Constructing artificial helical structures through hierarchical self-assembly and exploring the underlying mechanism are important, and they help gain insight from the structures, processes, and ...functions from the biological helices and facilitate the development of material science and nanotechnology. Herein, the two enantiomers of chiral Au(I) complexes ( S )-1 and ( R )-1 were synthesized, and they exhibited impressive spontaneous hierarchical self-assembly transitions from vesicles to helical fibers. An impressive chirality inversion and amplification was accompanied by the assembly transition, as elucidated by the results of in situ and time-dependent circular dichroism spectroscopy and scanning electron microscope imaging. The two enantiomers could serve as ideal chiral templates to co-assemble with other achiral luminogens to efficiently induce the resulting co-assembly systems to show circularly polarized luminescence (CPL). Our work has provided a simple but efficient way to explore the sophisticated self-assembly process and presented a facile and effective strategy to fabricate architectures with CPL properties.
Alkaline phosphatase (ALP) activity is regarded as an important biomarker in medical diagnosis. A ratiometric fluorescent probe is developed based on a phosphorylated chalcone derivative for ALP ...activity assay and visualization in living cells. The probe is soluble in water and emits greenish-yellow in aqueous buffers. In the presence of ALP, the emission of probe changes to deep red gradually with ratiometric fluorescent response due to formation and aggregation of enzymatic product, whose fluorescence involves both excited-state intramolecular proton transfer and aggregation-induced emission processes. The linear ratiometric fluorescent response enables in vitro quantification of ALP activity in a range of 0–150 mU/mL with a detection limit of 0.15 mU/mL. The probe also shows excellent biocompatibility, which enables it to apply in ALP mapping in living cells.
Life process is amazing, and it proceeds against the eternal law of entropy increase through molecular motion and takes energy from the environment to build high-order complexity from chaos to ...achieve evolution with more sophisticated architectures. Inspired from the elegance of life process and also to effectively exploit the undeveloped solid-state molecular motion, two unique chiral Au(I) complexes were elaborately developed in this study, in which their powders could realize a dramatic transformation from nonemissive isolated crystallites to emissive well-defined microcrystals under the stimulation of mechanical force. Such an unusual crystallization was presumed to be caused by molecular motions driven by the formation of strong aurophilic interactions as well as multiple C–H···F and π–π interactions. Such a prominent macroscopic off/on luminescent switching could also be achieved through extremely subtle molecular motions in the crystal state and presented a filament sliding that occurred in a layer-by-layer molecular stacking fashion with no involvement of any crystal phase transition. Additionally, it had been demonstrated that the manipulation of the solid-state molecular motions could result in the generation of circularly polarized luminescence.
X-ray fluorescence (XRF) scanning of unlithified, untreated sediment cores is becoming an increasingly common method used to obtain paleoproxy data from lake records. XRF-scanning is fast and ...delivers high-resolution records of relative variations in the elemental composition of the sediment. However, lake sediments display extreme variations in their organic matter content, which can vary from just a few percent to well over 50%. As XRF scanners are largely insensitive to organic material in the sediment, increasing levels of organic material effectively dilute those components that can be measured, such as the lithogenic material (the closed-sum effect). Consequently, in sediments with large variations in organic material, the measured variations in an element will to a large extent mirror the changes in organic material. It is therefore necessary to normalize the elements in the lithogenic component of the sediment against a conservative element to allow changes in the input of the elements to be addressed. In this study we show that Al, which is the lightest element that can be measured using the Itrax XRF-scanner, can be used to effectively normalize the elements of the lithogenic fraction of the sediment against variations in organic content. We also show that care must be taken when choosing resolution and exposure time to ensure optimal output from the measurements.
Abnormal remodeling of subchondral bone (SB) induced by estrogen deficiency has been shown to be involved in osteoarthritis (OA). Raloxifene (RAL) is commonly used to treat postmenopausal ...osteoporosis (OP). However, little is known about its effects on OA combined with estrogen deficiency. This study was performed to evaluate the efficacy of RAL on patella baja-induced patellofemoral joint OA (PFJOA) in an ovariectomized rat model.
Patellar ligament shortening (PLS) and ovariectomy (OVX) were performed simultaneously in 3-month-old female Sprague–Dawley rats, which were treated with RAL (10 mg/kg/day) or vehicle at 72 h postoperatively for 10 weeks. PFJOA was assessed by immunohistochemistry (IHC), real-time polymerase chain reaction (PCR), tartrate-resistant acid phosphatase (TRAP) staining, enzyme-linked immunosorbent assay (ELISA), micro-computed tomography (μCT), histomorphology and behavioral analyses.
