ABSTRACT
Smart materials enabling emission intensity or wavelength tuning by light stimulus have attracted attention in cutting-edge fields. However, due to the general limitation of the dense molecular stacking (in solid states, especially in crystals) on photoresponsivity, constructing rapidly phototunable solid-state luminescent systems remains challenging. Herein, we present a new luminophore that serves as both a photoresponsive and a luminous group with enhanced conformational freedom to attain this goal, namely, relying on photoexcitation-induced molecular conformational change of an ionized persulfurated arene based on weak intermolecular aliphatic C-Hâ â â π interaction. Together with the phosphorescence characteristic of the molecule itself, rapidly enhanced phosphorescence upon irradiation can be observed in a series of phase states, like solution state, crystal, and amorphous state, especially with a high photoresponsive rate of 0.033â s-1 in crystal state that is superior to the relevant reported cases. Moreover, a rapidly phototunable afterglow effect is achieved by extending this molecule into some polymer-based doping systems, endowing the system with unique dynamic imaging and fast photopatterning capabilities. This single-luminophore molecular engineering and underlying mechanism have implications for building other condensed functional materials, principally for those with stimuli responses in solid states.
ABSTRACT
We present here the synthesis and in-depth physicochemical characterization of a double hetero[7]helicene fused with four triazole rings at both helical ends. The comparison of this triazole-fused double helicene with the previously reported all-carbon and thiadiazole-fused analogs revealed the huge impact of the embedded aromatic rings on the photophysical features. The small structural variation of the terminal rings from thiadiazole to triazole caused a dramatic change of the photoluminescence quantum yields (PLQYs) from <1 % to 96 %, while the replacement of the terminal benzene rings with triazole rings induced a tenfold enhancement of the circularly polarized luminescence dissymmetry factor. These observations were well corroborated with transient absorption analysis and/or theoretic calculations. In addition, the triazole-fused double helicene exhibited ambipolar redox behavior, enabling the generation of radical cation and anion species by electrochemical and chemical methods and showing its potential for spin-related applications.
ABSTRACT
Regulated choice between cell fate maintenance and differentiation provides decision points in development to progress toward more restricted cell fates or to maintain the current one. Caenorhabditis elegans embryogenesis follows an invariant cell lineage where cell fate is generally more restricted upon each cell division. EMS is a progenitor cell in the four-cell embryo that gives rise to the endomesoderm. We recently found that when ubiquitin-mediated protein degradation is compromised, the anterior daughter of EMS, namely MS, reiterates the EMS fate. This observation demonstrates an essential function of ubiquitin-mediated protein degradation in driving the progression of EMS-to-MS differentiation. Here we report a genome-wide screen of the ubiquitin pathway and extensive lineage analyses. The results suggest a broad role of E3 ligases in driving differentiation progression. First, we identified three substrate-binding proteins for two Cullin-RING ubiquitin ligase (CRL) E3 complexes that promote the progression from the EMS fate to MS, namely LIN-23/ß-TrCP and FBXB-3 for the CRL1/SCF complex and ZYG-11/ZYG-11B for the CRL2 complex. Genetic analyses suggest these E3 ligases function through a multifunctional protein OMA-1 and the endomesoderm lineage specifier SKN-1 to drive differentiation. Second, we found that depletion of components of the CRL1/SCF complex induces fate reiteration in all major founder cell lineages. These data suggest that regulated choice between self-renewal and differentiation is widespread during C. elegans embryogenesis as in organisms with regulative development, and ubiquitin-mediated protein degradation drives the choice towards differentiation. Finally, bioinformatic analysis of time series gene expression data showed that expression of E3 genes is transiently enriched during time windows of developmental stage transitions. Transcription factors show similar enrichment, but not other classes of regulatory genes. Based on these findings we propose that ubiquitin-mediated protein degradation, like many transcription factors, function broadly as regulators driving developmental progression during embryogenesis in C. elegans.
