Polyoxometalate-mediated syntheses of three structurally new silver clusters.

Three structurally new polyoxometalate-templated silver clusters, homometallic [(SiW9O34)@Ag24(iPrS)11(DPPP)6Cl]2(SiW12O40) (Ag24), heterometallic [(SiW9O34)@Ag22Cu(iPrS)11(DPPP)6Cl](SbF6)2 (Ag22Cu) and {Ag16(iPrS)6(DPPP)8(CH3COO)4[Co4(OH)3(H2O)SiW9O33]2}·(CH3CN)4 (Ag16Co8) (iPrS- = isopropanethiolate, DPPP = 1,3-bis(diphenylphosphino)propane, SbF6- = hexafluoroantimonate) have been successfully synthesized using a facile solvothermal approach. The introduction of copper and cobalt ions can induce obvious changes in the molecular configuration of the obtained clusters, leading to distinct temperature-dependent photoluminescence and photothermal conversion properties.

Two structurally new Lindqvist hexaniobate-templated silver thiolate clusters.

Two structurally new Lindqvist hexaniobate-templated silver thiolate clusters, [Nb6O19@Ag45(iPrS)23(CH3COO)14] (Ag45) and (H3O)4[Nb6O19@Ag41KS2.5O2(H2O)7.5(iPrS)24(CH3COO)5] (Ag41), were synthesized using a facile one-pot solvothermal approach. Single crystal X-ray diffraction analyses revealed the presence of a classical Lindqvist-type [Nb6O19]8- anion template, with iPrS- and CH3COO- surface-protecting ligands in both silver clusters, which can further form two-dimensional Ag45 assembly and one-dimensional Ag41 chain packing structures. Both Ag45 and Ag41 clusters exhibited intriguing photothermal conversion properties and temperature-dependent emission behavior.

Atomically Precise Silver Clusters Stabilized by Lacunary Polyoxometalates with Photocatalytic CO2 Reduction Activity.

The syntheses of atomically precise silver (Ag) clusters stabilized by multidentate lacunary polyoxometalate (POM) ligands have been emerging as a promising but challenging research direction, the combination of redox-active POM ligands and silver clusters will render them unexpected geometric structures and catalytic properties. Herein, we report the successful construction of two structurally-new lacunary POM-stabilized Ag clusters, TBA6 H14 Ag14 (DPPB)4 (CH3 CN)9 [Ag24 (Si2 W18 O66 )3 ] ⋅ 10CH3 CN ⋅ 9H2 O ({Ag24 (Si2 W18 O66 )3 }, TBA=tetra-n-butylammonium, DPPB=1,4-Bis(diphenylphosphino)butane) and TBA14 H6 Ag9 Na2 (H2 O)9 [Ag27 (Si2 W18 O66 )3 ] ⋅ 8CH3 CN ⋅ 10H2 O ({Ag27 (Si2 W18 O66 )3 }), using a facile one-pot solvothermal approach. Under otherwise identical synthetic conditions, the molecular structures of two POM-stabilized Ag clusters could be readily tuned by the addition of different organic ligands. In both compounds, the central trefoil-propeller-shaped {Ag24 }14+ and {Ag27 }17+ clusters bearing 10 delocalized valence electrons are stabilized by three C-shaped {Si2 W18 O66 } units. The femtosecond/nanosecond transient absorption spectroscopy revealed the rapid charge transfer between {Ag24 }14+ core and {Si2 W18 O66 } ligands. Both compounds have been pioneeringly investigated as catalysts for photocatalytic CO2 reduction to HCOOH with a high selectivity.

Recent Advances in the Synthesis of Aromatic Azo Compounds.

Aromatic azo compounds have -N=N- double bonds as well as a larger π electron conjugation system, which endows aromatic azo compounds with wide applications in the fields of functional materials. The properties of aromatic azo compounds are closely related to the substituents on their aromatic rings. However, traditional synthesis methods, such as the coupling of diazo salts, have a significant limitation with respect to the structural design of aromatic azo compounds. Therefore, many scientists have devoted their efforts to developing new synthetic methods. Moreover, recent advances in the synthesis of aromatic azo compounds have led to improvements in the design and preparation of light-response materials at the molecular level. This review summarizes the important synthetic progress of aromatic azo compounds in recent years, with an emphasis on the pioneering contribution of functional nanomaterials to the field.

