Spin-related Cu-Co pair to increase electrochemical ammonia generation on high-entropy oxides.

The electrochemical conversion of nitrate to ammonia is a way to eliminate nitrate pollutant in water. Cu-Co synergistic effect was found to produce excellent performance in ammonia generation. However, few studies have focused on this effect in high-entropy oxides. Here, we report the spin-related Cu-Co synergistic effect on electrochemical nitrate-to-ammonia conversion using high-entropy oxide Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O. In contrast, the Li-incorporated MgCoNiCuZnO exhibits inferior performance. By correlating the electronic structure, we found that the Co spin states are crucial for the Cu-Co synergistic effect for ammonia generation. The Cu-Co pair with a high spin Co in Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O can facilitate ammonia generation, while a low spin Co in Li-incorporated MgCoNiCuZnO decreases the Cu-Co synergistic effect on ammonia generation. These findings offer important insights in employing the synergistic effect and spin states inside for selective catalysis. It also indicates the generality of the magnetic effect in ammonia synthesis between electrocatalysis and thermal catalysis.

Stiffness changes in internal rotation muscles of the shoulder and its influence on hemiplegic shoulder pain.

Background: Hemiplegic shoulder pain (HSP) is a common complication in patients with stroke. The pathogenesis of HSP is complex, and muscle hypertonia, especially the hypertonia of internal rotation muscles of the shoulder, may be one of the important causes of shoulder pain. However, the relationship between muscle stiffness and HSP has not been well studied. The purpose of this study is to explore the correlations between the stiffness of internal rotation muscles and clinical symptoms in patients with HSP. Methods: A total of 20 HSP patients and 20 healthy controls were recruited for this study. The stiffness of internal rotation muscles was quantified using shear wave elastography, and Young's modulus (YM) of the pectoralis major (PM), anterior deltoid (AD), teres major ™, and latissimus dorsi (LD) were measured. Muscle hypertonia and pain intensity were evaluated using the Modified Ashworth Scale (MAS) and Visual Analog Scale (VAS), respectively. The mobility of the shoulder was evaluated using the Neer score. The correlations between muscle stiffness and the clinical scales were analyzed. Results: YM of internal rotation muscles on the paretic side was higher than that of the control group in the resting and passive stretching positions (P < 0.05). YM of internal rotation muscles on the paretic side during passive stretching was significantly higher than that at rest (P < 0.05). YM of PM, TM, and LD during passive stretching were correlated with MAS (P < 0.05). In addition, the YM of TM during passive stretching was positively correlated with VAS and negatively correlated with the Neer score (P < 0.05). Conclusion: Increased stiffness of PM, TM, and LD was observed in patients with HSP. The stiffness of TM was associated with pain intensity of the shoulder and shoulder mobility.

LncRNA modulates Hippo-YAP signaling to reprogram iron metabolism.

Iron metabolism dysregulation is tightly associated with cancer development. But the underlying mechanisms remain poorly understood. Increasing evidence has shown that long noncoding RNAs (lncRNAs) participate in various metabolic processes via integrating signaling pathway. In this study, we revealed one iron-triggered lncRNA, one target of YAP, LncRIM (LncRNA Related to Iron Metabolism, also named ZBED5-AS1 and Loc729013), which effectively links the Hippo pathway to iron metabolism and is largely independent on IRP2. Mechanically, LncRIM directly binds NF2 to inhibit NF2-LATS1 interaction, which causes YAP activation and increases intracellular iron level via DMT1 and TFR1. Additionally, LncRIM-NF2 axis mediates cellular iron metabolism dependent on the Hippo pathway. Clinically, high expression of LncRIM correlates with poor patient survival, suggesting its potential use as a biomarker and therapeutic target. Taken together, our study demonstrated a novel mechanism in which LncRIM-NF2 axis facilitates iron-mediated feedback loop to hyperactivate YAP and promote breast cancer development.

Low-cost composite film triboelectric nanogenerators for a self-powered touch sensor.

