Aliphatic polyamides, or nylons, are typically highly crystalline and thermally robust polymers used in high-performance applications. Nylon 6, a high-ceiling-temperature (HCT) polyamide from ...ε-caprolactam, lacks expedient chemical recyclability, while low-ceiling temperature (LCT) nylon 4 from pyrrolidone exhibits complete chemical recyclability, but it is thermally unstable and not melt-processable. Here, we introduce a hybrid nylon, nylon 4/6, based on a bicyclic lactam composed of both HCT ε-caprolactam and LCT pyrrolidone motifs in a hybridized offspring structure. Hybrid nylon 4/6 overcomes trade-offs in (de)polymerizability and performance properties of the parent nylons, exhibiting both excellent polymerization and facile depolymerization characteristics. This stereoregular polyamide forms nanocrystalline domains, allowing optical clarity and high thermal stability, however, without displaying a melting transition before decomposition. Of a series of statistical copolymers comprising nylon 4/6 and nylon 4, a 50/50 copolymer achieves the greatest synergy in both reactivity and polymer properties of each homopolymer, offering an amorphous nylon with favorable properties, including optical clarity, a high glass transition temperature, melt processability, and full chemical recyclability.
In this study, Eu2+-doped barium silicate (Ba2SiO4:Eu2+) nanophosphors dispersed in a surfactant solution were spin-coated on commercially available silicon solar cells to form colloidal crystals on ...the surface. The crystals then act as luminescence down-shifting centers to generate low-energy photons for incident ultraviolet light. The fluorescence from the Ba2SiO4:Eu2+ nanophosphors was further enhanced by coating a metal-enhanced layer composed of Ag nanoparticles and a SiO2 spacer. The solar cells showed an enhancement of 0.86mA/cm2 in short-circuit current density and approximately 0.64% increase in power conversion efficiency when coated with nanophosphors, SiO2 spacers, and Ag nanoparticles. The properties of cells integrated with the metal-enhanced layer were characterized to identify the roles of nanophosphors and Ag nanoparticles in improved light harvesting. These experiments demonstrated that the colloids of Ba2SiO4:Eu2+ acted as luminescence down-shifting centers in the ultraviolet region and the metallic nanoparticles also helped to enhance fluorescence in the visible region to increase light absorption within the measured spectral regime.
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•Efficiency of solar cell is improved by metal-enhanced nanophosphor fluorescence.•Down-shifted PL emitted by the nanophosphors was strongly enhanced by Ag NPs.•Demonstration of Ba2SiO4:Eu2+ acted as luminescence down-shifting centers in UV.
Patterning of high-quality two-dimensional chalcogenide crystals with unique planar structures and various fascinating electronic properties offers great potential for batch fabrication and ...integration of electronic and optoelectronic devices. However, it remains a challenge that requires accurate control of the crystallization, thickness, position, orientation and layout. Here we develop a method that combines microintaglio printing with van der Waals epitaxy to efficiently pattern various single-crystal two-dimensional chalcogenides onto transparent insulating mica substrates. Using this approach, we have patterned large-area arrays of two-dimensional single-crystal Bi2Se3 topological insulator with a record high Hall mobility of ∼1,750 cm(2) V(-1) s(-1) at room temperature. Furthermore, our patterned two-dimensional In2Se3 crystal arrays have been integrated and packaged to flexible photodetectors, yielding an ultrahigh external photoresponsivity of ∼1,650 A W(-1) at 633 nm. The facile patterning, integration and packaging of high-quality two-dimensional chalcogenide crystals hold promise for innovations of next-generation photodetector arrays, wearable electronics and integrated optoelectronic circuits.