Microfluidic Wearable Devices for Sports Applications.

This study aimed to systematically review the application and research progress of flexible microfluidic wearable devices in the field of sports. The research team thoroughly investigated the use of life signal-monitoring technology for flexible wearable devices in the domain of sports. In addition, the classification of applications, the current status, and the developmental trends of similar products and equipment were evaluated. Scholars expect the provision of valuable references and guidance for related research and the development of the sports industry. The use of microfluidic detection for collecting biomarkers can mitigate the impact of sweat on movements that are common in sports and can also address the issue of discomfort after prolonged use. Flexible wearable gadgets are normally utilized to monitor athletic performance, rehabilitation, and training. Nevertheless, the research and development of such devices is limited, mostly catering to professional athletes. Devices for those who are inexperienced in sports and disabled populations are lacking. Conclusions: Upgrading microfluidic chip technology can lead to accurate and safe sports monitoring. Moreover, the development of multi-functional and multi-site devices can provide technical support to athletes during their training and competitions while also fostering technological innovation in the field of sports science.

The interaction between apigenin and PKM2 restrains progression of colorectal cancer.

Apigenin, a flavonoid that widely existed in vegetables and fruits, possesses anticarcinogenic, low toxicity, and no mutagenic properties, suggesting that apigenin is a potential therapeutic agent for tumors. However, the underlying anti-cancer molecular target of apigenin is still unclear. Therefore, to reveal the direct target and amino acid site of apigenin against colorectal cancer is the focus of this study. In the present study, the results proved that the anti-CRC activity of apigenin was positively correlated with pyruvate kinase M2 (PKM2) expression, characterized by the inhibition of cell proliferation and increase of apoptotic effects induced by apigenin in LS-174T cells of knock down PKM2. Next, pull-down and MALDI-TOF/TOF analysis determined that apigenin might interact directly with PKM2 in HCT-8 cells. Further, the study confirmed that lysine residue 433 (K433) was a key amino acid site for PKM2 binding to apigenin. Apigenin restricted the glycolysis of LS-174T and HCT-8 cells by targeting the K433 site of PKM2, thereby playing an anti-CRC role in vivo and in vitro. Meanwhile, apigenin markedly attenuated tumor growth without any adverse effects. Taken together, these findings reveal that apigenin is worthy of consideration as a promising PKM2 inhibitor for the prevention of CRC.

Metamaterials for light extraction and shaping of micro-scale light-emitting diodes: from the perspective of one-dimensional and two-dimensional photonic crystals.

Metamaterials have attracted broad attention owing to their unique versatile micro- and nano-structures. As a kind of typical metamaterial, photonic crystals (PhCs) are capable of controlling light propagation and constraining spatial light distribution from the chip level. However, introducing metamaterial into micro-scale light-emitting diodes (µLED) still exists many unknowns to explore. This paper, from the perspective of one-dimensional and two-dimensional PhCs, studies the influence of metamaterials on the light extraction and shaping of µLEDs. The µLEDs with six different kinds of PhCs and the sidewall treatment are analyzed based on finite difference time domain (FDTD) method, in which the optimal match between the PhCs type and the sidewall profile is recommended respectively. The simulation results show that the light extraction efficiency (LEE) of the µLEDs with 1D PhCs increases to 85.3% after optimizing the PhCs, and is further improved to reach 99.8% by the sidewall treatment, which is the highest design record so far. It is also found that the 2D air ring PhCs, as a kind of left-handed metamaterials, can highly concentrate the light distribution into 30° with the LEE of 65.4%, without help of any light shaping device. The surprising light extraction and shaping capability of metamaterials provides a new direction and strategy for the future design and application of µLED devices.

