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"Zheng, Zhikun"
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On-water surface synthesis of crystalline, few-layer two-dimensional polymers assisted by surfactant monolayers
by
Heine, Thomas
,
Qi, Haoyuan
,
Kaiser, Ute
in
639/638/298/923/1028
,
639/638/455/941
,
639/638/542/970
2019
Despite rapid progress in recent years, it has remained challenging to prepare crystalline two-dimensional polymers. Here, we report the controlled synthesis of few-layer two-dimensional polyimide crystals on the surface of water through reaction between amine and anhydride monomers, assisted by surfactant monolayers. We obtained polymers with high crystallinity, thickness of ~2 nm and an average crystal domain size of ~3.5 μm
2
. The molecular structure of the materials, their grain boundaries and their edge structures were characterized using X-ray scattering and transmission electron microscopy techniques. These characterizations were supported by computations. The formation of crystalline polymers is attributed to the pre-organization of monomers at the water–surfactant interface. The surfactant, depending on its polar head, promoted the arrangement of the monomers—and in turn their polymerization—either horizontally or vertically with respect to the water surface. The latter was observed with a surfactant bearing a carboxylic acid group, which anchored amine monomers vertically through a condensation reaction. In both instances, micrometre-sized, few-layer two-dimensional polyamide crystals were grown.
It is difficult to prepare 2D polymers that are crystalline over large areas. Now, few-layer 2D polyimides and polyamides with good crystallinity on the micrometre scale have been synthesized on a water surface. A surfactant monolayer is used to organize amine monomers before their polymerization with anhydride moieties.
Journal Article
Engineering crystalline quasi-two-dimensional polyaniline thin film with enhanced electrical and chemiresistive sensing performances
2019
Engineering conducting polymer thin films with morphological homogeneity and long-range molecular ordering is intriguing to achieve high-performance organic electronics. Polyaniline (PANI) has attracted considerable interest due to its appealing electrical conductivity and diverse chemistry. However, the synthesis of large-area PANI thin film and the control of its crystallinity and thickness remain challenging because of the complex intermolecular interactions of aniline oligomers. Here we report a facile route combining air-water interface and surfactant monolayer as templates to synthesize crystalline quasi-two-dimensional (q2D) PANI with lateral size ~50 cm
2
and tunable thickness (2.6–30 nm). The achieved q2D PANI exhibits anisotropic charge transport and a lateral conductivity up to 160 S cm
−1
doped by hydrogen chloride (HCl). Moreover, the q2D PANI displays superior chemiresistive sensing toward ammonia (30 ppb), and volatile organic compounds (10 ppm). Our work highlights the q2D PANI as promising electroactive materials for thin-film organic electronics.
Large area and homogeneous PANI thin films are important in high-performance organic electronics, but controlling the thickness and crystallinity in PANI thin films is challenging. Here the authors use air-water interface and surfactant monolayer templates to synthesize large area crystalline PANI films with tunable thickness.
Journal Article
Growth of single-crystal imine-linked covalent organic frameworks using amphiphilic amino-acid derivatives in water
2023
A core feature of covalent organic frameworks (COFs) is crystallinity, but current crystallization processes rely substantially on trial and error, chemical intuition and large-scale screening, which typically require harsh conditions and low levels of supersaturation, hampering the controlled synthesis of single-crystal COFs, particularly on large scales. Here we report a strategy to produce single-crystal imine-linked COFs in aqueous solutions under ambient conditions using amphiphilic amino-acid derivatives with long hydrophobic chains. We propose that these amphiphilic molecules self-assemble into micelles that serve as dynamic barriers to separate monomers in aqueous solution (nodes) and hydrophobic compartments of the micelles (linkers), thereby regulating the polymerization and crystallization processes. Disordered polyimines were obtained in the micelle, which were then converted into crystals in a step-by-step fashion. Five different three-dimensional COFs and a two-dimensional COF were obtained as single crystals on the gram scale, with yields of 92% and above.Covalent organic frameworks (COFs) have remained difficult to grow as single crystals. Now, amphiphilic amino-acid derivatives that assemble in micelles in aqueous solutions have been shown to promote the growth of a variety of imine-bridged COFs into single crystals, in a step-by-step fashion, within their hydrophobic compartment.
