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Background Dendritic cell (DC) vaccines for cancer therapy offer the possibility to let the patient’s own immune system kill cancer cells. However, DC vaccines have shown less efficacy than expected due to failure to induce cancer cell killing and by activating T regulatory cells. Methods We tested if inhibition of signalling via WASp and Arp2/3 using the small molecule CK666 would enhance DC-mediated killing of tumour cells in vitro and in vivo. Results Using CK666 during the ex vivo phase of antigen processing of ovalbumin (OVA), murine and human DCs showed decreased phagosomal acidification, indicating activation of the cross-presentation pathway. When compared to untreated DCs, DCs treated with CK666 during uptake and processing of OVA-induced increased proliferation of OVA-specific CD8+ OT-I T cells in vitro and in vivo. Using the aggressive B16-mOVA melanoma tumour model, we show that mice injected with CK666-treated DCs and OVA-specific CD8+ OT-I T cells showed higher rejection of B16 melanoma cells when compared to mice receiving non-treated DCs. This resulted in the prolonged survival of tumour-bearing mice receiving CK666-treated DCs. Moreover, combining CK666-treated DCs with the checkpoint inhibitor anti-PD1 further prolonged survival. Conclusion Our data suggest that the small molecule inhibitor CK666 is a good candidate to enhance DC cross-presentation for cancer therapy.

ObjectiveRevealing the single-cell immune ecosystems in true versus de novo hepatocellular carcinoma (HCC) recurrences could help the optimal development of immunotherapies.DesignWe performed 5’and VDJ single-cell RNA-sequencing on 34 samples from 20 recurrent HCC patients. Bulk RNA-sequencing, flow cytometry, multiplexed immunofluorescence, and in vitro functional analyses were performed on samples from two validation cohorts.ResultsAnalyses of mutational profiles and evolutionary trajectories in paired primary and recurrent HCC samples using whole-exome sequencing identified de novo versus true recurrences, some of which occurred before clinical diagnosis. The tumour immune microenvironment (TIME) of truly recurrent HCCs was characterised by an increased abundance in KLRB1+CD8+T cells with memory phenotype and low cytotoxicity. In contrast, we found an enrichment in cytotoxic and exhausted CD8+T cells in the TIME of de novo recurrent HCCs. Transcriptomic and interaction analyses showed elevated GDF15 expression on HCC cells in proximity to dendritic cells, which may have dampened antigen presentation and inhibited antitumour immunity in truly recurrent lesions. In contrast, myeloid cells’ cross talk with T cells-mediated T cell exhaustion and immunosuppression in the TIME ofde novorecurrent HCCs. Consistent with these findings, a phase 2 trial of neoadjuvant anti-PD-1 immunotherapy showed more responses in de novo recurrent HCC patients.ConclusionTrue and de novo HCC recurrences occur early, have distinct TIME and may require different immunotherapy strategies. Our study provides a source for genomic diagnosis and immune profiling for guiding immunotherapy based on the type of HCC recurrence and the specific TIME.

Supplementary Figure from Combination Neoantigen-Based Dendritic Cell Vaccination and Adoptive T-Cell Transfer Induces Antitumor Responses Against Recurrence of Hepatocellular Carcinoma

A high rate of recurrence after curative therapy is a major challenge for the management of hepatocellular carcinoma (HCC). Currently, no effective adjuvant therapy is available to prevent HCC recurrence. We designed a personalized neoantigen-loaded dendritic cell vaccine and neoantigen-activated T-cell therapy, and used it as adjuvant therapy to treat 10 patients with HCC who had undergone curative resection or radiofrequency ablation in the first stage of a phase II trial (NCT03067493). The primary outcomes were safety and neoantigen-specific immune response. Disease-free survival (DFS) was also evaluated. The immunotherapy was successfully administered to all the patients without unexpected delay and demonstrated a reasonable safety profile with no grade ≥3 treatment-related side effects reported. Seventy percent of patients generated de novo circulating multiclonal neoantigen-specific T-cell responses. Induced neoantigen-specific immunity was maintained over time, and epitope spreading was observed. Patients who generated immune responses to treatment exhibited prolonged DFS compared with nonresponders (P = 0.012), with 71.4% experiencing no relapse for 2 years after curative treatment. High expression of an immune stimulatory signature, enhanced immune-cell infiltration (i.e., CD8+ T cells), and upregulated expression of T-cell inflammatory gene profiles were found in the primary tumors of the responders. In addition, neoantigen depletion (immunoediting) was present in the recurrent tumors compared with the primary tumors (7/9 vs. 1/17, P = 0.014), suggesting that immune evasion occurred under the pressure of immunotherapy. Our study indicates that neoantigen-based combination immunotherapy is feasible, safe, and has the potential to reduce HCC recurrence after curative treatment.

