer-scale integrated full-Stokes polarimeter by the synergy of unprecedented chiral 3D perovskites (R/S-PyEA)Pb2Br6 and one-step capillary-bridge assembly technology. Compared with the chiral low-dimensional perovskites, chiral 3D perovskites present smaller exciton binding energies of 57.3 meV and excellent circular dichroism (CD) absorption properties, yielding excellent circularly polarized light (CPL) photodetectors with an ultrahigh responsivity of 86.7 A W-1, an unprecedented detectivity exceeding 4.84 × 1013 Jones, a high anisotropy factor of 0.42, and high-fidelity CPL imaging with 256 pixels. Moreover, the anisotropic crystal structure also enables chiral 3D perovskites to have a large linear-polarization response with a polarized ratio of 1.52. The combination of linear-polarization and circular-polarization discrimination capabilities guarantees the achievement of a full-Stokes polarimeter. Our study provides new research insights for the large-scale patterning wafer integration of high-performance chiroptical devices.

Prognostic analysis of cT1-3N1M0 breast cancer patients who have responded to neoadjuvant therapy undergoing various axillary surgery and breast surgery based on propensity score matching and competitive risk model.

Background: Sentinel lymph node biopsy (SLNB) in breast cancer patients with positive clinical axillary lymph nodes (cN1+) remains a topic of controversy. The aim of this study is to assess the influence of various axillary and breast surgery approaches on the survival of cN1+ breast cancer patients who have responded positively to neoadjuvant therapy (NAT). Methods: Patients diagnosed with pathologically confirmed invasive ductal carcinoma of breast between 2010 and 2020 were identified from the Surveillance, Epidemiology, and End Results (SEER) database. To mitigate confounding bias, propensity score matching (PSM) analysis was employed. Prognostic factors for both overall survival (OS) and breast cancer-specific survival (BCSS) were evaluated through COX regression risk analysis. Survival curves were generated using the Kaplan-Meier method. Furthermore, cumulative incidence and independent prognostic factors were assessed using a competing risk model. Results: The PSM analysis matched 4,890 patients. Overall survival (OS) and BCSS were slightly worse in the axillary lymph node dissection (ALND) group (HR = 1.10, 95% CI 0.91-1.31, p = 0.322 vs. HR = 1.06, 95% CI 0.87-1.29, p = 0.545). The mastectomy (MAST) group exhibited significantly worse OS and BCSS outcomes (HR = 1.25, 95% CI 1.04-1.50, p = 0.018 vs. HR = 1.37, 95% CI 1.12-1.68, p = 0.002). The combination of different axillary and breast surgery did not significantly affect OS (p = 0.083) but did have a significant impact on BCSS (p = 0.019). Competing risk model analysis revealed no significant difference in the cumulative incidence of breast cancer-specific death (BCSD) in the axillary surgery group (Grey's test, p = 0.232), but it showed a higher cumulative incidence of BCSD in the MAST group (Grey's test, p = 0.001). Multivariate analysis demonstrated that age ≥ 70 years, black race, T3 stage, ER-negative expression, HER2-negative expression, and MAST were independent prognostic risk factors for both OS and BCSS (all p < 0.05). Conclusion: For cN1+ breast cancer patients who respond positive to NAT, the optimal surgical approach is combining breast-conserving surgery (BCS) with SLNB. This procedure improves quality of life and long-term survival outcomes.

Polymeric nanoparticles (PNPs) for oral delivery of insulin.

Successful oral insulin administration can considerably enhance the quality of life (QOL) of diabetes patients who must frequently take insulin injections. Oral insulin administration, on the other hand, is seriously hampered by gastrointestinal enzymes, wide pH range, mucus and mucosal layers, which limit insulin oral bioavailability to ≤ 2%. Therefore, a large number of technological solutions have been proposed to increase the oral bioavailability of insulin, in which polymeric nanoparticles (PNPs) are highly promising for oral insulin delivery. The recently published research articles chosen for this review are based on applications of PNPs with strong future potential in oral insulin delivery, and do not cover all related work. In this review, we will summarize the controlled release mechanisms of oral insulin delivery, latest oral insulin delivery applications of PNPs nanocarrier, challenges and prospect. This review will serve as a guide to the future investigators who wish to engineer and study PNPs as oral insulin delivery systems.

Modulating the gut microbiota is involved in the effect of low-molecular-weight Glycyrrhiza polysaccharide on immune function.

