Abstract
Surface plasmons are coherent and collective electron oscillations confined at the dielectric–metal interface. Benefitting from the inherent subwavelength nature of spatial profile, surface ...plasmons can greatly accumulate the optical field and energy on the nanoscale and dramatically enhance various light–matter interactions. The properties of surface plasmons are strongly related to materials and structures, so that metals, semiconductors and two-dimensional materials with various morphologies and structures can have alternating plasmonic wavelengths ranging from ultraviolet, visible, near infrared to far infrared. Because the electric field can be enhanced by orders of magnitude within plasmonic structures, various light–matter interaction processes including fluorescence, Raman scattering, heat generation, photoacoustic effects, photocatalysis, nonlinear optical conversion, and solar energy conversion, can be significantly enhanced and these have been confirmed by both theoretical, computational and experimental studies. In this review, we present a concise introduction and discussion of various plasmon-enhanced light–matter interaction processes. We discuss the physical and chemical principles, influencing factors, computational and theoretical methods, and practical applications of these plasmon-enhanced processes and phenomena, with a hope to deliver guidelines for constructing future high-performance plasmonic devices and technologies.
Superelastic carbon aerogels have been widely explored by graphitic carbons and soft carbons. These soft aerogels usually have delicate microstructures with good fatigue resistance but ultralow ...strength. Hard carbon aerogels show great advantages in mechanical strength and structural stability due to the sp3‐C‐induced turbostratic “house‐of‐cards” structure. However, it is still a challenge to fabricate superelastic hard carbon‐based aerogels. Through rational nanofibrous structural design, the traditional rigid phenolic resin can be converted into superelastic hard carbon aerogels. The hard carbon nanofibers and abundant welded junctions endow the hard carbon aerogels with robust and stable mechanical performance, including superelasticity, high strength, extremely fast recovery speed (860 mm s−1), low energy‐loss coefficient (<0.16), long cycle lifespan, and heat/cold‐endurance. These emerging hard carbon nanofiber aerogels hold a great promise in the application of piezoresistive stress sensors with high stability and wide detection range (50 kPa), as well as stretchable or bendable conductors.
A family of hard carbon aerogels with nanofibrous structure templated by various nanofibers is fabricated, displaying robust and stable mechanical performances, including high strength, extremely fast recovery speed (860 mm s−1), and ultralow energy loss coefficient (<0.16). After being compressed for 104 cycles (50% strain), they show only ≈2% plastic deformation and retain ≈93% stress.
Gastric cancer is a deadly disease and remains the third leading cause of cancer-related death worldwide. The 5-year overall survival rate of patients with early-stage localized gastric cancer is ...more than 60%, whereas that of patients with distant metastasis is less than 5%. Surgical resection is the best option for early-stage gastric cancer, while chemotherapy is mainly used in the middle and advanced stages of this disease, despite the frequently reported treatment failure due to chemotherapy resistance. Therefore, there is an unmet medical need for identifying new biomarkers for the early diagnosis and proper management of patients, to achieve the best response to treatment. Long non-coding RNAs (lncRNAs) in body fluids have attracted widespread attention as biomarkers for early screening, diagnosis, treatment, prognosis, and responses to drugs due to the high specificity and sensitivity. In the present review, we focus on the clinical potential of lncRNAs as biomarkers in liquid biopsies in the diagnosis and prognosis of gastric cancer. We also comprehensively discuss the roles of lncRNAs and their molecular mechanisms in gastric cancer chemoresistance as well as their potential as therapeutic targets for gastric cancer precision medicine.
Aim
Rapid anthropogenic warming coupled with changes in land use is altering the distributions of species, with consequences for ecosystem functioning and services. It is crucial to evaluate species ...range shifts based on understanding of the interaction of temperature with non‐climatic factors such as habitat availability and dispersal potential. Here, we aim to investigate roles of environmental temperature, habitat availability and population connectivity on the distributions of hard‐shore intertidal animals. We further examine potential roles of extensive artificial seawall construction in enabling poleward expansion of species in China, thus reshaping coastal biogeography.
Location
Chinese coast.
Time period
2013–2017.
Major taxa studied
Intertidal invertebrates.
Methods
We took an integrative approach encompassing distributional ecology, thermal physiology, molecular genetics, heat budget modelling and larval dispersal to elucidate how interacting multiple drivers, including temperature, habitat availability and larval dispersal, determine distributions of hard‐shore invertebrates, focusing on what sets their range edges at a boundary between biogeographic provinces.