Table S5 shows detailed information of structure variations in the six HCC patients with WGS analysis.

Fig.S1 shows flow chart of enrollment for multifocal HCC patients with anti-PD-1 therapy. Fig.S2 shows CT images of the six HCC patients with two tumors in the liver. Fig.S3 shows purity of tumor content of the six HCC patients with two tumors in the liver. Fig.S4 shows HBV integration sites in the six HCC patients with two tumors in the liver. Fig.S5 shows expression level of TERT in the six HCC patients with two tumors in the liver. Fig.S6 shows landscape of inter-chromosomal translocations and copy number alterations in small and large tumors of four cases. Fig.S7 shows number and types of chromosomal rearrangement in the six HCC patients with two tumors in the liver. Fig.S8 shows copy number aberrations in the six HCC patients with two tumors in the liver. Fig.S9 shows mutational landscape of the six HCC patients with two tumors in the liver. Fig.S10 shows non-silent mutations in the six HCC patients with two tumors in the liver. Fig.S11 shows profile of mutational cancer cell fractions of small and large tumors in the six HCC patients. Fig.S12 shows unsupervised clustering of RNA expression in tumors and adjacent normal liver tissues of 12 multifocal HCC patients. Fig.S13 shows expression level of immune functional genes in small and large tumors of 12 multifocal HCC patients. Fig.S14 shows expression level of immune stimulators in small and large tumors of 12 multifocal HCC patients. Fig.S15 shows expression level of immune inhibitors in small and large tumors of 12 multifocal HCC patients. Fig.S16 shows mutations of immune-related genes in the six HCC patients with two tumor nodules in the liver. Fig.S17 shows images of the small and large tumors before and after anti-PD-1 therapy.

Purpose:Targeted therapy and immunotherapy are transforming the treatment approach for intrahepatic cholangiocarcinoma (ICC). However, little is known about the intertumor heterogeneity (ITH) of multifocal ICC and its impacts on patient response to these treatments. We aimed to characterize the immunogenomic and epigenomic heterogeneity of multifocal ICC to guide treatment decision making.Experimental Design:We obtained 66 tumor samples from 16 patients with multifocal ICC and characterized the tumor and immune heterogeneity using whole-exome sequencing, bulk and single-cell RNA sequencing, methylation microarray, and multiplex immunostaining. Patients were divided into high- or low-ITH groups according to the median ITH index. Two independent cohorts were used to validate findings. Responses to anti-PD-1 therapy were assessed.Results:Multifocal ICC presented considerable intertumor genomic, transcriptional, and epigenomic heterogeneity within a patient in high ITH group. The immune profile among multiple tumors within a patient was relatively less heterogeneous in high- or low-ITH group, and consistent responses of multiple tumors to anti-PD-1 immunotherapy were observed. Unsupervised clustering of immune markers identified one low and one high immune subtype, with higher immune cell infiltration, closer tumor–immune cell interactions, and upregulated IFN-signature expression in high-immune subtype. Determining expression levels of CD8B and ICOS facilitated this immune classification and prediction of patient prognosis. Finally, promoter DNA methylation contributed to different immune profiles of two subtypes by regulating immune-gene expression.Conclusions:There is comprehensive heterogeneity in the genome, transcriptome, and epigenome of multifocal ICC. On the basis of the less heterogeneous immune profile of ICC, we suggest an immune classification that stratifies patients' prognosis and may support personalized immunotherapy.