Case Report: Life-threatening hypercalcemia associated with MMR-deficient endometrial carcinoma secreting parathyroid hormone.

Ectopic secretion of parathyroid hormone (PTH) is a rare cause of hypercalcemia in malignancy patients. A 56-year-old woman with life-threatening hypercalcemia was caused by poorly-differentiated endometrial carcinoma secreting PTH with concomitant nodular goiter mimic parathyroid tumors. The elevated level of PTH and calcium decreased immediately after cytoreductive surgery (CRS). The pathology confirmed mismatch repair (MMR)-deficient endometrial carcinoma with PTH expression. The patient received four-course chemotherapy and one-course immunotherapy after CRS. The disease progression led to multiple organ failure and death about five months after CRS. To our knowledge, this is the first case of hypercalcemia caused by MMR-deficient endometrial carcinoma with ectopic PTH secreting and the first report of malignancy associated hypercalcemia complicated with nodular goiter.

The Use of Sports Rehabilitation Robotics to Assist in the Recovery of Physical Abilities in Elderly Patients with Degenerative Diseases: A Literature Review.

The increase in the number of elderly patients with degenerative diseases has brought additional medical and financial pressures, which are adding to the burden on society. The development of sports rehabilitation robotics (SRR) is becoming increasingly sophisticated at the technical level of its application; however, few studies have analyzed how it works and how effective it is in aiding rehabilitation, and fewer individualized exercise rehabilitation programs have been developed for elderly patients. The purpose of this study was to analyze the working methods and the effects of different types of SRR and then to suggest the feasibility of applying SRR to enhance the physical abilities of elderly patients with degenerative diseases. The researcher's team searched 633 English-language journal articles, which had been published over the past five years, and they selected 38 of them for a narrative literature review. Our summary found the following: (1) The current types of SRR are generally classified as end-effector robots, smart walkers, intelligent robotic rollators, and exoskeleton robots-exoskeleton robots were found to be the most widely used. (2) The current working methods include assistant tools as the main intermediaries-i.e., robots assist patients to participate; patients as the main intermediaries-i.e., patients dominate the assistant tools to participate; and sensors as the intermediaries-i.e., myoelectric-driven robots promote patient participation. (3) Better recovery was perceived for elderly patients when using SRR than is generally achieved through the traditional single-movement recovery methods, especially in strength, balance, endurance, and coordination. However, there was no significant improvement in their speed or agility after using SRR.

Expression and significance of CDX2, FXR, and TGR5 in esophageal cancer.

This study explored the expression and significance of three critical morphogenesis genes in normal esophagus, reflux esophagitis (RE), Barrett's esophagus (BE), esophageal adenocarcinoma (EA), and esophageal squamous cell carcinoma (ESCC). Esophageal tissue samples and tissue microarrays were used. CDX2, FXR, and TGR5 protein expression were measured by immunohistochemistry in normal esophageal, RE, BE, EA, and ESCC tissues. All 3 proteins had markedly changed expression during the progression of EA. The expressions of CDX2 and FXR were positively correlated in EA. In addition, TGR5 expression was positively correlated with CDX2 in RE and BE. The expressions of CDX2 and FXR were also positively correlated in ESCC. Although CDX2, FXR, and TGR5 were upregulated in ESCC, these factors might not be markers for the prognosis of ESCC. These results suggested that CDX2, FXR, and TGR5 might play different roles in EA and ESCC. They may represent novel therapeutic targets for patients with these cancers.

Propofol Augments Paclitaxel-Induced Cervical Cancer Cell Ferroptosis In Vitro.