Results
Our results untangle the complex interactions of global climate change with the impacts of regional scale coastal development. Temperature, larval transport and habitat availability are the major proximate factors controlling the range limits of coastal marine species. The artificial shorelines provide suitable habitats for hard‐shore species on the Yangtze River Delta, and minimum temperature in winter is an important factor setting the new northern range limit of these hard‐shore species along the Chinese coast.
Main conclusions
In the face of global warming and global sprawl of marine hard infrastructure, species distributions, community structures and biogeographic patterns are experiencing dramatic changes. The combined influence of multiple human stressors including climate change and artificial shorelines can be evaluated by using a multidisciplinary framework, including ecological distribution, physiological sensitivity of species to these stressors, and the role of dispersal in maintaining population connectivity.
Conspectus Macrocyclic compounds are fundamental tools in supramolecular chemistry and have been widely used in molecular recognition, biomedicine, and materials science. The construction of new ...macrocycles with distinctive structures and properties would unleash new opportunities for supramolecular chemistry. Traditionally popular macrocycles, e.g., cyclodextrins, calixarenes, cucurbiturils, and pillararenes, possess specific cavities that are usually less than 10 Å in diameter; they are normally suitable for accommodating small- or medium-sized guests but cannot engulf giant molecules or structures. Furthermore, the skeletons of traditional macrocycles are impoverished and incapable of being changed; functional substituents can be introduced only on their portals. Thus, it is very challenging to construct macrocycles with customizable cavity sizes and/or diverse backbones. We have developed a versatile and modular strategy for synthesizing macrocycles, namely, biphennarenes (n = 3–8), based on the structure- or function-oriented replacement of reaction modules, functional modules, and linking modules. First, two reaction modules and one functional module are connected by Suzuki–Miyaura coupling to obtain a monomer having two reaction sites. Then Friedel–Crafts alkylation between the monomer and an aldehyde (linking module) serves to afford diversely functionalized macrocycles. Moreover, large macrocycles can be achieved by using long and rigid oligo(para-phenylene) monomers. Because of the modular synthesis and plentiful molecular supplies, the biphennarenes showed interesting recognition properties for both small molecules and large polypeptides. Customizable functional backbones and binding sites endowed this new family of macrocycles with peculiar self-assembly properties and potential applications in gas chromatography, pollutant capture, and physisorptive separation. Biphennarenes would be a promising family of workhorses in supramolecular chemistry. In this Account, we summarize our recent work on the chemistry of biphennarenes. We introduce their design and modular synthesis, including systematic exploration for reaction modules, customizable cavity sizes, skeleton functionalization, pre- and postmodification, and molecular cages. Thereafter, we discuss their host–guest properties, involving the binding for small guests by cationic/anionic/neutral biphennarenes, as well as the complexation of polypeptides by large quaterphennarenes. In addition, we outline the self-assembly and potential applications of this new family of macrocycles. Finally, we forecast their further development. The chemistry of biphennarenes is still in its infancy. Continued exploration will not only further expand the supramolecular toolbox but also open new avenues for the use of biphennarenes in the fields of biology, pharmaceutical science, and materials science.
Advanced kirigami/origami provides an automated technique for modulating the mechanical, electrical, magnetic and optical properties of existing materials, with remarkable flexibility, diversity, ...functionality, generality, and reconfigurability. In this paper, we review the latest progress in kirigami/origami on the microscale/nanoscale as a new platform for advanced 3D microfabrication/nanofabrication. Various stimuli of kirigami/origami, including capillary forces, residual stress, mechanical stress, responsive forces, and focussed-ion-beam irradiation-induced stress, are introduced in the microscale/nanoscale region. These stimuli enable direct 2D-to-3D transformations through folding, bending, and twisting of microstructures/nanostructures, with which the occupied spatial volume can vary by several orders of magnitude compared to the 2D precursors. As an instant and direct method, ion-beam irradiation-based tree-type and close-loop nano-kirigami is highlighted in particular. The progress in microscale/nanoscale kirigami/origami for reshaping the emerging 2D materials, as well as the potential for biological, optical and reconfigurable applications, is briefly discussed. With the unprecedented physical characteristics and applicable functionalities generated by kirigami/origami, a wide range of applications in the fields of optics, physics, biology, chemistry and engineering can be envisioned.