Journal Article
Wafer-sized multifunctional polyimine-based two-dimensional conjugated polymers with high mechanical stiffness
2016
One of the key challenges in two-dimensional (2D) materials is to go beyond graphene, a prototype 2D polymer (2DP), and to synthesize its organic analogues with structural control at the atomic- or molecular-level. Here we show the successful preparation of porphyrin-containing monolayer and multilayer 2DPs through Schiff-base polycondensation reaction at an air–water and liquid–liquid interface, respectively. Both the monolayer and multilayer 2DPs have crystalline structures as indicated by selected area electron diffraction. The monolayer 2DP has a thickness of∼0.7 nm with a lateral size of 4-inch wafer, and it has a Young’s modulus of 267±30 GPa. Notably, the monolayer 2DP functions as an active semiconducting layer in a thin film transistor, while the multilayer 2DP from cobalt-porphyrin monomer efficiently catalyses hydrogen generation from water. This work presents an advance in the synthesis of novel 2D materials for electronics and energy-related applications.
Forming 2D polymers in a controlled manner on the atomic and molecular level is difficult. Here, Feng and others have used Schiff-base polycondensation reactions at an air-water or liquid-liquid interface to form porphyrin containing monolayer and multilayer 2D polymers.
Journal Article
Tumor-associated macrophage-derived exosomes LINC01592 induce the immune escape of esophageal cancer by decreasing MHC-I surface expression
2023
Background
TAMs (tumor-associated macrophages) infiltration promotes the progression of esophageal cancer (EC). However, the underlying mechanisms remain unclear.
Methods
Abnormal expression of LINC01592 from EC microarrays of the TCGA database was analyzed. LINC01592 expression level was validated in both EC cell lines and tissues. Stable LINC01592 knockdown and overexpression of EC cell lines were established. In vitro and in vivo trials were conducted to test the impact of LINC01592 knockdown and overexpression on EC cells. RNA binding protein immunoprecipitation (RIP), RNA pulldown assays, and Immunofluorescence (IF) were used to verify the combination of E2F6 and LINC01592. The combination of E2F6 and NBR1 was verified through the utilization of ChIP and dual luciferase reporter assays.
Results
LINC01592 is carried and transferred by exosomes secreted by M2-TAMs to tumor cells. The molecular mechanism underlying the promotion of NBR1 transcription involves the direct binding of LINC01592 to E2F6, which facilitates the nuclear entry of E2F6. The collaborative action of LINC01592 and E2F6 results in improved NBR1 transcription. The elevation of NBR1 binding to the ubiquitinated protein MHC-I via the ubiquitin domain caused a higher degradation of MHC-I in autophagolysosomes and a reduction in MHC-I expression on the exterior of cancerous cell. Consequently, this caused cancerous cells to escape from CD8
+
CTL immune attack. The tumor-promoting impacts of LINC01592, as well as the growth of M2-type macrophage-driven tumors, were significantly suppressed by the interruption of E2F6/NBR1/MHC-I signaling through the effect of siRNA or the corresponding antibody blockade. Significantly, the suppression of LINC01592 resulted in an upregulation of MHC-I expression on the tumor cell membrane, thereby enhancing the efficacy of CD8+ T cell reinfusion therapy.
Conclusions
The investigation conducted has revealed a significant molecular interaction between TAMs and EC via the LINC01592/E2F6/NBR1/MHC-I axis, which facilitates the progression of malignant tumors. This suggests that a therapeutic intervention targeting this axis may hold promise for the treatment of the disease.