Subject(s)
Caenorhabditis elegans Proteins/metabolism , Caenorhabditis elegans/cytology , Caenorhabditis elegans/embryology , Cell Differentiation , Embryonic Development , Ubiquitin-Protein Ligases/metabolism , Animals , Caenorhabditis elegans/enzymology , Caenorhabditis elegans Proteins/genetics , Cell Lineage , Embryo, Nonmammalian/cytology , Embryo, Nonmammalian/metabolism , Endoderm/embryology , Gene Expression Regulation, Developmental , Mesoderm/embryology , RNA Interference , Ubiquitination , Wnt Signaling PathwayABSTRACT
Preclinical Research Epidermal growth factor receptor (EGFR), a validated target for anticancer drugs, plays a critical role in tumorigenesis and tumor development. A series of p-O-alkyl salicylanilide derivatives were designed and synthesized as novel EGFR inhibitors using a salicylic acid scaffold. A simulated six-membered ring strategy formed through intramolecular hydrogen bonds was employed to mimic the planar quinazoline of the EGFR antagonist, gefitinib. The derived compounds with hydroxyl at the ortho position were more potent than ones with methoxyl group. In particular, compounds 5d and 5b displayed significant EGFR inhibitory (IC50 values = 0.30 and 0.45 µM, respectively) activity as well as potent antiproliferative activity in A431 and HCT-116 tumor cells. These salicylanilides could be considered as promising lead compounds for developing novel EGFR inhibitors.
Subject(s)
Antineoplastic Agents/chemical synthesis , ErbB Receptors/antagonists & inhibitors , Protein Kinase Inhibitors/chemical synthesis , Salicylanilides/chemical synthesis , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Cell Line, Tumor , Cell Proliferation/drug effects , HCT116 Cells , Humans , Hydrogen Bonding , Molecular Structure , Protein Kinase Inhibitors/chemistry , Protein Kinase Inhibitors/pharmacology , Salicylanilides/chemistry , Salicylanilides/pharmacology , Structure-Activity RelationshipABSTRACT
BACKGROUND: Imaging and image analysis advances are yielding increasingly complete and complicated records of cellular events in tissues and whole embryos. The ability to follow hundreds to thousands of cells at the individual level demands a spatio-temporal data infrastructure: tools to assemble and collate knowledge about development spatially in a manner analogous to geographic information systems (GIS). Just as GIS indexes items or events based on their spatio-temporal or 4D location on the Earth these tools would organize knowledge based on location within the tissues or embryos. Developmental processes are highly context-specific, but the complexity of the 4D environment in which they unfold is a barrier to assembling an understanding of any particular process from diverse sources of information. In the same way that GIS aids the understanding and use of geo-located large data sets, software can, with a proper frame of reference, allow large biological data sets to be understood spatially. Intuitive tools are needed to navigate the spatial structure of complex tissue, collate large data sets and existing knowledge with this spatial structure and help users derive hypotheses about developmental mechanisms. RESULTS: Toward this goal we have developed WormGUIDES, a mobile application that presents a 4D developmental atlas for Caenorhabditis elegans. The WormGUIDES mobile app enables users to navigate a 3D model depicting the nuclear positions of all cells in the developing embryo. The identity of each cell can be queried with a tap, and community databases searched for available information about that cell. Information about ancestry, fate and gene expression can be used to label cells and craft customized visualizations that highlight cells as potential players in an event of interest. Scenes are easily saved, shared and published to other WormGUIDES users. The mobile app is available for Android and iOS platforms. CONCLUSION: WormGUIDES provides an important tool for examining developmental processes and developing mechanistic hypotheses about their control. Critically, it provides the typical end user with an intuitive interface for developing and sharing custom visualizations of developmental processes. Equally important, because users can select cells based on their position and search for information about them, the app also serves as a spatially organized index into the large body of knowledge available to the C. elegans community online. Moreover, the app can be used to create and publish the result of exploration: interactive content that brings other researchers and students directly to the spatio-temporal point of insight. Ultimately the app will incorporate a detailed time lapse record of cell shape, beginning with neurons. This will add the key ability to navigate and understand the developmental events that result in the coordinated and precise emergence of anatomy, particularly the wiring of the nervous system.