In the last two decades, nanogenerators have been studied inorder to solve the power supply problems of electronic devices. Triboelectric nanogenerators (TENGs) have gained widespread attention due to their excellent properties and wide range of applications. However, previous studies frequently ignored numerous application-related issues and even wasted some of the benefits of the TENG itself in favor of enhanced performance. Here, we propose a TENG based on BaTiO3 (BTO)-polydimethylsiloxane (PDMS) composite films with low cost and simple preparation, where its maximum output performance is obtained when the mass proportion of BTO to PDMS is 40%. In addition, we demonstrate how the single-electrode TENG may be used as a self-powered touch sensor that can communicate with a microcontroller unit (MCU) to turn LED lights on and off. This practical example will provide a valuable reference for the application of low-cost self-powered sensors in wearable devices, Internet of Things, human-machine interactions and other fields. Furthermore, we discovered a number of issues that were rarely or never addressed in previous studies and provide some solutions, such as a signal processing method for a TENG-based self-powered sensor. It serves as a foundation for future investigations on the performance assessment and application of TENGs.

lncRNA BREA2 promotes metastasis by disrupting the WWP2-mediated ubiquitination of Notch1.

Notch has been implicated in human cancers and is a putative therapeutic target. However, the regulation of Notch activation in the nucleus remains largely uncharacterized. Therefore, characterizing the detailed mechanisms governing Notch degradation will identify attractive strategies for treating Notch-activated cancers. Here, we report that the long noncoding RNA (lncRNA) BREA2 drives breast cancer metastasis by stabilizing the Notch1 intracellular domain (NICD1). Moreover, we reveal WW domain containing E3 ubiquitin protein ligase 2 (WWP2) as an E3 ligase for NICD1 at K1821 and a suppressor of breast cancer metastasis. Mechanistically, BREA2 impairs WWP2-NICD1 complex formation and in turn stabilizes NICD1, leading to Notch signaling activation and lung metastasis. BREA2 loss sensitizes breast cancer cells to inhibition of Notch signaling and suppresses the growth of breast cancer patient-derived xenograft tumors, highlighting its therapeutic potential in breast cancer. Taken together, these results reveal the lncRNA BREA2 as a putative regulator of Notch signaling and an oncogenic player driving breast cancer metastasis.

Multi-objective cluster based bidding algorithm for E-commerce search engine marketing system.

Search engine marketing (SEM) is an important channel for the success of e-commerce. With the increasing scale of catalog items, designing an efficient modern industrial-level bidding system usually requires overcoming the following hurdles: 1. the relevant bidding features are of high sparsity, preventing an accurate prediction of the performances of many ads. 2. the large volume of bidding requests induces a significant computation burden to offline and online serving. In this article, we introduce an end-to-end structure of a multi-objective bidding system for search engine marketing for Walmart e-commerce, which successfully handles tens of millions of bids each day. The system deals with multiple business demands by constructing an optimization model targeting a mixture of metrics. Moreover, the system extracts the vector representations of ads via the Transformer model. It leverages their geometric relation to building collaborative bidding predictions via clustering to address performance features' sparsity issues. We provide theoretical and numerical analyzes to discuss how we find the proposed system as a production-efficient solution.

Increased Stiffness of the Superficial Cervical Extensor Muscles in Patients With Cervicogenic Headache: A Study Using Shear Wave Elastography.

Background: Cervicogenic headache (CEH) is a secondary headache caused by lesions of the cervical spine and surrounding soft tissues. Cervical muscle dysfunction may be related to the onset of CEH. However, whether cervical muscle stiffness changes in patients with CEH has not been well studied. The purpose of this study was to explore changes in superficial cervical extensor muscle stiffness in patients with CEH using shear wave elastography (SWE). Methods: In this study, 19 patients with CEH and 20 healthy controls were recruited. Superficial cervical extensor muscle stiffness was obtained from SWE, and the SuperLinear SL10-2 MHz linear array probe in the musculoskeletal muscle mode was chosen as the transducer. Regions of interest in the trapezius (TRAP), splenius capitis (SPL), semispinalis capitis (SCap), and semispinalis cervicis (SCer) were manually segmented. Correlations between superficial cervical extensor muscle stiffness and visual analog scale (VAS) scores, age, and body mass index (BMI) were analyzed using Pearson's correlation. Receiver operating characteristic (ROC) curve was used to investigate the diagnostic ability of superficial cervical extensor stiffness for CEH. Results: Superficial cervical extensor muscle stiffness on the headache side of patients with CEH was higher than that on the non-headache side and in healthy controls (p < 0.05). Increased stiffness was also observed in SCer on the non-headache side of patients with CEH compared to healthy controls (p < 0.01). In patients with CEH, SCer stiffness was positively correlated with VAS scores (r = 0.481, p = 0.037), but no correlation was found between other muscles and VAS scores (p > 0.05). The areas under the curve of TRAP, SPL, SCap, and SCer in diagnosing CEH were 0.766, 0.759, 0.964, and 1.000, respectively. Conclusions: Increased stiffness was observed in the superficial cervical extensor muscles on the headache side of patients with CEH. SCer stiffness was correlated with headache intensity in patients with CEH and may provide clues for the diagnosis of CEH.