Journal Article
Stabilized Molybdenum Trioxide Nanowires as Novel Ultrahigh‐Capacity Cathode for Rechargeable Zinc Ion Battery
2019
Exploration of high‐performance cathode materials for rechargeable aqueous Zn ion batteries (ZIBs) is highly desirable. The potential of molybdenum trioxide (MoO3) in other electrochemical energy storage devices has been revealed but held understudied in ZIBs. Herein, a demonstration of orthorhombic MoO3 as an ultrahigh‐capacity cathode material in ZIBs is presented. The energy storage mechanism of the MoO3 nanowires based on Zn2+ intercalation/deintercalation and its electrochemical instability mechanism are particularly investigated and elucidated. The severe capacity decay of the MoO3 nanowires during charging/discharging cycles arises from the dissolution and the structural collapse of MoO3 in aqueous electrolyte. To this end, an effective strategy to stabilize MoO3 nanowires by using a quasi‐solid‐state poly(vinyl alcohol)(PVA)/ZnCl2 gel electrolyte to replace the aqueous electrolyte is developed. The capacity retention of the assembled ZIBs after 400 charge/discharge cycles at 6.0 A g−1 is significantly boosted, from 27.1% (in aqueous electrolyte) to 70.4% (in gel electrolyte). More remarkably, the stabilized quasi‐solid‐state ZIBs achieve an attracting areal capacity of 2.65 mAh cm−2 and a gravimetric capacity of 241.3 mAh g−1 at 0.4 A g−1, outperforming most of recently reported ZIBs. Orthorhombic MoO3 nanowires are demonstrated as an ultrahigh‐capacity cathode material in Zn ion batteries (ZIBs). Benefiting from the unique layered structure and the stabilized MoO3 nanowires, a high‐performance quasisolid state Zn//MoO3 battery with attracting capacity of 2.65 mAh cm−2 (243.1 mAh g−1) and energy density of 14.4 mWh cm−3 as well as decent durability is constituted.
Journal Article
Copper-surface-mediated synthesis of acetylenic carbon-rich nanofibers for active metal-free photocathodes
2018
The engineering of acetylenic carbon-rich nanostructures has great potential in many applications, such as nanoelectronics, chemical sensors, energy storage, and conversion, etc. Here we show the synthesis of acetylenic carbon-rich nanofibers via copper-surface-mediated Glaser polycondensation of 1,3,5-triethynylbenzene on a variety of conducting (e.g., copper, graphite, fluorine-doped tin oxide, and titanium) and non-conducting (e.g., Kapton, glass, and silicon dioxide) substrates. The obtained nanofibers (with optical bandgap of 2.51 eV) exhibit photocatalytic activity in photoelectrochemical cells, yielding saturated cathodic photocurrent of ca. 10 µA cm
−2
(0.3–0 V vs. reversible hydrogen electrode). By incorporating thieno[3,2-b]thiophene units into the nanofibers, a redshift (ca. 100 nm) of light absorption edge and twofold of the photocurrent are achieved, rivalling those of state-of-the-art metal-free photocathodes (e.g., graphitic carbon nitride of 0.1–1 µA cm
−2
). This work highlights the promise of utilizing acetylenic carbon-rich materials as efficient and sustainable photocathodes for water reduction
While photoelectrochemical devices combine light-absorption with fuel and electricity generation, their implementation is hampered by high costs and low output. Here, the authors synthesized acetylene-rich carbon fibers by copper-mediated polymerization for high-activity, metal-free photocathodes.
Journal Article
Comparative Study on Thermal Runaway Characteristics of Lithium Iron Phosphate Battery Modules Under Different Overcharge Conditions
2020
In order to study the thermal runaway characteristics of the lithium iron phosphate (LFP) battery used in energy storage station, here we set up a real energy storage prefabrication cabin environment, where thermal runaway process of the LFP battery module was tested and explored under two different overcharge conditions (direct overcharge to thermal runaway and overcharge to safety vent open-standing–recharge to thermal runaway). In this experiment, surveillance cameras, infrared imagers, temperature detectors, and gas detectors were used to guarantee all-around online observation. The experimental results show that under the conditions of these experiments, stop the overcharging process in time after the first battery safety vent is opened can effectively suppress the further development of thermal runaway, and maintain a safe state within 2 h. It also indicates that the thermal runaway process of LFP battery module changes with heat accumulation which needs reaction time, if the heat accumulation could be stopped in time, the occurrence of thermal runaway accidents would be avoided. This provides effective theoretical guidance for safety warning and fire protection of electrochemical energy storage stations with LFP battery system.