Abstract
Adenosine is an immunosuppressive factor that limits anti-tumor immunity through the suppression of multiple immune subsets including T cells via activation of the adenosine A
2A
receptor (A
...2A
R). Using both murine and human chimeric antigen receptor (CAR) T cells, here we show that targeting A
2A
R with a clinically relevant CRISPR/Cas9 strategy significantly enhances their in vivo efficacy, leading to improved survival of mice. Effects evoked by CRISPR/Cas9 mediated gene deletion of A
2A
R are superior to shRNA mediated knockdown or pharmacological blockade of A
2A
R. Mechanistically, human A
2A
R-edited CAR T cells are significantly resistant to adenosine-mediated transcriptional changes, resulting in enhanced production of cytokines including IFNγ and TNF, and increased expression of JAK-STAT signaling pathway associated genes. A
2A
R deficient CAR T cells are well tolerated and do not induce overt pathologies in mice, supporting the use of CRISPR/Cas9 to target A
2A
R for the improvement of CAR T cell function in the clinic.
Nickel-iron oxides/hydroxides are among the most active electrocatalysts for the oxygen evolution reaction. In an effort to gain insight into the role of Fe in these catalysts, we have performed ...operando Mössbauer spectroscopic studies of a 3:1 Ni:Fe layered hydroxide and a hydrous Fe oxide electrocatalyst. The catalysts were prepared by a hydrothermal precipitation method that enabled catalyst growth directly on carbon paper electrodes. Fe(4+) species were detected in the NiFe hydroxide catalyst during steady-state water oxidation, accounting for up to 21% of the total Fe. In contrast, no Fe(4+) was detected in the Fe oxide catalyst. The observed Fe(4+) species are not kinetically competent to serve as the active site in water oxidation; however, their presence has important implications for the role of Fe in NiFe oxide electrocatalysts.
Because angiotensin-converting enzyme (ACE) activity is implicated widely in biological systems, we aimed to identify its novel quantitative trait loci for the purposes of understanding ACE activity ...regulation and pharmacogenetics relating to ACE inhibitor (ACEI). We performed a two-stage genome-wide association study: (1) from 400 young-onset hypertension (YOH) subjects and (2) a confirmation study with an additional 623 YOH subjects. In the first stage, eight single nucleotide polymorphisms (SNPs) of the ACE structural gene and one SNP of ABO genes were significantly associated with ACE activity. SNP rs4343 in exon17 near the well-known insertion/deletion polymorphism had the strongest association. We confirmed in the second stage that three SNPs: rs4343 in ACE gene (P=3.0 x 10⁻²⁵), rs495828 (P=3.5 x 10⁻⁸) and rs8176746 (P=9.3 x 10⁻⁵) in ABO gene were significantly associated with ACE activity. We further replicated the association between ABO genotype/blood types and ACE activity in an independent YOH family study (428 hypertension pedigrees), and showed a potential differential blood pressure response to ACEI in subjects with varied numbers of ACE-activity-raising alleles. These findings may broaden our understanding of the mechanisms controlling ACE activity and advance our pharmacogenetic knowledge on ACEI.
Signal transducer and activator of transcription 3 (STAT3) is constitutively activated in malignant tumors and has important roles in multiple aspects of cancer aggressiveness. Thus targeting STAT3 ...promises to be an attractive strategy for treatment of advanced metastatic tumors. Although many STAT3 inhibitors targeting the SH2 domain have been reported, few have moved into clinical trials. Targeting the DNA-binding domain (DBD) of STAT3, however, has been avoided due to its 'undruggable' nature and potentially limited selectivity. In a previous study, we reported an improved in silico approach targeting the DBD of STAT3 that resulted in a small-molecule STAT3 inhibitor (inS3-54). Further studies, however, showed that inS3-54 has off-target effect although it is selective to STAT3 over STAT1. In this study, we describe an extensive structure and activity-guided hit optimization and mechanistic characterization effort, which led to identification of an improved lead compound (inS3-54A18) with increased specificity and pharmacological properties. InS3-54A18 not only binds directly to the DBD and inhibits the DNA-binding activity of STAT3 both in vitro and in situ but also effectively inhibits the constitutive and interleukin-6-stimulated expression of STAT3 downstream target genes. InS3-54A18 is completely soluble in an oral formulation and effectively inhibits lung xenograft tumor growth and metastasis with little adverse effect on animals. Thus inS3-54A18 may serve as a potential candidate for further development as anticancer therapeutics targeting the DBD of human STAT3 and DBD of transcription factors may not be 'undruggable' as previously thought.