Supplementary Data from Multiomic Analysis Reveals Comprehensive Tumor Heterogeneity and Distinct Immune Subtypes in Multifocal Intrahepatic Cholangiocarcinoma

Table S9 shows potentially functional mutations of immune-related genes in the six HCC patients with WGS analysis.

Table S3 shows summary of whole genome sequencing in the six patients with two tumor nodules in the liver.

Table S1 shows clinicopathologic information of 12 multifocal HCC patients. Table S2 shows PCR primers used for validation of HBV integration sites. Table S4 shows HBV integration analysis in HCC patients with WGS data. Table S8 shows P-value of pathways enrichment analysis in the small and large tumors of 12 multifocal HCC patients. Table S10 shows correlation between the number of rearrangements and immune activity. Table S11 shows detailed clinical data of eight patients with anti-PD-1 therapy.

Table S6 shows detailed information of copy number alterations in the six HCC patients with WGS analysis.

Purpose:Immune checkpoint inhibitor therapy is emerging as the promising option for patients with advanced hepatocellular carcinoma. We aimed to investigate the heterogeneity of different tumor nodules of the same patient with multifocal hepatocellular carcinomas in response to immunotherapy and its molecular mechanisms.Experimental Design:We attained 45 surgical tumor samples including 33 small and 12 large nodules from 12 patients with multifocal hepatocellular carcinoma and evaluated genomic and immune heterogeneity among tumors through whole-genome sequencing and RNA sequencing. IHC was performed to validate the expression of immune markers. The responses to anti–programmed cell death protein-1 (PD-1) therapy in patients with multifocal hepatocellular carcinoma were evaluated.Results:The small and large tumors within the same patient presented with similar genomic characteristics, indicating their same genomic origin. We further found the small tumors had higher immune cell infiltration including more CD8+ T cells, M1 macrophages, and monocytes as compared with large tumors. Besides, the expression of interferon signature predictive of response to anti–PD-1 therapy was significantly upregulated in the small tumors. Moreover, the immune pathways were more vigorous along with less active proliferation pathways in the small tumors. In keeping with this, we found that small nodules were more sensitive to anti–PD-1 therapy than large nodules in patients with multifocal hepatocellular carcinoma.Conclusions:The small tumors in patients with multifocal hepatocellular carcinoma had higher immune cell infiltration and upregulation of immune pathways as compared with the large tumors, which can partially explain the different responses of small and large tumors in the same case to anti–PD-1 therapy.

Table S7 shows detailed information of candidate somatic mutations in the six HCC patients with WGS analysis.

Liquid-free ionic conductors (LFICs) have promising applications in flexible electronics because most ionic conductors currently suffer from ionic liquid leakage or water evaporation issues. However, it has been a formidable challenge for LFICs to achieve long-term repeated self-adhesion on different substrates, especially on soft biological tissues. Based on the double-network design concept, we first fabricate a series of repeatable self-adhesive liquid-free double-network ionic conductors (SALFDNICs), consisting of stretchable first poly(AA-ChCl)-type supramolecular deep eutectic polymer networks and stiff second polydopamine (PDA) networks, which can maintain sufficient dynamic hydrogen bonds and catechol groups in the ionic conductors by preventing the overoxidation of dopamine, thus balancing the contradiction between adhesion and cohesion in liquid-free ionic conductors. Therefore, SALFDNICs can instantly form various interface interaction forces with multiple substrates (adhesion strength up to 757 N/m) and firmly adhere to various substrates for 20 detachment-reattachment cycles with a reduction in adhesion strength of less than 15%. Furthermore, SALFDNICs also have other comprehensive properties, such as optimum self-healing properties (self-healing efficiency of 90%), good stretchability (strain at break of 1200%), and promising conductivity (2.31 × 10