Journal Article
Interfacially Locked Metal Aerogel Inside Porous Polymer Composite for Sensitive and Durable Flexible Piezoresistive Sensors
2022
Flexible pressure sensors play significant roles in wearable devices, electronic skins, and human‐machine interface (HMI). However, it remains challenging to develop flexible piezoresistive sensors with outstanding comprehensive performances, especially with excellent long‐term durability. Herein, a facile “interfacial locking strategy” has been developed to fabricate metal aerogel‐based pressure sensors with excellent sensitivity and prominent stability. The strategy broke the bottleneck of the intrinsically poor mechanical properties of metal aerogels by grafting them on highly elastic melamine sponge with the help of a thin polydimethylsiloxane (PDMS) layer as the interface‐reinforcing media. The hierarchically porous conductive structure of the ensemble offered the as‐prepared flexible piezoresistive sensor with a sensitivity as high as 12 kPa−1, a response time as fast as 85 ms, and a prominent durability over 23 000 compression cycles. The excellent comprehensive performance enables the successful application of the flexible piezoresistive sensor as two‐dimensional (2D) array device as well as three‐dimensional (3D) force‐detecting device for real‐time monitoring of HMI activities. An “interfacial locking strategy” is developed to design metal aerogel‐based flexible piezoresistive sensors with both high sensitivity and prominent durability. The interpenetrated interface‐reinforcing PDMS layer tightly grafts the metal aerogels on the highly elastic and mechanically stable sponge, breaking the bottleneck of intrinsically poor mechanical strength of metal aerogels, and significantly expanding their applications in emerging fields.
Journal Article
CDKL1 potentiates the antitumor efficacy of radioimmunotherapy by binding to transcription factor YBX1 and blocking PD-L1 expression in lung cancer
2024
Background
The evasion of the immune response by tumor cells through programmed death-ligand 1 (PD-L1) has been identified as a factor contributing to resistance to radioimmunotherapy in lung cancer patients. However, the precise molecular mechanisms underlying the regulation of PD-L1 remain incompletely understood. This study aimed to investigate the role of cyclin-dependent kinase-like 1 (CDKL1) in the modulation of PD-L1 expression and the response to radioimmunotherapy in lung cancer.
Methods
The tumorigenic roles of CDKL1 were assessed via cell growth, colony formation, and EdU assays and an in vivo nude mouse xenograft model. The in vitro radiosensitization effect of CDKL1 was evaluated using a neutral comet assay, γH2AX foci formation analysis, and a clonogenic cell survival assay. The protein‒protein interactions were confirmed via coimmunoprecipitation and GST pulldown assays. The regulation of PD-L1 by CDKL1 was evaluated via chromatin immunoprecipitation (ChIP), real-time quantitative PCR, and flow cytometry analysis. An in vitro conditioned culture model and an in vivo C57BL/6J mouse xenograft model were developed to detect the activation markers of CD8
+
T cells and evaluate the efficacy of CDKL1 overexpression combined with radiotherapy (RT) and an anti-PD-L1 antibody in treating lung cancer.
Results
CDKL1 was downregulated and suppressed the growth and proliferation of lung cancer cells and increased radiosensitivity in vitro and in vivo. Mechanistically, CDKL1 interacted with the transcription factor YBX1 and decreased the binding affinity of YBX1 for the
PD-L1
gene promoter, which consequently inhibits the expression of PD-L1, ultimately leading to the activation of CD8
+
T cells and the inhibition of immune evasion in lung cancer. Moreover, the combination of CDKL1 overexpression, RT, and anti-PD-L1 antibody therapy exhibited the most potent antitumor efficacy against lung cancer.
Conclusions
Our findings demonstrate that CDKL1 plays a crucial role in regulating PD-L1 expression, thereby enhancing the antitumor effects of radioimmunotherapy. These results suggest that CDKL1 may be a promising therapeutic target for the treatment of lung cancer.
Journal Article