ANGPTL4 regulate glutamine metabolism and fatty acid oxidation in nonsmall cell lung cancer cells.

Angiopoietin-like protein (ANGPTL) 4 is a key factor in the regulation of lipid and glucose metabolism in metabolic diseases. ANGPTL4 is highly expressed in various cancers, but the regulation of energy metabolism in tumours remains to be determined. This study explored the role of ANGPTL4 in aerobic glycolysis, glutamine consumption and fatty acid oxidation in nonsmall cell lung cancer (NSCLC) cells. Two NSCLC cell lines (A549 and H1299) were used to investigate the role of ANGPTL4 in energy metabolism by tracer techniques and with Seahorse XF technology in ANGPTLs4 knockdown cells. RNA microarrays and specific inhibitors were used to identify targets in ANGPTLs4-overexpressing cells. The results showed that knockdown of ANGPTLs4 could inhibit energy metabolism and proliferation in NSCLC. ANGPTLs4 had no significant effect on glycolysis but affected glutamine consumption and fatty acid oxidation. Knockdown of ANGPTLs4 also significantly inhibited tumour metastasis and energy metabolism in mice and had a weak effect on glycolysis. RNA microarray analysis showed that ANGPTLs4 significantly affected glutaminase (GLS) and carnitine palmitoyl transferase 1 (CPT1). ANGPTLs4-overexpressing cells were exposed to a glutamine deprivation environment, and cell proliferation and energy metabolism were significantly decreased but still differed from normal NSCLC cells. Treatment of ANGPTLs4-overexpressing cells with GLS and CPT1 inhibitors simultaneously prevented the regulatory effects on cell proliferation and energy metabolism. ANGPTLs4 could promote glutamine consumption and fatty acid oxidation but not glycolysis or accelerate energy metabolism in NSCLC.

Stopped-Flow Dynamics Study on the Escape Behavior of Polyelectrolyte Macromolecules from Microgels: The Influence of the Path Length and Size.

We reported the fabrication of several monodispersed poly(2-vinyl pyridine)-poly(N-isopropylacrylamide) (P2VP-PNIPAM) microgels including the P2VP core (non-cross-linked) and PNIPAM (cross-linked) shell by mature emulsion polymerization. The fast escape behavior (diffusion process) of linear P2VP chains through a porous PNIPAM layer was investigated by a pH jump stopped-flow apparatus. The time-dependent dynamic traces (corresponding to the scattered light intensity) decreased at the initial timescale of several seconds and then reached an apparent equilibrium, confirming the efficient escape of P2VP chains from microgels. Compared with the previously reported literature, such an accelerated escape process resulted from the sharply increased internal charge repulsive force caused by the protonation of P2VP moieties under acidic conditions. The obtained characteristic relaxation times by single exponential fitting of these kinetic traces were dependent on the final pH values, equilibrium temperatures, shell thickness (path length), and cross-linking density (mesh size). We believe that this work can provide an efficient way to investigate hindered diffusion, especially the initial rapid diffusion stage. Not only that, the proposed model can also provide theoretical guidance to some practical applications, such as membrane separation and the exocytosis phenomenon of intracellular proteins or macromolecular substances.

Kruppel-like factor 2 disturb non-small cell lung cancer energy metabolism by inhibited glutamine consumption.

