Piezochromic materials that exhibit pressure‐dependent luminescence variations are attracting interest with wide potential applications in mechanical sensors, anticounterfeiting and storage devices. ...Crystalline porous materials (CPMs) have been widely studied in piezochromism for highly tunable luminescence. Nevertheless, reversible and high‐contrast emission response with a wide pressure range is still challenging. Herein, the first example of hierarchical porous cage‐based πOF (Cage‐πOF‐1) with spring structure was synthesized by using aromatic chiral cages as building blocks. Its elastic properties evaluated based on the bulk modulus (9.5 GPa) is softer than most reported CPMs and the collapse point (20.0 GPa) significantly exceeds ever reported CPMs. As smart materials, Cage‐πOF‐1 displays linear pressure‐dependent emission and achieves a high‐contrast emission difference up to 154 nm. Pressure‐responsive limit is up to 16 GPa, outperforming the CPMs reported so far. Dedicated experiments and density functional theory (DFT) calculations illustrate that π–π interactions‐dominated controllable structural shrinkage and porous‐spring‐structure‐mediated elasticity is responsible for the outstanding piezofluorochromism.
Hierarchical porous aromatic chiral cage‐based πOF with spring‐like structure presents outstanding elasticity and reversible pressure‐dependent emission with high‐contrast emission difference over a wide pressure range.
Nanotechnology provides potential benefits for enhanced oil recovery (EOR) in low-permeability reservoirs. In this paper, SiO2/P(MBAAm-co-AM) composite nanoparticles were prepared using the ...distillation precipitation polymerization method. Scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis were employed to characterize the morphology and microstructure of nanoparticles. The swelling behavior of polymeric nanoparticles in brine was investigated to evaluate the effect of salinity and temperature. Kinetic and thermodynamic analyses were employed to reveal the swelling mechanism. Displacement experiments were performed to investigate their performance in EOR in low-permeability reservoirs. The results show that the swelling ratio of SiO2/P(MBAAm-co-AM) composite nanoparticles is higher at low salinity and high temperature, which can be explained by the Flory theory. The swelling process is spontaneous and endothermic, being controlled by physical adsorption involving the diffusion of water molecules, which complies with the first-order kinetics model. The suspension of SiO2/P(MBAAm-co-AM) composite nanoparticles can improve incremental oil recovery from 10.28 to 21.97% with an increase of the swelled particle size from 580 to 1160 nm. It is feasible that core–shell polymeric nanoparticles can be used for EOR in low-permeability reservoirs.
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•Higher tumor mutational burden indicated worse prognosis in diffuse glioma.•A gene risk score model was constructed based on the expression of hub genes.•Combined with clinical ...features, a prognostic nomogram was built and validated.•Immune infiltration was correlated to tumor mutational burden and prognosis.•An immune risk score model was constructed based on the proportion of immune cells.
Immune checkpoint inhibitors (ICIs) have been used as a novel treatment for diffuse gliomas, but the efficacy varies with patients, which may be associated with the tumor mutational burden (TMB) and immune infiltration. We aimed to explore the relationship between the two and their impacts on the prognosis.
The data of the training set were downloaded from The Cancer Genome Atlas (TCGA). “DESeq2” R package was used for differential analysis and identification of differentially expressed genes (DEGs). A gene risk score model was constructed based on DEGs, and a nomogram was developed combined with clinical features. With the CIBERSORT algorithm, the relationship between TMB and immune infiltration was analyzed, and an immune risk score model was constructed. Two models were verification in the validation set downloaded from the Chinese Glioma Genome Atlas (CGGA).
Higher TMB was related to worse prognosis, older age, higher grade, and higher immune checkpoint expression. The gene risk score model was constructed based on BIRC5, SAA1, and TNFRSF11B, and their expressions were all negatively correlated with prognosis. The nomogram was developed combined with age and grade. The immune risk score model was constructed based on M0 macrophages, neutrophils, naïve CD4+ T cells, and activated mast cells. The proportions of the first two were higher in the high-TMB group and correlated with worse prognosis, while the latter two were precisely opposite.
In diffuse gliomas, TMB was negatively correlated with prognosis. The association of immune infiltration with TMB and prognosis varied with the type of immune cells. The nomogram and risk score models can accurately predict prognosis. The results can help identify patients suitable for ICIs and potential therapeutic targets, thus improve the treatment of diffuse gliomas.
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•Nanoparticles coated with red blood cell membranes (RmGIB NPs) were developed.•RmGIB NPs loaded indocyanine green and a gambogic acid.•RmGIB NPs could prolong long-term circulation ...in vivo.•RmGIB NPs could provide synergistic chemo-photothermal therapy for tumor.