Introduction: Cervical cancer is common in women. The present standardized therapies including surgery, chemotherapy, and radiotherapy are still not enough for treatment. Propofol is the most commonly used intravenous anesthetic agent for induction and maintenance of anesthesia and has been shown to exert anti-malignancy effects on cancer cells, inducing oxidative stress and apoptosis. However, the biological effects of propofol have not yet been systematically assessed. In this study, we examined the ferroptosis-related changes caused by propofol and the chemotherapeutic agent paclitaxel besides apoptosis in vitro. Methods: Cervical cancer cell lines (C-33A and HeLa) were treated with propofol alone (1, 2, 5, 10, and 20 µg/ml) or in combination with paclitaxel (0.5, 1, and 5 µg/ml). The viability was assessed using cell counting kit-8 (CCK8), apoptosis was detected by flow cytometry, morphological changes of mitochondria were examined using transmission electron microscope (TEM), cellular reactive oxygen species (ROS), and intracellular ferrous ions were determined by fluorescence microscope or confocal microscopy. The expression and cellular localization of apoptosis and ferroptosis-related molecules were detected by Western blot and multiplex immunohistochemistry (mIHC), respectively. Calcusyn software was used to determine whether propofol has a synergistic effect with paclitaxel. Results: Propofol and paclitaxel inhibited C-33A and HeLa cell viability. There were also synergistic effects when propofol and paclitaxel were used in combination at certain concentrations. In addition, propofol promoted paclitaxel-induced cervical cancer cell death via apoptosis. ROS level and Fe2+ concentrations were also influenced by different drug treatments. Furthermore, propofol, propofol injectable emulsion, and paclitaxel induced ferroptosis-related morphological changes of mitochondria in C-33A and HeLa cells. Ferroptosis-related signaling pathways including SLC7A11/GPX4, ubiquinol/CoQ10/FSP1, and YAP/ACSL4/TFRC were found to be changed under drug treatments. Conclusion: Propofol showed synergistic anticancer effects with paclitaxel in cervical cancer cells. Propofol and paclitaxel may induce ferroptosis of cervical cancer cells besides apoptosis.

Propofol Inhibits Proliferation and Augments the Anti-Tumor Effect of Doxorubicin and Paclitaxel Partly Through Promoting Ferroptosis in Triple-Negative Breast Cancer Cells.

Background: Triple-negative breast cancer (TNBC) is relatively common in women and is associated with a poor prognosis after surgery and adjuvant chemotherapy. Currently, the mechanism underlying the relationship between propofol and breast cancer is controversial and limited to cell apoptosis. Moreover, there are only a few studies on the effect of propofol on the chemotherapeutic sensitivity of TNBC cells. Therefore, this study explored whether propofol and its commonly used clinical formulations affect the proliferation and chemotherapeutic effects on TNBC cells by regulating cell ferroptosis. Methods: We selected MDA-MB-231 cells, and the effects of propofol, propofol injectable emulsion (PIE), or fospropofol disodium, alone or combined with doxorubicin or paclitaxel on cell viability, apoptosis, intracellular reactive oxygen species (ROS) accumulation, ferroptosis-related morphological changes, intracellular Fe2+ levels, and the expression and localization of ferroptosis-related proteins were investigated. Results: We found that propofol significantly inhibited MDA-MB-231 cell proliferation, and all three propofol formulations augmented the anti-tumor effects of doxorubicin and paclitaxel. The results from the ROS assay, transmission electron microscopy, intracellular Fe2+ assay, western blotting, and multiplex immunohistochemistry revealed that propofol not only induced apoptosis but also triggered ferroptosis-related changes, including morphological changes of mitochondria, increased intracellular ROS levels, and intracellular iron accumulation in MDA-MB-231 cells. The ferroptosis-related p53-SLC7A11-GPX4 pathway was also altered under different treatment propofol, doxorubicin, or paclitaxel regimens. Conclusion: Propofol showed anti-proliferation effects on TNBC cells and could be a potential adjuvant to enhance the chemotherapeutic sensitivity of TNBC cells partly by promoting cell ferroptosis.

Regional anesthesia and cancer recurrence in patients with late-stage cancer: a systematic review and meta-analysis.