X-ray examinations showed that patella baja was successfully established by PLS. Histomorphological analysis revealed that PFJOA was significantly exacerbated by OVX and markedly alleviated by RAL. Moreover, RAL improved cartilage metabolism by decreasing MMP-13, ADAMTS-4, and caspase-3 and increasing Col-II and aggrecan at both the protein and mRNA levels. Furthermore, RAL markedly improved bone mass and SB microarchitecture and reduced osteoclast numbers and the serum osteocalcin and CTX-I levels. Although RAL showed a trend toward reducing pain sensitivity based on mechanical allodynia testing, this result was not statistically significant.
These findings demonstrate that RAL treatment retards PFJOA progression in an ovariectomized rat model, suggesting that it may be a potential candidate for amelioration of the progression of PFJOA accompanied by postmenopausal OP.
We report on the observation of new properties of secondary cosmic rays Li, Be, and B measured in the rigidity (momentum per unit charge) range 1.9 GV to 3.3 TV with a total of 5.4×10^{6} nuclei ...collected by AMS during the first five years of operation aboard the International Space Station. The Li and B fluxes have an identical rigidity dependence above 7 GV and all three fluxes have an identical rigidity dependence above 30 GV with the Li/Be flux ratio of 2.0±0.1. The three fluxes deviate from a single power law above 200 GV in an identical way. This behavior of secondary cosmic rays has also been observed in the AMS measurement of primary cosmic rays He, C, and O but the rigidity dependences of primary cosmic rays and of secondary cosmic rays are distinctly different. In particular, above 200 GV, the secondary cosmic rays harden more than the primary cosmic rays.
Perfluorooctanesulfonylfluoride (POSF)-based compounds have been manufactured and used in a variety of industrial applications. These compounds degrade to perfluorooctanesulfonate (PFOS) which is ...regarded as a persistent end-stage metabolite and is found to accumulate in tissues of humans and wildlife. PFOS, perfluorohexanesulfonate (PFHxS), perfluorooctanoate (PFOA), and perfluorooctanesulfonamide (PFOSA) have been found in human sera from the United States. In this study, concentrations of PFHxS, perfluorobutanesulfonate (PFBS), PFOS, perfluorohexanoic acid (PFHxA), PFOA, perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA), and PFOSA were measured in 85 samples of whole human blood collected from nine cities (eight provinces) in China, including Shenyang (Liaoning), Beijing (Hebei), Zhengzhou (Henan), Jintan (Jiangsu), Wuhan (Hubei), Zhoushan (Zhejiang), Guiyang (Guizhou), Xiamen (Fujian), and Fuzhou (Fujian). Among the 10 perfluorinated compounds (PFCs) measured, PFOS was the predominant compound. The mean concentration of PFOS was greatest in samples collected from Shenyang (79.2 ng/mL) and least in samples from Jintan (3.72 ng/mL). PFHxS was the next most abundant perfluorochemical in the samples. No age-related differences in the concentrations of PFOA, PFOS, PFOSA, and PFHxS were observed. Gender-related differences were found, with males higher for PFOS and PFHxS, and females higher in PFUnDA. Concentrations of PFHxS were positively correlated with those of PFOS, while concentrations of PFNA, PFDA, and PFUnDA were positively correlated with those of PFOA. There were differences in the concentration profiles (percentage composition) of various PFCs in the samples among the nine cities.
Exploring approaches to utilize abundant water to synthesize functional molecules and polymers with efficient clusteroluminescence properties is highly significant but has yet to be reported. Herein, ...a chemistry of water and alkyne is developed. The synthesized products are proven as nonaromatic clusteroluminogens that could emit visible light. Their emission colors and luminescent efficiency could be adjusted by manipulating through-space interaction using different starting materials. Besides, the free-standing polymeric films with much high photoluminescence quantum yields (up to 45.7%) are in situ generated via a water-involved interfacial polymerization. The interfacial polymerization-enhanced emission of the polymeric films is observed, where the emission red-shifts and efficiency increases when the polymerization time is prolonged. The synthesized polymeric film is also verified as a Janus film. It exhibits a vapor-triggered reversible mechanical response which could be applied as a smart actuator. Thus, this work develops a method to synthesize clusteroluminogens using water, builds a clear structure-property relationship of clusteroluminogens, and provides a strategy to in situ construct functional water-based polymeric films.
ABSTRACT
Based on Insight-HXMT data, we report on the pulse fraction evolution during the 2017–2018 outburst of the newly discovered first Galactic ultraluminous X-ray (ULX) source Swift ...J0243.6+6124. The pulse fractions of 19 observation pairs selected in the rising and fading phases with similar luminosity are investigated. The results show a general trend of the pulse fraction increasing with luminosity and energy at supercritical luminosity. However, the relative strength of the pulsation between each pair evolves strongly with luminosity. The pulse fraction in the rising phase is larger at luminosity below 7.71 × 1038 erg s−1, but smaller at above. A transition luminosity is found to be energy independent. Such a phenomenon is first confirmed by Insight-HXMT observations and we speculate that it may have relation with the radiation-pressure-dominated accretion disc.
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