Subject(s)
Caenorhabditis elegans/growth & development , Nervous System/cytology , Single-Cell Analysis/methods , Software , User-Computer Interface , Animals , Databases, FactualABSTRACT
Since the first confirmed case was reported in January 2020, Hong Kong has experienced multiple waves of COVID-19 outbreaks. Recent literature has explored the spatial patterns of disease incidence and their relationships with the built environment and demographic characteristics. Nonetheless, few studies aim at the comparative patterns of different epidemic waves occurring in the same spatial context. This study analyses spatial patterns of the third and fourth COVID-19 epidemic waves and then evaluates the spatial relationship between case incidence and built environment and socio-demographic characteristics. By collecting local-related cases, this study incorporates a two-fold analytical strategy: (1) Using rank-size distribution and log-odd ratio to depict the spatial pattern of COVID-19 incidence rates; (2) through global and local regression models, investigating incidence's associations with the urban built environment and socio-demographic characteristics. The results reveal that the two different epidemic waves have far distinct spatial tendencies to their infection risk factors, reflecting location-specific associations with the built environments and socio-demographics. Collectively, we discover that the third and fourth COVID-19 waves are likely associated with residential context and urban activities, respectively. Practical implications are discussed that would be of interest to policymakers and health professionals.
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Mechanistic probing of surface potential changes arising from dynamic charge transport is the key to understanding and engineering increasingly complex nanoscale materials and devices. Spatiotemporal averaging in conventional heterodyne detection-based Kelvin probe force microscopy (KPFM) inherently limits its time resolution, causing an irretrievable loss of transient response and higher-order harmonics. Addressing this, we report a wavelet transform (WT)-based methodology capable of quantifying the sub-ms charge dynamics and probing the elusive transient response. The feedback-free, open-loop wavelet transform KPFM (OL-WT-KPFM) technique harnesses the WT's ability to simultaneously extract spatial and temporal information from the photodetector signal to provide a dynamic mapping of surface potential, capacitance gradient, and dielectric constant at a temporal resolution 3 orders of magnitude higher than the lock-in time constant. We further demonstrate the method's applicability to explore the surface-photovoltage-induced sub-ms hole-diffusion transient in bismuth oxyiodide semiconductor. The OL-WT-KPFM concept is readily applicable to commercial systems and can provide the underlying basis for the real-time analysis of transient electronic and electrochemical properties.
ABSTRACT
Notably, the intermolecular charge transfer between pyrene (Py) and benzophonenes (BPs) can significantly enhance the quantum yield of the triplet state of Py, which will convert Py from a fluorescence molecule to a phosphorescence molecule. The intermolecular charge transfer is confirmed by steady-state and time-resolved spectroscopy and theoretical study. Based on these foundations, Py is doped into BPs systems and a large Stokes-shift organic room temperature phosphorescence (ORTP) is observed. By using different benzophenone derivatives, a series of host-guest ORTP materials with different luminescent properties adjusted by intermolecular charge transfer features are developed. Fortunately, these host-guest ORTP systems from benzophenone derivatives and pyrene are readily fabricated, and the red gradient color lasting as long as 3 s is observed after removing UV excitation. This host-guest charge transfer strategy plays an important role in the mechanism of the luminous type shift. Our strategy paves the way to design ORTP materials conveniently and apply these materials in encryption and temperature alarm device.