BACKGROUND: Whether regional anesthesia may help to prevent disease recurrence in cancer patients is still controversial. The stage of cancer at the time of diagnosis is a key factor that defines prognosis and is one of the most important sources of heterogeneity for the treatment effect. We sought to update existing systematic reviews and clarify the effect of regional anesthesia on cancer recurrence in late-stage cancer patients. METHODS: Medline, Embase, and Cochrane Library were searched from inception to September 2020 to identify randomized controlled trials (RCTs) and cohort studies that assessed the effect of regional anesthesia on cancer recurrence and overall survival (OS) compared with general anesthesia. Late-stage cancer patients were primarily assessed according to the American Joint Committee on Cancer Cancer Staging Manual (eighth edition), and the combined hazard ratio (HR) from random-effects models was used to evaluate the effect of regional anesthesia. RESULTS: A total of three RCTs and 34 cohort studies (including 64,691 patients) were identified through the literature search for inclusion in the analysis. The risk of bias was low in the RCTs and was moderate in the observational studies. The pooled HR for recurrence-free survival (RFS) or OS did not favor regional anesthesia when data from RCTs in patients with late-stage cancer were combined (RFS, HR = 1.12, 95% confidence interval [CI]: 0.58-2.18, P = 0.729, I2 = 76%; OS, HR = 0.86, 95% CI: 0.63-1.18, P = 0.345, I2 = 48%). Findings from observational studies showed that regional anesthesia may help to prevent disease recurrence (HR = 0.87, 95% CI: 0.78-0.96, P = 0.008, I2 = 71%) and improve OS (HR = 0.88, 95% CI: 0.79-0.98, P = 0.022, I2 = 79%). CONCLUSIONS: RCTs reveal that OS and RFS were similar between regional and general anesthesia in late-stage cancers. The selection of anesthetic methods should still be based on clinical evaluation, and changes to current practice need more support from large, well-powered, and well-designed studies.

Neuromuscular Blockade Correlates with Hormones and Body Composition in Acromegaly.

Tumor resection is the first-line therapy for acromegaly patients. In some cases, unsatisfactory intraoperative neuromuscular blockades (NMBs) lead to failed operations. The purpose of this study was to investigate and quantify the NMB status of acromegaly patients and explore the relationship between NMB status and hormone levels and body composition. Twenty patients with untreated acromegaly and seventeen patients with nonfunctioning pituitary adenomas as controls were enrolled in this study. NMB was assessed using the train-of-four (TOF) technique with TOF-Watch® SX. The onset time of NMB, deep neuromuscular blockade duration (DNMBD), and clinical neuromuscular blockade duration (CNMBD) were monitored. We found a significantly longer onset time (110.25 ± 54.90 vs. 75.00 ± 27.56, s, p=0.017), shorter DNMBD (21.99 ± 5.67 vs. 34.96 ± 11.04, min, p < 0.001), and shorter CNMBD (33.26 ± 8.09 vs. 46.21 ± 10.89, min, p < 0.001) in acromegaly patients compared with the controls. DNMBD and CNMBD decreased in patients with decreasing body fat percentage and increasing growth hormone (GH) level, insulin-like growth factor 1 (IGF-1) level, and GH and IGF-1 burden. The onset time increased with increasing IGF-1 level and GH and IGF-1 burden. Taken together, a unique NMB status was identified in acromegaly patients with the following characteristics: prolonged onset time and shortened DNMBD and CNMBD. Changes in the levels and burdens of GH and IGF-1 and body composition were linearly correlated with intraoperative NMB in acromegaly patients.

Sarcomatous carcinoma in biliary system: A retrospective study.

Sarcomatous carcinoma in biliary system, including sarcomatous intrahepatic cholangiocarcinoma (SIC) and sarcomatous choledochal carcinoma (SCC), is extremely rare and malignant.This retrospective study included 5 patients with SIC and 4 patients with SCC. Their basic characteristics, preoperative lab tests, preoperative imaging features, perioperative status, and follow-up information have been collected and analyzed.Lesions at different locations induced various preoperative symptoms. The history of choledocholithiasis or hepatolithiasis was remarkable in patients with SIC. Cancer antigen 19-9 appeared to be a key factor for both SIC and SCC. However, preoperative lab tests or imaging features could not distinguish SIC from intrahepatic cholangiocarcinoma, or SCC from choledochal carcinoma. Surgical treatments for all 9 patients were successful. Efficacy of adjuvant chemotherapy was not ideal. The prognosis of sarcomatous biliary carcinoma was enormously poor.Sarcomatous carcinoma in biliary system is extremely rare and malignant. Chronic inflammation could be critical in the currently unknown occurrence mechanism. Further research is urgently needed to improve the prognosis.