A high rate of recurrence after curative therapy is a major challenge for the management of hepatocellular carcinoma (HCC). Currently, no effective adjuvant therapy is available to prevent HCC recurrence. We designed a personalized neoantigen-loaded dendritic cell vaccine and neoantigen-activated T-cell therapy, and used it as adjuvant therapy to treat 10 patients with HCC who had undergone curative resection or radiofrequency ablation in the first stage of a phase II trial (NCT03067493). The primary outcomes were safety and neoantigen-specific immune response. Disease-free survival (DFS) was also evaluated. The immunotherapy was successfully administered to all the patients without unexpected delay and demonstrated a reasonable safety profile with no grade ≥3 treatment-related side effects reported. Seventy percent of patients generated de novo circulating multiclonal neoantigen-specific T-cell responses. Induced neoantigen-specific immunity was maintained over time, and epitope spreading was observed. Patients who generated immune responses to treatment exhibited prolonged DFS compared with nonresponders (P = 0.012), with 71.4% experiencing no relapse for 2 years after curative treatment. High expression of an immune stimulatory signature, enhanced immune-cell infiltration (i.e., CD8+ T cells), and upregulated expression of T-cell inflammatory gene profiles were found in the primary tumors of the responders. In addition, neoantigen depletion (immunoediting) was present in the recurrent tumors compared with the primary tumors (7/9 vs. 1/17, P = 0.014), suggesting that immune evasion occurred under the pressure of immunotherapy. Our study indicates that neoantigen-based combination immunotherapy is feasible, safe, and has the potential to reduce HCC recurrence after curative treatment.

The use of functional biodegradable wastes to treat environmental problems would create minimal extra burden to our environment. In this paper, we propose a sustainable and practical strategy to turn spent coffee ground (SCG) into a multifunctional palladium-loaded catalyst for water treatment instead of going into landfill as solid waste. Bleached delignified coffee ground (D-SCG) has a porous structure and a good capability to reduce Pd (II) to Pd (0). A large amount of nanocellulose is formed on the surface of SCG after bleaching by H2O2, which anchors and disperses the palladium nanoparticles (Pd NPs). The D-SCG loaded with Pd NPs (Pd-D-SCG) is superhydrophilic, which facilitates water transport and thus promotes efficient removal of organic pollutants dissolved in water. Pd-D-SCG exhibits excellent room temperature catalytic activity for the removal of 4-nitrophenol (4-NP) and methylene blue (MB) in water and shows good chemical stability and recyclability in water, with no obvious decrease even after five repeated cycles.

By the photopolymerization 3D printing of photopolymerizable deep eutectic solvents, a stable and sensitive solid-state capacitive ionic skin is reported.

SummaryRevealing differential tumor immune microenvironment (TIME) characteristics between true versus de novo hepatocellular carcinoma (HCC) recurrence could help optimal development and use of immunotherapies. Here, we studied the TIME of recurrent HBV-related HCCs by 5’and VDJ single-cell and bulk RNA-sequencing, flow cytometry, and multiplexed immunofluorescence. Analyses of mutational profiles, evolutionary trajectories, and clonal architecture using whole-exome sequencing identified de novo versus true recurrences, some of which occurred before clinical diagnosis. The TIME of truly recurrent HCCs was characterized by an increased abundance in KLRB1+CD8+ T cells with memory phenotype and low cytotoxicity. In contrast, we found an enrichment in cytotoxic and exhausted CD8+ T cells in the TIME of de novo recurrent HCCs. Transcriptomic and interaction analyses showed an upregulated GDF15 expression level on HCC cells in proximity to dendritic cells, which may have dampened antigen presentation and inhibited anti-tumor immunity in the TIME of truly recurrent lesions. In contrast, we found that myeloid cells’ crosstalk with T cells mediated T cell exhaustion and immunosuppression in the TIME of de novo recurrent HCC. In conclusion, our results support genomic diagnosis and immune profiling for guiding immunotherapy implementation based on the type of HCC recurrence and TIME.HighlightsTruly recurrent lesions are seeded before primary tumor diagnosis, and that de novo cancer can occur earlier than the clinically used 2-year limit.ScRNA-seq unravels distinct immune ecosystems in true versus de novo HCC recurrences, highlighting the need for different immunotherapy strategies for two types of HCC recurrence.CD8+ T cells in de novo recurrence displayed cytotoxic and exhausted phenotypes while those in truly recurrent lesions showed a memory phenotype with weak cytotoxicity.HCC cells expressing the inhibitory molecule GDF15 were in the proximity of DCs only in truly recurrent lesions.High GDF15 expression level was associated with truly recurrent HCC and worse prognosis.Graphical abstract

Ionic skin with a high performance has been extensively explored due to its ability to convert external stimuli into obvious electrical signals for wearable electronics and intelligent detection. H...