Recently, the fabrication of nanotechnology-based co-delivery systems has garnered enormous interest for efficacious cancer therapy. However, these systems still face certain challenges such as codelivery of drugs with different chemistries, inadequate loading efficiency, immune rejection resulting in rapid clearance and substantially poor bioavailability in vivo. To address the challenges, we have developed a biomimetic and stable design based on bovine serum albumin (BSA) nanoparticles that are encapsulated with a hydrophilic photothermal agent, indocyanine green (ICG), as well as a hydrophobic agent, gambogic acid (GA), via the desolvation method. Furthermore, these nanoconstructs have been coated with the red blood cell membranes (RBCm), which exhibit pronounced long-term circulation in addition to avoiding premature leakage of drugs. RBCm-coated BSA nanoparticles show a higher affinity towards both GA and ICG (RmGIB NPs), resulting in high loading efficiencies of 24.3 ± 1.2 % and 25.0 ± 1.2 %, respectively. Moreover, the bio-efficacy investigations of these biomimetic constructs (RmGIB NPs) in cells in vitro as well as in tumor-bearing mice in vivo confirm augmented inhibition, demonstrating potential synergistic chemo-photothermal therapeutic efficacy. Altogether, we provide an efficient delivery platform for designing and constructing BSA nanovehicles toward synergistic and effective co-delivery of therapeutics.
Thiocyanate anion (SCN–) can coordinate to solid surfaces in various coordination modes, endowing the solid surfaces with different structures and electronic and catalytic properties, but the rules ...that dictate the coordination preference are poorly understood due to the multiple coordination sites of both SCN– and the solid surfaces as well as the SCN–-lattice mismatch. In this article, extensive density functional theory calculations are performed to study the coordination modes of SCN– on some selected solid surfaces. In particular, the influence of surface stress, coverage, and counter cations is discussed at length. It is found that the time-honored principle of hard soft acid base can only partly account for the preference of sulfur or nitrogen coordination to the solid surfaces due to its failure to treat the Lewis acids and bases located at the borderline and to deal with the multiple coordination sites and the SCN–-lattice mismatch. Specific to solid surfaces, the coordination number and coordination strength can be gradually changed by applying stress. Moreover, the interactions of SCN– with the counter cations and solvent (water) can modify its coordination mode, which generally favors sulfur coordination owing to the stronger interaction between the more electronegative dangling nitrogen and the counter cations or water. The coordination of SCN– could modify the electronic and geometric properties of the solid surface, which would benefit the design of catalysts. For example, the SCN– coordination improved the conductivity of β-Ni(OH)2, which is potentially useful in electrocatalysis. This work sheds light on the coordination mode of SCN– with significant implications on a variety of applications that can exploit the coordination chemistry.
The utilization of extracellular vesicles (EVs) in clinical theranostics has rapidly advanced in the past decade. In November 2018, the International Society for Extracellular Vesicles (ISEV) held a ...workshop on "EVs in Clinical Theranostic". Here, we report the conclusions of roundtable discussions on the current advancement in the analysis technologies and we provide some guidelines to researchers in the field to consider the use of EVs in clinical application. The main challenges and the requirements for EV separation and characterization strategies, quality control and clinical investigation were discussed to promote the application of EVs in future clinical studies.
Mechanical properties are some of the most important parameters for understanding well drilling and hydraulic fracturing designs in unconventional reservoir development. As an effective tool, ...nanoindentation has been used to determine the mechanical properties of rocks at the nanoscale. In this study, the Longmaxi Formation shale samples from the Yibin area of China were collected and analyzed to obtain the multiphase mechanical properties. The mineral compositions and organic geochemistry of the shale samples were studied using X-ray diffraction, energy-dispersive X-ray spectrometry, and a carbon/sulfur analyzer. The pore structures of the shale samples at the micro- and nanoscales were characterized by field-emission scanning electron microscopy. The mechanical parameters of the shale samples, such as the hardness and elastic modulus, were investigated using the nanoindentation method to identify three mineral phases: brittle minerals, soft matters, and complex minerals at the interfaces between brittle minerals and soft matters. The uncertainty characteristics of the mechanical parameters of the three mineral phases were evaluated using the Weibull model, and the factors interfering with the mechanical parameters were analyzed for the different shale samples. The results showed that the brittle minerals had the largest recovered elastic deformations and the smallest residual deformations, while the soft matters had the largest residual deformations and the smallest recovered elastic deformations. The analysis results of the coefficients of variation and the Weibull modulus both confirmed that the scatter of the hardness was higher than that of the elastic modulus because of the uncertain contact area, and the hardness and elastic modulus of the soft matters had the highest uncertainty among the three mineral phases. The elastic modulus increased nonlinearly with increasing hardness according to a power function for the whole shale sample. The elastic modulus and hardness both had a favorable linear relationship with the total organic carbon (TOC) content, illustrating that the TOC content was one of the significant factors that affected the mechanical parameters of the shale samples.