Low molecular weight (6.5 kDa) Glycyrrhiza polysaccharide (GP) exhibits good immunomodulatory activity, however, the mechanism underlying GP-mediated regulation of immunity and gut microbiota remains unclear. In this study, we aimed to reveal the mechanisms underlying GP-mediated regulation of immunity and gut microbiota using cyclophosphamide (CTX)-induced immunosuppressed and intestinal mucosal injury models. GP reversed CTX-induced intestinal structural damage and increased the number of goblet cells, CD4+, CD8+ T lymphocytes, and mucin content, particularly by maintaining the balance of helper T lymphocyte 1/helper T lymphocyte 2 (Th1/Th2). Moreover, GP alleviated immunosuppression by down-regulating extracellular regulated protein kinases/p38/nuclear factor kappa-Bp50 pathways and increasing short-chain fatty acids level and secretion of cytokines, including interferon-γ, interleukin (IL)-4, IL-2, IL-10, IL-22, and transforming growth factor-ß3 and immunoglobulin (Ig) M, IgG and secretory immunoglobulin A. GP treatment increased the total species and diversity of the gut microbiota. Microbiota analysis showed that GP promoted the proliferation of beneficial bacteria, including Muribaculaceae_unclassified, Alistipes, Lachnospiraceae_NK4A136_group, Ligilactobacillus, and Clostridia_vadinBB60_group, and reduced the abundance of Proteobacteria and CTX-derived bacteria (Clostridiales_unclassified, Candidatus_Arthromitus, Firmicutes_unclassified, and Clostridium). The studies of fecal microbiota transplantation and the pseudo-aseptic model conformed that the gut microbiota is crucial in GP-mediated immunity regulation. GP shows great potential as an immune enhancer and a natural medicine for treating intestinal inflammatory diseases.

Chiral Hybrid Germanium(II) Halide with Strong Nonlinear Chiroptical Properties.

Due to the pronounced anisotropic response to circularly polarized light, chiral hybrid organic-inorganic metal halides have been regarded as promising candidates for the application in nonlinear chiroptics, especially for the second-harmonic generation circular dichroism (SHG-CD) effect. However, designing novel lead-free chiral hybrid metal halides with large anisotropy factors and high laser-induced damage thresholds (LDT) of SHG-CD remains challenging. Herein, we develop the first chiral hybrid germanium halide, (R/S-NEA)3 Ge2 I7 ⋅H2 O (R/S-NGI), and systematically investigated its linear and nonlinear chiroptical properties. S-NGI and R-NGI exhibit large anisotropy factors (gSHG-CD ) of 0.45 and 0.48, respectively, along with a high LDT of 38.46 GW/cm2 ; these anisotropy factors were the highest values among the reported lead-free chiral hybrid metal halides. Moreover, the effective second-order nonlinear optical coefficient of S-NGI could reach up to 0.86 pm/V, which was 2.9 times higher than that of commercial Y-cut quartz. Our findings facilitate a new avenue toward lead-free chiral hybrid metal halides, and their implementation in nonlinear chiroptical applications.

Development of a difficulty scoring system for laparoscopic pancreatoduodenectomy in the initial stage of the learning curve: a retrospective cohort study.

BACKGROUND: It remains uncertain how surgeons can safely pass the learning curve of laparoscopic pancreatoduodenectomy (LPD) without potentially harming patients. We aimed to develop a difficulty scoring system (DSS) to select an appropriate patient for surgeons. MATERIALS AND METHODS: A total of 773 elective pancreatoduodenectomy surgeries between July 2014 and December 2019, including 346 LPD and 427 open pancreatoduodenectomy cases, were included. A 10-level DSS for LPD was developed, and an additional 77 consecutive LPD surgeries which could provide information of the learning stage I of LPD externally validated its performance between December 2019 and December 2021. RESULTS: The incidences of postoperative complications (Clavien-Dindo≥III) gradually decreased from the learning curve stage I-III (20.00, 10.94, 5.79%, P =0.008, respectively). The DSS consisted of the following independent risk factors: (1) tumor location, (2) vascular resection and reconstruction, (3) learning curve stage, (4) prognostic nutritional index, (5) tumor size, and (6) benign or malignant tumor. The weighted Cohen's κ statistic of concordance between the reviewer's and calculated difficulty score index was 0.873. The C -statistics of DSS for postoperative complication (Clavien-Dindo≥III) were 0.818 in the learning curve stage I. The patients with DSS<5 had lower postoperative complications (Clavien-Dindo≥III) than those with DSS≥5 (4.35-41.18%, P =0.004) in the training cohort and had a lower postoperative pancreatic fistula (19.23-57.14%, P =0.0352), delayed gastric emptying (19.23-71.43%, P =0.001), and bile leakage rate (0.00-21.43%, P =0.0368) in validation cohort in the learning curve stage I. CONCLUSION: We developed and validated a difficulty score model for patient selection, which could facilitate the stepwise adoption of LPD for surgeons at different stages of the learning curve.