Conductive elastomers (CEs) with strong mechanical properties have been fabricated and used in flexible electronics. However, the development of CEs with both super-high mechanical strength and extreme stretchability remains challenging. This paper reports on the development of a series of mechanically strong and tough CEs based on photopolymerizable deep eutectic solvents (PDESs) with dense hydrogen bonding interactions. One of these CEs exhibits the highest reported mechanical performance for elastomers, with tensile strength, strain at break and toughness up to 31.21 MPa, 3645% and 615 MJ m−3, respectively. Notably, this CE tolerates puncture and can lift a 10.5 kg weight (9500 times its own weight) without any failure. In addition, the series of CEs also shows excellent transparency (>94% in the visible range), favorable conductivity (0.007–0.04 S m−1), tunable stretchability (strain from 22% to 6164%) and good self-healing capability (electrical healing efficiency of 99% within 0.26 s). In view of the comprehensive properties of the CEs, we demonstrate the practical suitability of CEs by including them in a strain sensor to detect human motion. Based on their extremely facile preparation process and practical functionalities, we believe that CEs will not only contribute new methods for the development of mechanically strong conductors, but also open up novel avenues for flexible electronics.

Simultaneously achieving transparency, high mechanical strength and self-healing capability in conductive elastomers with simple and green features is a challenge. Here we develop a novel strategy for a tough yet self-healing supramolecular network by introducing Al(III)-carboxyl complexes into photo-polymerizable deep eutectic solvent (PDES). The resulting polymer simultaneously exhibits high transparency, ionic conductivity, and high stretchability. Notably, due to synergetic interactions of the H-bonds and coordination bonds in the polymer matrix, the supramolecular network shows a high stress at break while achieving good self-healing capability. In view of the outstandingly comprehensive properties, we continue to verify the practicability of our prepared materials as strain sensors to monitor external stimuli such as human motions. Our methodology is simple, green and time-saving, and the fundamental design concept derived from the multifunctional PDES will contribute to the development of tough, self-healing transparent materials and flexible electronics.

Ionic conductors are normally prepared from water-based materials in the solid form and feature a combination of intrinsic transparency and stretchability. The sensitivity toward humidity inevitably leads to dehydration or deliquescence issues, which will limit the long-term use of ionic conductors. Here, a novel ionic conductor based on natural bacterial cellulose (BC) and polymerizable deep eutectic solvents (PDESs) is developed for addressing the abovementioned drawbacks. The superstrong three-dimensional nanofiber network and strong interfacial interaction endow the BC-PDES ionic conductor with significantly enhanced mechanical properties (tensile strength of 8 × 105 Pa and compressive strength of 6.68 × 106 Pa). Furthermore, compared to deliquescent PDESs, BC-PDES composites showed obvious mechanical stability, which maintain good mechanical properties even when exposed to high humidity for 120 days. These materials were demonstrated to possess multiple sensitivity to external stimulus, such as strain, pressure, bend, and temperature. Thus, they can easily serve as supersensitive sensors to recognize physical activity of humans such as limb movements, throat vibrations, and handwriting. Moreover, the BC-PDES ionic conductors can be used in flexible, patterned electroluminescent devices. This work provides an efficient strategy for making cellulose-based sustainable and functional ionic conductors which have broad application in artificial flexible electronics and other products.

In this paper, nanochitin was used as an alternative natural nanomaterial to combine with cellulose fibers for fabricating high-strength paper. Two typical chitin nanowhiskers having contrasting sign of surface charge were compared to evaluate the enhancement performance on paper in details. The results show that nanochitin with positive charges on the surface has a significant effect on the strength properties of the prepared paper, especially on wet strength. When the dosage of chitin nanowhiskers was 2%, the wet strength index was increased to 2.48 N·m/g, which is important for paper-based analytical devices with the common use in liquid analysis. Typical colorimetric glucose assays were successfully performed, suggesting the improved analytical performance on these prepared paper.