An organic molecular electrode (OME) is obtained, in which the polyhydric organic molecules (3,4,5-trihydroxybenzamide, THBA) act as a guest molecule to decorate graphene hydrogel (rGO1). The THBA ...acts as a spacer to prevent the rGO sheet from aggregation and provides an active center for OME. In the three-electrode configuration, the prepared OME (rGO1-THBA) presents a capacitance of 390.6 F g–1 and has a capacitance retention of 73.7% even when the scanning rate increases from 5 to 100 mV s–1. Furthermore, we synthesize an organic molecule 1,4,5,8-naphthalenetetracarboxylic diimide (NDP) and immobilize it onto the rGO surface to form another OME (rGO-NDP) as the counter electrode. An all-carbon asymmetric supercapacitor (rGO1-THBA//rGO-NDP: ASC) is constructed by using rGO1-THBA and rGO-NDP as the positive and negative electrodes, respectively. The resultant device achieves a capacitance of 70.8 F g–1 and delivers an energy density of 14 W h kg–1, supplying the power of 590 W kg–1. More importantly, the two asymmetric devices in series connection are able to light up 24 LED lights for 100 s.
Organic synthesis strategy can tune electrochemical behavior of organic molecules by molecular level design, which can offer more material choices for sustainable supercapacitors. Herein, an organic ...polymer (Poly-perylene-3,4,9,10-tetracarboxydiimide-anthraquinone, PPA) is designed and synthesized as an electrode material that can achieve Faraday reaction with 4 electron transfers in a structural unit. When the PPA is directly used as electrode material, the specific capacitance can be up to 245 F g−1 at 5 mV s−1 within a more negative potential. Furthermore, PPA is modified on reduced graphene oxide (rGO) to prepare an Organic Molecule Electrode (OME, PPA/rGO-1), which can reach higher specific capacitance (604 F g−1 at 5 mV s−1) with good cycle stability (capacitance retention of 69.9% at 5 A g−1, over 10,000 cycles). Besides, a 2,6-dihydroxynaphthalene (DN) modified graphene hydrogel (GH) is prepared as positive electrode to match with resultant OME for fabricating an asymmetrical supercapacitor (ASC). The device can deliver an energy density of ~20 Wh kg−1. Two ASCs (in series) light 40 Light Emitting Diodes (LEDs), suggesting a potential application.
A novel organic polymer (Poly-perylene-3,4,9,10-tetracarboxydiimide-anthraquinone, PPA) is designed and synthesized that can achieve Faraday reaction with 4 electron transfers in a structural unit. Furthermore, PPA is modified on reduced graphene oxide (rGO) to prepare an Organic Molecule Electrode (OME, PPA/rGO-1). A 2,6-dihydroxynaphthalene (DN) modified graphene hydrogel (GH) is prepared as positive electrode to match with resultant PPA/rGO-1 for fabricating an asymmetrical supercapacitor. The device can deliver an energy density of ~20 Wh kg−1 and present good cycling stability (80%, over 5000 cycles). Two ASCs can light 40 Light Emitting Diodes. Display omitted
•An organic polymer PPA was designed and synthesized as electroactive material.•An organic molecule electrode with higher specific capacitance and better cyclic stability was further prepared.•The fabricated ACS exhibits good energy storage performance.
With an extensive application of flooding technologies in oil recovery, traditional emulsion flooding has seen many limits due to its poor stability and easy demulsification. Pursuing a new robust ...emulsion plays a fundamental role in developing highly effective emulsion flooding technology. In this work, a novel Pickering emulsion with special magnetic nanoparticles Fe
3
O
4
@PDA@Si was designed and prepared. To disclose the flooding mechanism from magnetic nanoparticles, the physico-chemical characterization of Fe
3
O
4
@PDA@Si was systematically examined. Meanwhile, the flooding property of the constructed Pickering emulsion was evaluated on the basis of certain downhole conditions. The results showed that the synthesis of Fe
3
O
4
@PDA@Si nanoparticles was found to have a hydrophobic core-shell structure with a diameter of 30 nm. Pickering emulsions based on Fe
3
O
4
@PDA@Si nanoparticles at an oil-to-water ratio of 5:5, 50°C, the water separation rate was only 6% and the droplet diameter of the emulsion was approximately 15 μm in the ultra-depth-of-field microscope image. This demonstrates the excellent stability of Pickering emulsions and improves the problem of easy demulsification. We further discussed the oil displacement mechanism and enhanced oil recovery effect of this type of emulsion. The microscopic flooding experiment demonstrated that profile control of the Pickering emulsion played a more important role in enhanced recovery than emulsification denudation, with the emulsion system increasing oil recovery by 10.18% in the micro model. Core flooding experiments have established that the incremental oil recovery of the Pickering emulsion increases with decreasing core permeability, from 12.36% to 17.39% as permeability drops from 834.86 to 219.34 × 10
−3
μm
2
. This new Pickering emulsion flooding system stabilized by Fe
3
O
4
@PDA@Si nanoparticles offers an option for enhanced oil recovery (EOR).
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