ABSTRACT
Localized surface plasmon resonance (LSPR) of metallic nanostructures is a unique phenomenon that controls the light in sub-wavelength volumes and enhances the light-matter interactions. Traditionally, the excitation and measurement of LSPR require bulky external light sources, and efforts to scale down to nano-plasmonic devices have predominantly relied on the system's miniaturization and associated accessories. Addressing this, here we show the generation and detection of LSPR wavelength (λLSPR) shifts in large-area nanostructured Au surfaces using frictional charges generated by triboelectric surfaces. We observe a complex interplay of the localized surface plasmons with frictional charges via concurrent spectroscopic and triboelectric measurements undertaken for the detection of bioconjugation in the streptavidin-biotin complex. When subjected to multivariate principal component analysis, a strong correlation between the triboelectric peak-to-peak voltage output response and the λLSPR shift is observed. Furthermore, we reveal a landscape of the interfacial events involved in the electrical generation/detection of the LSPR by using theoretical models and surface characterization. The demonstrated concept of electrification of plasmon resonance thus provides the underlying basis for the subsequent development of self-powered nano-plasmonic sensors and opens new horizons for advanced nanophotonic applications.
Subject(s)
Nanostructures , Surface Plasmon Resonance , Surface Plasmon Resonance/methods , Streptavidin/chemistry , Nanostructures/chemistry , Biotin/chemistry , Models, TheoreticalABSTRACT
With the COVID-19 vaccination widely implemented in most countries, propelled by the need to revive the tourism economy, there is a growing prospect for relieving the social distancing regulation and reopening borders in tourism-oriented countries and regions. This need incentivizes stakeholders to develop border control strategies that fully evaluate health risks if mandatory quarantines are lifted. In this study, we have employed a computational approach to investigate the contact tracing integrated policy in different border-reopening scenarios in Hong Kong, China. Explicitly, by reconstructing the COVID-19 transmission from historical data, specific scenarios with joint effects of digital contact tracing and other concurrent measures (i.e., controlling arrival population and community nonpharmacological interventions) are applied to forecast the future development of the pandemic. Built on a modified SEIR epidemic model with a 30% vaccination coverage, the results suggest that scenarios with digital contact tracing and quick isolation intervention can reduce the infectious population by 92.11% compared to those without contact tracing. By further restricting the inbound population with a 10,000 daily quota and applying moderate-to-strong community nonpharmacological interventions (NPIs), the average daily confirmed cases in the forecast period of 60 days can be well controlled at around 9 per day (95% CI: 7-12). Two main policy recommendations are drawn from the study. First, digital contact tracing would be an effective countermeasure for reducing local virus spread, especially when it is applied along with a moderate level of vaccination coverage. Second, implementing a daily quota on inbound travelers and restrictive community NPIs would further keep the local infection under control. This study offers scientific evidence and prospective guidance for developing and instituting plans to lift mandatory border control policies in preparing for the global economic recovery.
Subject(s)
COVID-19 , Quarantine , COVID-19 Vaccines , China , Contact Tracing , Hong Kong , Humans , Models, Theoretical , Policy , Prospective Studies , SARS-CoV-2ABSTRACT
OBJECTIVE: To investigate the effect of pH value and fluoride ions on the corrosion resistance of pure Ti and Ni-Cr-Ti alloy in the artificial saliva. METHODS: Electrochemical technique was used to measure the electric potential of corrosion (Ecorr), current density of corrosion (Icorr) and polarization resistance (Rp) of pure titanium and Ti-Ni-Cr alloy in the artificial saliva with different pH value and fluoride concentrations. After electrochemical analysis, microstructure and phase diffraction were examined by FSEM. RESULTS: With the lower pH value, the Ecorr and Icorr of pure titanium and Ti-Ni-Cr alloy increased, the Rp decreased, there was a significant difference (P<0.05). The Ecorr and Icorr increased markedly, the Rp significantly reduced in the artificial saliva containing 0.2% NaF (P<0.01). FSEM showed that pure titanium and Ti-Ni-Cr alloy surface corrosion, pure titanium in the artificial saliva containing 0.2% NaF was most serious. CONCLUSION: Lower pH value decreases the corrosion resistance of pure titanium and Ti-Ni-Cr alloy and the artificial saliva containing fluoride ions decreases the corrosion resistance of pure titanium.