It is a challenge to synthesize all-in-one molecular networks that are autonomously self-healable over a wide temperature range (from subzero to high), transparent, stretchable, and conductive. Her...

A new type of supramolecular elastomer, photopolymerized from two rationally designed polymerizable deep eutectic solvent (PDES) monomers, was reported. The resultant network was highly transparent, intrinsically conductive, stretchable, and self-healable. In particular, the healing process can even take place in various organic solvents, simultaneously with enhanced adaptability.

Three-dimensional covalent organic frameworks (3D COFs) have gained increasing attention for their attractive features. However, the development of 3D COFs is strongly restricted, mainly due to their synthetic difficulty and complicated structure determination. Post-synthetic modification, which can avoid these problems by incorporating functional moieties into a predetermined framework, provides an alternative way to construct 3D COFs with specific functions. Herein, we report the designed synthesis and characterization of a series of highly crystalline 3D COFs with different loadings of ethynyl groups. Notably, these alkyne-tagged 3D COFs provide a platform for targeted anchoring various specific groups onto the pore walls via click reactions. Moreover, the pore surface engineering can accordingly change their properties, for example, the obtained click products exhibited higher CO2 /N2 selectivity. We describe a simple but powerful strategy to build functional 3D COFs, which will certainly advance them for a ranging of interesting applications in the future.

With the gradual construction of the land and space planning system and the acceleration of the urban-rural integrated development process, China’s rural land planning and preparation have ushered in substantial innovations, and at the same time, they are also facing huge challenges. Among them, the low utilization rate of rural land and cultural desertification are the crux of the lagging rural development. This paper takes Guifengshan Village in Macheng City, Hubei Province as an example. Through the analysis of the current advantages of the village, the analysis of challenges, and the evaluation of the suitability of land use, this paper proposes to promote the mutual benefit of agriculture, culture and tourism, and promote the revitalization of Guifengshan Village, forming a “agricultural industry + characteristic cultural creation + red ecology”. “Tourism” jointly develops rural planning strategies. It aims to link rural agriculture, tourism and cultural industries closely on the basis of people-oriented and ecological protection, with income generation as the goal of rural revitalization, to achieve the establishment and extension of the industrial chain, and to promote rural revitalization.

Both lncRNAs and the N6-methyladenosine (m6A) modification are key regulators of tumorigenesis and innate immunity. However, little is known about the m6A modification of lncRNAs and their clinical and immune relevance in bladder cancer. In this study, we identified m6A-related lncRNAs using Pearson correlation analysis in The Cancer Genome Atlas (TCGA) and the IMvigor210 datasets. Next, univariate Cox regression was performed using the TCGA dataset to filter prognostic m6A-related lncRNAs, which were further subjected to the least absolute shrinkage and selection operator (LASSO) Cox regression to establish a 12 m6A-related lncRNA prognostic score (m6A-LRS). The m6A-LRS was validated in the IMvigor210 dataset. In addition, high m6A-LRS tumors, characterized by decreased tumor mutation load and neoantigen load, showed poorer response to immunotherapy than those with low m6A-LRS in the IMvigor210 dataset. Further, we constructed an m6A-LRS-based nomogram that demonstrated a strong ability to predict overall survival in patients with bladder cancer. Moreover, enrichment analysis revealed that tumor-associated biological processes, oncogenic signaling, and tumor hallmarks were commonly associated with a high m6A-LRS. Gene set variation analysis also indicated that high m6A-LRS was associated with activation of canonical oncogenic signatures, such as the epithelial-to-mesenchymal transition, cell cycle regulators, and DNA replication, as well as activation of immunosuppressive signatures, such as the T-cell exhaustion and pan-fibroblast-TGF-β response signatures. Furthermore, we observed distinct tumor microenvironment cell infiltration characteristics between high- and low-risk tumors. High m6A-LRS tumors showed reduced infiltration of CD8+ T-cells and enhanced infiltration of macrophages and fibroblasts. Additionally, we established a competing endogenous RNA network based on the12 m6A-related lncRNAs. Finally, three lncRNAs (SNHG16, SBF2-AS1, and BDNF-AS) were selected for further validation. The qualitative PCR assay on 10 pairs of bladder cancer and adjacent normal control samples validated the differential expression, and methylated RNA immunoprecipitation (MeRIP) analysis demonstrated a robust m6A enrichment in T24 bladder cancer cells compared with normal uroepithelial cells (SVHUC-1). In conclusion, this study introduced an m6A-related lncRNA signature that identified a subgroup of patients with poor prognoses and suboptimal immune responses, thus providing novel approaches for treatment response prediction and patient stratification in bladder cancer.