Sarcomatous intrahepatic cholangiocarcinoma: Case report and literature review.

RATIONALE: Sarcomatous intrahepatic cholangiocarcinoma is a rare histological variant of cholangiocarcinoma (ICC). Previous medical literature has not mentioned the prevalence of this kind of disease, but a poorer prognosis than that of ordinary ICC was indicated. The diagnosis of the sarcomatous ICC is established on histopathological and immunohistochemical examinations. In this article, we present a new case of a patient with sarcomatous ICC who had no radiographic sign of intrahepatic tumor preoperatively. PATIENT CONCERNS: A 63-year-old man was noted with cholecystolithiasis and right upper abdominal pain. Liver function was within normal limits, although the gamma-glutamyl transpeptidase level was elevated. Serum carbohydrate antigen 19-9 level was elevated. Radiography showed atrophy of the left lobe of the liver, high-intensity signals on T1 weighted images, and low/high-intensity signals on T2 weighted images in hepatic ducts. DIAGNOSES: The preoperative diagnoses were hepatolithiasis, choledocholithiasis, and cholecystolithiasis. INTERVENTIONS: Exploratory laparotomy, adhesion release, cholecystectomy, choledocholithotomy, and T tube drainage were performed. During the surgery, an ill-defined tumor was detected on the atrophic left lateral lobe of the liver. Hepatic left lateral lobectomy was performed to remove the mass. OUTCOMES: The final diagnosis of sarcomatous ICC was made by histopathology after surgery. No evidence of local recurrence or distant metastasis was noted on imaging during follow-up. LESSONS: Although rare, sarcomatous ICC does exist in patients presented with cholecystolithiasis and liver atrophy. Surgeons should be aware of the existence of sarcomatous ICC due to the poor prognosis. We recommend that multidisciplinary approaches may be key to improve prognosis, including adjuvant chemotherapy or radiotherapy.

Preventative effect of Astragalus flavescens on hepatic fibrosis in rats and its mechanism of action.

The aim of this study was to investigate the preventative effect of Astragalus flavescens on hepatic fibrosis in rats and its mechanism of action. A total of 60 rats were randomly divided into normal control, model control, high-dose treatment and low-dose treatment groups, and a hepatic fibrosis model was established. The high- and low-dose treatment groups were treated with 2 g/100 g and 0.5 g/100 g Astragalus flavescens, respectively, once a day. Eight weeks following the initiation of treatment, the liver specimens of the rats were stained and observed under a light microscope. Hepatic fibrosis indices, specifically, type III precollagen (PC III), type IV collagen (C IV), hyaluronic acid (HA) and laminin (LN), were detected. Furthermore, the expression and localization of the hepatic fibrosis-related factors transforming growth factor-ß1 (TGF-ß1), connective tissue growth factor (CTGF) and platelet-derived growth factor-BB (PDGF-BB) were determined. The serum levels of hepatic fibrosis indices, and the liver tissue levels of hepatic fibrosis-related factors and collagen surface density in the model control group and the high- and low-dose treatment groups were significantly higher compared with those of the normal control group (P<0.05). In addition, the values in the two treatment groups were significantly lower compared with those of the model control group (P<0.05). The present study demonstrated that Astragalus flavescens effectively prevents hepatic fibrosis in rats. A possible mechanism for this is that it may reduce the expression levels of TGF-ß1, PDGF-BB and CTGF, thereby inhibiting the activation of hepatic stellate cells and specifically blocking the signal transduction pathway of hepatic fibrosis.