OBJECTIVES: Metabolic reprogramming is well accepted as a hallmark of cancer. This study aimed to explore the role of Kruppel-like factor 2 (KLF2) in aerobic glycolysis and glutamine consumption of energy metabolism in non-small cell lung cancer (NSCLC) cells. METHODS: Two different NSCLC cells, A549 and NCI-H1299, were used to investigate the role of KLF2 in glycolysis and glutamine consumption by tracer technique and KLF2 transfection. KEY FINDINGS: The results showed that overexpression KLF could inhibit the energy metabolism and proliferation of NSCLC cells, but had no significant effect on glycolysis reaction and only affected the glutamine consumption of NSCLC cells. In NSCLC cells exposed to glutamine deprivation, the effect of overexpression of KLF2 on cell proliferation and energy metabolism disappeared. It was found that KLF2 could inhibit the expression of glutaminase (GLS) by metabolite tracing technique and so on. However, when GLS inhibitors were given to overexpressing KLF2 NSCLC cells, the intervention effect of KLF2 disappeared. CONCLUSIONS: Kruppel-like factor 2 could decrease the level of glutamine, participate in the consumption of glutamine by cancer cells, and then inhibit the energy metabolism of cancer cells.

Bta-miR-885 promotes proliferation and inhibits differentiation of myoblasts by targeting MyoD1.

The proliferation and differentiation of myoblasts are essential for the regeneration and development of skeletal muscles. However, the process of skeletal muscle development in cattle is complex and needs to be further investigated. The microRNAs (miRNAs) are endogenous, small noncoding RNAs that play a critical role during skeletal muscle development. In this study, we evaluated the function of miR-885 in muscle development in cattle. The results found that the expression of miR-885 was gradually upregulated during myoblast proliferation, whereas progressively downregulated during myoblast differentiation. The overexpression of miR-885 promoted cell proliferation of myoblast in cattle. Moreover, we further noted that the overexpression miR-885 triggered the expression level of various marker genes involved in cell proliferation, including proliferating cell nuclear antigen (PCNA), cyclin-dependent kinase 2 (CDK2), and cyclin B1 (CCNB1). Furthermore, it was observed that overexpression of miR-885 inhibited cell differentiation, and significantly decreased messenger RNA and protein expression levels of myogenic differentiation 1 (MyoD1) and myogenin (MyoG) in primary bovine myoblasts. Moreover, the miR-885 inhibitor revealed that miR-885 inhibited cell proliferation and promoted cell differentiation. In addition, the overexpression of miR-885 markedly decreased MyoD1 expression in primary bovine myoblasts. The luciferase reporter assay, quantitative real-time polymerase chain reaction, and western blot (WB) further indicated that miR-885 directly binding to 3' UTR of MyoD1 gene during transcriptional regulation. Conclusively, these results signified that miR-885 could be critical for the proliferation and differentiation in primary bovine myoblast cells by targeting the MyoD1 gene in cattle.

Anatomical study and clinical application of medial sural artery perforator flap for oral cavity reconstruction.

The present study aims to provide anatomical evidence for clinical application of the medial sural artery perforator (MSAP) flap. The current study investigated the vascular anatomy of the flap, evaluated the postoperative appearance and function of the donor and recipient sites, and investigate the clinical value in reconstruction of oral cavity. Six lower limbs of Chinese adult cadavers were microsurgically dissected. The locations and courses of the medial sural artery perforators were identified and recorded, which provided an anatomical basis for clinical application. Then, 16 clinical cases employing this flap were evaluated, ranging from 3×4cm to 6×8cm, and were employed for defects in the oral cavity region. Sixteen clinical cases with intraoral soft tissue defects, which included four clinical cases with inner cheek defects, were successfully followed up for 10-47 months (24 months on average). The donor site function, contour of recipient site and oral function recovery were evaluated as acceptable or better in cases with intraoral soft tissue defect, which were further verifying the value of clinical application of MSAP in repairing oral cavity defects. Moreover, two typical clinical cases were described in detail. To conclude, the MSAP flap is a favorable choice for small- to medium-size defects based on minor donor site morbidity, satisfactory oral function recovery, perforator stability and adaptation of the pedicle for anastomosis in the oral cavity region.

Phenylboronic Acid-Dopamine Dynamic Covalent Bond Involved Dual-Responsive Polymeric Complex: Construction and Anticancer Investigation.