Stretchable and antifreezing conductive hydrogels, especially prepared from natural polymers, are beneficial for important and rapidly growing stretchable electronic devices. Unfortunately, the pot...

Garnet electrolyte is a promising candidate for the development of all-solid-state Li-metal batteries, because of its safety and stability against Li metal. However, its practical application is limited by the difficulty in production of its high-density thin sheet. In this work, we have fabricated garnet thin sheet electrolytes (Li6.4La3Zr1.4Ta0.6O12, LLZTO) by tape-casting technique. By using Li2O as a liquid-phase sintering additive, a high relative density up to 99% was achieved. Electrochemical results show the LLZTO sheets have an ionic conductivity of 5.2 × 10−4 S cm−1 at 30 °C and good cycling stability against Li metal. Based on the sheets, all-solid-state Li/LLZTO/LiFePO4 batteries exhibit excellent reversible cycles at 60 °C and 0.1C with an initial discharge specific capacity of 125.8 mA h g−1 and a retention of 92.3% after 50 cycles. These results indicate that the tape-casting process demonstrated here provides an effective method of producing high-density garnet thin sheet electrolytes for high-performance all-solid-state Li-metal batteries.

Garnets are promising solid electrolytes for developing solid state Li batteries, owing to their features of relatively high conductivity and stability against lithium metal. However, they show shortcoming of Li penetration through garnets during Li plating and stripping, which limits their practice application. Herein, we present a strategy to solve such problem by coating SnO2 films on the surfaces of the Li6·4La3Zr1·4Ta0·6O12 pellets. Through conversion reaction of SnO2 with Li at 200 °C, the nanocomposite layers consisting of crosslinked LixSn and Li2O are formed between the Li and the Li6·4La3Zr1·4Ta0·6O12 electrolytes. This leads to transition from lithiophobicity to lithiophilicity, thus greatly reducing interfacial resistance from 1100 Ω cm2 to 25 Ω cm2. Furthermore, taking advantage of suppressing volume change of LixSn alloy which is about 260%, the intermediate layers maintain integrity under the current densities of 0.2 mA cm−2 for 650 h cycles. In addition, the critical current density of Li/SnO2-Li6.4La3Zr1·4Ta0·6O12-SnO2/Li can be as high as 1.15 mA cm−2. As a proof-of-concept, this effective interface modification based on conversion reaction method contributes to a useful way of solving the Li/garnet interface problem and promoting the solid state Li batteries development.

Recently, flutter-driven triboelectric nanogenerator (TENG) has shown huge potential in wind energy harvesting from ambient environments. However, almost all the reported devices are based on parallel structure which suffers from a critical problem of insufficient contact between triboelectric surfaces. In this work, we propose an angle-shaped TENG (AS-TENG) with the above issue resolved. The device is based on two Al layers stacked to form an angle shape and a FEP film positioned in between by sharing a common side. Thanks to this design, the FEP film can contact fully and intimately with the Al layers to facilitate the effect of contact electrification and electrostatic induction. Compared with the existing parallel-structured TENG, the AS-TENG shows an overwhelming output performance because of the enhanced contact area. Furthermore, the AS-TENG is introduced a wedge-shaped wind guide channel which can provide a driving force for the flutter and hence lower the start-up wind speed largely. To further enhance the electric output, the AS-TENGs can be facilely integrated into a 360° radial array, showing an enlarged windward area and a high level of integration. The AS-TENG array can be applied to harvest outdoor weak wind and act as a direct power source to charge a capacitor or drive electronic devices. This work provides a design strategy for natural weak wind scavenging which may push forward the practical applications of TENG for wind power.