ABSTRACT
We studied the 2018 outburst of the black hole transient H 1743 − 322 with a series of Insight-HXMT, NICER, and NuSTAR observations, covering the 1–120 keV band. With our broad-band X-ray ...spectral modelling, we confirm that the source remained in the low/hard state throughout the month-long outburst, although it became marginally softer at peak flux. We detected Type-C quasi-periodic oscillations (QPOs) and followed the evolution of their properties. The QPO frequency increased from ∼0.1 to ∼0.4 Hz during the rising phase of the outburst and decreased again in the decline. Continuum X-ray flux, power-law photon index, QPO frequency, and QPO root-mean-square amplitude were positively correlated. The QPO amplitude was slightly higher in the soft X-ray band (typical values of 12–16 per cent, compared with 8–10 per cent in the hard band). Our spectral-timing results shed light on the initial rising phase in the low/hard state, which has rarely been monitored with such high cadence, time resolution, and broad-band coverage. Combining spectral and timing properties, we find that ‘failed’ (hard state only) and ‘successful’ outbursts follow the same initial evolutionary track, although the former class of outburst never reaches the threshold for a transition to softer (thermally dominated) accretion regimes.
Extracting sentiment from text is a hard semantic problem. We develop a methodology for extracting small investor sentiment from stock message boards. The algorithm comprises different classifier ...algorithms coupled together by a voting scheme. Accuracy levels are similar to widely used Bayes classifiers, but false positives are lower and sentiment accuracy higher. Time series and cross-sectional aggregation of message information improves the quality of the resultant sentiment index, particularly in the presence of slang and ambiguity. Empirical applications evidence a relationship with stock values—tech-sector postings are related to stock index levels, and to volumes and volatility. The algorithms may be used to assess the impact on investor opinion of management announcements, press releases, third-party news, and regulatory changes.
Austenite stability is essentially important in improving the cryogenic toughness of cryogenic Ni steels and guiding the development of Ni-saving cryogenic steels. The austenite stability in the ...cryogenic Ni steels is influenced by many microstructure features, making it a complicated issue which is lack of a systematic discussion. In this article, the microstructural effects on the thermal and mechanical stability of austenite in the cryogenic Ni steels are reviewed and discussed. The thermal stability of austenite (TSA) will be enhanced by the enrichment of austenite-stabilizing elements in the austenite which decreases the martensite-start (
M
s
) temperature. The grain refinement enhances the TSA by synergistically increasing the nonchemical driving force for the martensite transformation and the concentrations of austenite-stabilizing elements in the austenite. The excessive increase in the volume fraction of austenite weakens the TSA by decreasing the concentrations of austenite-stabilizing elements in the austenite. The film austenite is usually thermally more stable than the block austenite owing to its higher concentrations of austenite-stabilizing elements. The mechanical stability of austenite (MSA) is also influenced by the concentrations of austenite-stabilizing elements which affect the
M
s
temperature. The reports on the effect of grain size of austenite on the MSA are inconsistent. Both negligible and important effects of the grain size of austenite on the MSA are analyzed. The grain orientation of austenite affects the MSA via changing the Schmid factor and the additional driving force for the martensite transformation. The orientation which yields a larger value of Schmid factor would exhibit a lower MSA. The MSA is affected by the matrix or the neighboring phase due to the stress and strain partitioning among austenite and other constituent phases. The dislocation multiplication could weaken the MSA by assisting the nucleation and growth of martensite embryo and enhance the MSA by hindering the motion of embryo/austenite interfaces when dislocation density is sufficiently large. Austenite with a combination of a high TSA and a moderate or high MSA is considered to be effective strategies to enhance cryogenic toughness of the cryogenic Ni steels.
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