In cancer treatment, prolonging the retention time of therapeutic agents in tumor tissues is a key point in enhancing the therapeutic efficacy. However, drug delivery by intravenous injection is always subjected to a "CAPIR" cascade, including circulation, accumulation, penetration, internalization, and release. Intratumoral administration has gradually emerged as an ideal alternative approach for nanomedicine because of its independence of blood constituents and minimal systemic toxicities. In this contribution, based on the dynamically reversible interaction between boronic acid (BA) and dopamine (DA), a thermo- and pH-responsive polymeric complex is rationally obtained by facile mixing of phenylboronic acid (PBA)- and tetraphenylethene (TPE)-modified poly(N-isopropylacrylamide)-b-poly(phenyl isocyanide)s block copolymers, PNIPAM-b-P(PBAPI-co-TPEPI), and tetra(ethylene glycol) methyl ether acrylate (OEGA)- and DA-containing hydrophilic P(DA-co-OEGA) copolymers. The resultant complex exhibited temperature- and pH-dependent size change as well as sustained nile red (NR) release profiles in a mimic tumor environment. Moreover, thanks to the opposite optical behavior of TPE and NR molecules, the complex could be served as a fluorescence ratiometric cell imaging agent, avoiding the interference of background fluorescence and improving correlated resolution. After encapsulation of camptothecin (anticancer drug), the efficient killing on HeLa cells was achieved in vitro, and the structural integrity of the complex endowed its extended retention time in tumor tissues. Considering these advantages, the reversible covalent interaction between PBA and diols can be used as an efficient driving force to form dynamic drug-delivery vectors, which are promising to be an effective nanoplatform for injectable medical treatments.

Direct thiocarbamation of imidazoheterocycles via dual C-H sulfurization.

A copper-catalyzed DTBP oxidative dual C-H sulfurization has been developed for the direct thiocarbamation of imidazopyridines using a combination of elemental sulfur and formamides as carbamothioyl surrogates. NBS (bromo succinimide) was found to promote the thiocarbamation in good yields. This dual C-H sulfurization strategy enables access to a wide range of carbamothioyl imidazoheterocycles without the use of highly toxic phosgene.

Gallic acid-assisted synthesis of Pd uniformly anchored on porous N-rGO as efficient electrocatalyst for microbial fuel cells.

The sluggish kinetic rate-limiting oxygen reduction reaction (ORR) at the cathode remains the foremost issue hindering the commercialization of microbial fuel cells (MFCs). Utilization of the effect of micromolecule conjugation and the synergistic effect between Pd nanoparticles and N-rGO (nitrogen-doped reduced graphene oxide) to stabilize a precious metal onto carbon materials is a promising strategy to design and synthesize highly efficient cathode catalysts. In this study, gallic acid is used to facilitate the coupling of palladium (Pd) with N-rGO to form GN@Pd-GA via a simple hydrothermal process. Notably, the as-synthesized GN@Pd-GA as a cathode catalyst shows an approximately direct four-electron feature and demonstrates a high ORR performance in 0.1 M KOH. Furthermore, the stability and methanol tolerance of GN@Pd-GA are superior to those of the commercial Pt/C catalysts. In addition, a maximum power density of 391.06 ± 0.2 mW m-2 of MFCs equipped with GN@Pd-GA was obtained, which was 96.2% of the power density of MFCs equipped with a commercial Pt/C catalyst.

Sleep problems in children with attention-deficit hyperactivity disorder: associations with parenting style and sleep hygiene.

We aimed to examine the association between sleep problems and parenting and sleep hygiene in children with attention-deficit/hyperactivity disorder (ADHD). Participants included 5-13-year-old children with DSM 5 defined ADHD and a parent-reported moderate-to-severe sleep problem (N = 361). Sleep was assessed using the parent-reported Children's Sleep Habits Questionnaire. Parents also completed checklists assessing sleep hygiene, parenting consistency, and parenting warmth. Linear regression established prediction models controlling for confounding variables including child age and sex, ADHD symptom severity, comorbidities, medication use, and socio-demographic factors. More consistent parenting was associated with decreased bedtime resistance (ß = -0.16) and decreased sleep anxiety (ß = -0.14), while greater parental warmth was associated with increased parasomnias (ß = +0.18) and sleep anxiety (ß = +0.13). Poorer sleep hygiene was associated with increased bedtime resistance (ß = +0.20), increased daytime sleepiness (ß = +0.12), and increased sleep duration problems (ß = +0.13). In conclusion, sleep hygiene and parenting are important modifiable factors independently associated with sleep problems in children with ADHD. These factors should be considered in the management of sleep problems in children with ADHD.