Ferroptosis is a programmed cell death pathway discovered in recent years, and ferroptosis‐inducing agents have great potential as new antitumor candidates. Here, we report a IrIII complex (Ir1) ...containing a ferrocene‐modified diphosphine ligand that localizes in lysosomes. Under the acidic environments of lysosomes, Ir1 can effectively catalyze Fenton‐like reaction, produce hydroxyl radicals, induce lipid peroxidation, down‐regulate glutathione peroxidase 4, and result in ferroptosis. RNA sequencing analysis shows that Ir1 can significantly affect pathways related to ferroptosis and cancer immunity. Accordingly, Ir1 can induce immunogenic cells death and suppress tumor growth in vitro, regulate T cell activity and immune microenvironments in vivo. In conclusion, we show the potential of small molecules with ferroptosis‐inducing capabilities for effective cancer immunotherapy.
Ferroptosis‐inducing agents have potential as antitumor candidates. A ferrocene‐modified IrIII complex with Fenton‐like catalytic activity is used to disturb the cellular redox balance, which leads to lipid peroxidation and ferroptosis of cancer cells. Ferroptosis induced by the IrIII complex causes immunogenic cell death (ICD) of cancer cell in vitro, which enhances cancer immune response in vivo.
Surface plasmon resonance (SPR) in noble metal nanoparticles and nanostructures offers an efficient means to transport and localize the energy of light into some nanoscale space regions called hot ...spots, where the electromagnetic field is enhanced by many orders of magnitude upon the incident light. This local field enhancement can induce very huge enhancement of Raman signal for a molecule embedded within the hot spot, which has tremendous applications in surface‐enhanced Raman spectroscopy (SERS) and tip‐enhanced Raman spectroscopy (TERS). Here, a discussion is presented on how to engineer this SPR‐enhanced Raman scattering from both the mesoscopic and microscopic levels. The mesoscopic level focuses on engineering and optimizing the geometric and physical configurations of plasmonic nanoparticles in order to have as large as possible electromagnetic field enhancement factor in the hot spot. The microscopic level focuses on investigating the light–molecule interaction (both chemical and physical) in the microscopic level, either classical or quantum, in order to have deep and complete understanding of the key microscopic issues influencing the Raman scattering and then exploring microscopic means to further enhance the Raman scattering as large as possible. Although in many situations these two scopes can be considered separately, there are also many situations where these two scopes need to be considered together. A prominent example, discussed here, is the critical role of molecule Rayleigh scattering in a plasmonic nanogap. Furthermore, several important issues are pointed out that need attention and caution in exploring and evaluating the quantitative SPR‐based Raman enhancement, including the quantum plasmonics correction, surface and interface electron scattering correction, and the validity of classical electromagnetics and electrodynamics approaches used in single and few atom scale plasmonics.
An overview and perspective on harnessing and engineering the surface plasmon resonance (SPR) of metal nanostructures to enhance molecule Raman scattering via the scheme of surface‐enhanced and tip‐enhanced Raman spectroscopy are presented. Mesoscopic strategies for engineering SPR via geometric and physical routes and microscopic strategies for engineering the optical, chemical and electronic interaction of molecule with plasmon are discussed.
Atomically precise copper clusters are highly desirable catalysts for electrocatalytic CO2 reduction reaction (CO2RR) and provide an ideal platform for elaborating structure–activity relationships. ...However, systematic comparative studies of Cu cluster isomers for electrocatalytic CO2RR are lacking because they are challenging to synthesize. A group of structurally precise Cu8 cluster isomers with different core structures (cube‐ and ditetrahedron‐shaped) were developed and investigated for highly active and selective CO2 reduction. Electrocatalytic measurements showed that the ditetrahedron‐shaped Cu8 cluster exhibited a higher FEHCOOH (≈92 %) at −1.0 V and higher selectivity than the cube‐shaped cluster. Theoretical investigations revealed different levels of competitiveness with the hydrogen evolution reaction on the respective core‐shaped Cu8 clusters and decreased free energies for the adsorbed HCOO* intermediates on the ditetrahedron‐shaped Cu8 clusters.
A group of atomically precise Cu8 cluster isomers with two core structures (cube‐ and ditetrahedron‐shaped) were investigated for highly active and selective CO2 reduction. A difference in catalytic performance was attributed to variable metal core arrangements hidden in Cu8 nanoclusters. The ditetrahedron‐shaped cluster exhibits a high Faradaic efficiency for formic acid generation (FEHCOOH) almost two times that of the cube‐shaped cluster.
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