Highly Efficient and Stable FA-Based Quasi-2D Ruddlesden-Popper Perovskite Solar Cells by the Incorporation of ß-Fluorophenylethanamine Cations.

2D Ruddlesden-Popper (2D RP) perovskite, with attractive environmental and structural stability, has shown great application in perovskite solar cells (PSCs). However, the relatively inferior photovoltaic efficiencies of 2D PSCs limit their further application. To address this issue, ß-​fluorophenylethanamine (ß-​FPEA) as a novel spacer cation is designed and employed to develop stable and efficient quasi-2D RP PSCs. The strong dipole moment of the ß-​FPEA enhances the interactions between the cations and [PbI6 ]4- octahedra, thus improving the charge dissociation of quasi-2D RP perovskite. Additionally, the introduction of the ß-​FPEA cation optimizes the energy level alignment, improves the crystallinity, stabilizes both the mixed phase and a-FAPbI3 phase of the quasi-2D RP perovskite film, prolongs the carrier diffusion length, increases the carrier lifetime and decreases the trap density. By incorporating the ß-​FPEA, the quasi-2D RP PSCs exhibit a power conversion efficiency (PCE) of 16.77% (vs phenylethylammonium (PEA)-based quasi-2D RP PSCs of 12.81%) on PEDOT:PSS substrate and achieve a champion PCE of 19.11% on the PTAA substrate. It is worth noting that the unencapsulated ß-​FPEA-based quasi-2D RP PSCs exhibit considerably improved thermal and moisture stability. These findings provide an effective strategy for developing novel spacer cations for high-performance 2D RP PSCs.

Calycosin-7-glucoside promotes mitochondria-mediated apoptosis in hepatocellular carcinoma by targeting thioredoxin 1 to regulate oxidative stress.

Thioredoxin1 (TRX1) is a key protein that regulates redox and is considered to be a key target for cancer therapy. Flavonoids have been proven to have good antioxidant and anticancer activities. This study aimed to investigate whether the flavonoid calycosin-7-glucoside (CG) exerts an anti-hepatocellular carcinoma (HCC) role by targeting TRX1. Different doses of CG were used to treat HCC cell lines Huh-7 and HepG2 to calculate the IC50. On this basis, the effects of low, medium and high doses of CG on cell viability, apoptosis, oxidative stress and TRX1 expression of HCC cells were investigated in vitro. Also, HepG2 xenograft mice were used to evaluate the role of CG on HCC growth in vivo. The binding mode of CG and TRX1 was explored by molecular docking. Then si-TRX1 was used to further discover the effects of TRX1 on CG inhibition of HCC. Results found that CG dose-dependent decreased the proliferation activity of Huh-7 and HepG2 cells, induced apoptosis, significantly activated oxidative stress and inhibited TRX1 expression. In vivo experiments also showed that CG dose-dependent regulated oxidative stress and TRX1 expression, and promoted the expression of apoptotic proteins to inhibit HCC growth. Molecular docking confirmed that CG had a good binding effect with TRX1. Intervention with TRX1 significantly inhibited the proliferation of HCC cells, promoted apoptosis, and further promoted the effect of CG on the activity of HCC cells. In addition, CG significantly increased ROS production, reduced mitochondrial membrane potential, regulated the expression of Bax, Bcl-2 and cleaved-caspase-3, and activated mitochondria-mediated apoptosis. And si-TRX1 enhanced the effects of CG on mitochondrial function and apoptosis of HCC, suggesting that TRX1 participated in the inhibitory effect of CG on mitochondria-mediated apoptosis of HCC. In conclusion, CG exerts anti-HCC activity by targeting TRX1 to regulate oxidative stress and promote mitochondria-mediated apoptosis.