Tetrandrine inhibits glioma stem-like cells by repressing ß-catenin expression.

Cancer stem cells (CSCs) in glioma are often responsible for relapse and resistance to therapy. The purpose of the present study was to confirm the self-renewal and migration inhibitory effects of tetrandrine (Tet), which is a compound extracted from the dried root of Stephania tetrandra S. Moore, toward glioma stem-like cells (GSLCs) and to examine the associated molecular mechanisms. Using a neurosphere culture technique, we enriched the GSLC population from the human glioblastoma cell lines U87 and U251. Cells were analyzed using cell counting kit-8 (CCK-8), western blotting, flow cytometry, transwell assay and immunofluorescence staining. GSLCs displayed properties of neural stem cells, including elevated expression of the cancer stem cell marker ALDH1 and ß-catenin. We found that Tet treatment decreased sphere formation in GSLCs in a dose-dependent manner using tumor spheroid formation assay. The GSK3ß inhibitor BIO maintained sphere formation and migration capacity in GSLCs, whereas the ß-catenin/TCF transcription inhibitor ICG-001 decreased sphere formation and the migration capacity of GSLCs. The proportion of apoptotic GSLCs also increased in response to ICG-001 treatment. These results indicate that ß-catenin activity is vital in maintaining neural stem cell traits of GSLCs. Tet inhibits cell viability, neurosphere formation and migration of GSLCs in vitro. Importantly, Tet treatment significantly repressed the nuclear translocation and expression of ß-catenin and induced apoptosis in GSLCs, as indicated in part by the upregulation of Bax, the cleavage of PARP and the downregulation of Bcl-2. The present study demonstrates that the inhibition of ß-catenin in CSCs by Tet could be an effective strategy for the treatment of glioma.

Multicomponent reactions of phosphines, enynedioates and benzylidene malononitriles generated highly substituted cyclopentenes through an unexpected phosphine α-addition-δ-evolvement of an anion pathway.

Multicomponent reactions of phosphines, enynedioates and benzylidene malononitriles provide highly substituted syn-selective cyclopentenes appending the phosphorus ylide moiety in good yield with a diastereoselectivity of up to 100% through resonance-derived 1,5-dipolar species as the key intermediates, via the nucleophilic α(δ')-attack of phosphines toward enynedioates followed by addition to benzylidene malononitriles and 5-exo-dig cyclization. Through computational analyses, the overall reactions for the formation of syn- and anti-diastereomers are both exothermic with 65.6 and 66.3 kcal mol(-1) at the B3LYP-D3/6-31G(d) level of theory and were found to be kinetically controlled, which favours the formation of syn-diastereomers.

Using multiple combined analytical techniques to characterize water extractable organic nitrogen from Lake Erhai sediment.

In this study, UV-vis absorbance, fluorescence, and FT-IR spectroscopy were combined to characterize the components and structure of the water extractable organic nitrogen (WEON) in Lake Erhai sediment. Lake Erhai sediment WEON comprised predominantly high molecular weight WEON, with the fraction with a molecular weight>1kDa accounting for 87.7% of the total. It was mainly composed of humic acid-like substances, with fewer simple aromatic proteins. Large amounts of aliphatic and amide compounds were detected by IR in the sediments. There were more polymerizable aromatic rings and carbonyl, carboxyl, hydroxyl, and ester compounds in the high molecular weight WEON than in the low molecular weight WEON. Additionally, fluorescence regional integration results implied that the ratio PIII+V,n/PI+II+IV,n can be indirectly taken as an indicator for WEON content in Erhai sediments. Furthermore, the composition and structural characteristics of the WEON were found to be closely related with their properties in the sediment. The large amount of aliphatic compounds in the sediment as well as the relatively high humification and aromatic degree in high molecular weight WEON, stabilizes the WEON in Lake Erhai sediment. Compared with other lake sediments of different trophic statues (such as Lake Dianchi, Lake Poyang, Lake Taihu and Lake Donghu), Erhai sediment exhibited a higher degree of humification, which benefited for reducing sediment WEON releasing risk. And it can be regarded as the reason why the nutrient content in Erhai sediment is very high, but its water quality is still good.