An accurate quantification method with a wide linearity range is paramount for the development of low-cost, portable and point-of-care sensors. This work reports a new approach to analyze the colorimetric assays on paper-based sensors using the quantification from a light transmission method. Compared to the commonly-developed color intensity measurement on scanned digital images, a portable transmission densitometer is capable of directly quantifying the optical density of colorimetric results. The detection of heavy metals in an aqueous system, including Fe(ii), Cu(ii), and Ni(ii), was carried out to demonstrate the good performance and reliability of this method. Our measurements show that the linear quantification range spans from 0.5-500 mg L-1 for the assays of Cu(ii) and Fe(ii) and from 2-500 mg L-1 for Ni(ii) based on the reading of transmitted light through the assay spot. As a comparison, the linear range is restricted to 0.5-50 mg L-1 for the same assays when analysed by the common reflection method, suggesting a significant improvement in the accuracy and sensitivity of high analyte concentrations from the light transmission method. By expanding the linearity range, this method further streamlines the sampling procedure during analysis and will greatly advance the future development of paper-based analytical sensors.

The development of porous MOFs exhibiting highly selective C2H2/CH4 and CO2/CH4 separations is quite important to meet the requirement of high-purity C2H2 and CH4 in various industries. By employing a ligand heterobifunctionalization strategy, we designed and synthesized an aminopyridine-functionalized diisophthalate ligand, and successfully targeted its corresponding copper-based NbO-type MOF ZJNU-98. Gas adsorption studies revealed that ZJNU-98 exhibited significantly enhanced adsorption of C2H2 and CO2 over CH4 compared to its parent MOF, NOTT-101. At 298 K and 1 atm, C2H2 and CO2 uptakes of ZJNU-98 are 10.0% and 16.7% higher than the corresponding values of NOTT-101, while 14.2% and 18.8% increases in C2H2/CH4 and CO2/CH4 adsorption selectivities were observed for the equimolar gas mixtures in ZJNU-98 compared to NOTT-101. Furthermore, the contribution of the functional group effect on gas adsorption has been assessed, demonstrating that the amine group plays a more important role than the pyridinic-N atom despite its lower Lewis basicity. This work provided an effective way and significant experimental evidence for the design of new porous MOFs with highly enhanced gas adsorption performance.

The design and construction of porous materials for high-efficient adsorption-based separation of CH4 from C2H2 and CO2 is a fundamental goal in the chemical industry. In this work, a lactam-functionalized bent diisophthalate linker, 5,5'-(1-methylpyridin-2(1H)-one-3,5-diyl) diisophthalic acid, was judiciously designed and utilized to construct a dicopper paddlewheel-based MOF under solvothermal conditions. Single-crystal X-ray diffraction revealed that the resulting solid is a three-dimensional mfj-type network incorporating Lewis-acidic copper sites and accessible lactam groups as two different kinds of functional sites. Furthermore, gas adsorption studies indicated that the material exhibited great promise for C2H2/CH4 and CO2/CH4 separations. In particular, compared to the unmodified parent compound, the resultant MOF exhibits 9.4% and 12.9% higher C2H2 and CO2 uptake capacities and 48.0% and 28.3% higher C2H2/CH4 and CO2/CH4 adsorption selectivities for the equimolar gas mixtures at 298 K and 1 atm, despite the lower specific surface area and pore volume. This work reported the first lactam-functionalized MOF displaying significantly enhanced adsorption of CO2 and C2H2 over CH4.

The structure–property relationship investigation is of prime importance to development of porous MOFs exhibiting better performance. In this work, two regioisomeric diisophthalate ligands, with the only difference being the position of methyl and amino groups with respect to isophthalate moieties, were rationally designed and synthesized, and their corresponding dicopper paddlewheel-based MOFs were successfully fabricated under suitable solvothermal conditions. Single-crystal X-ray diffraction studies showed that they displayed the same network topology of ssa type, thus providing a platform to investigate the impact of the substituent's arrangement on gas adsorption properties. As revealed by gas adsorption studies, the pore textural properties and gas uptake capacities with respect to C2H2, CO2, and CH4 of ZJNU-11 are significantly higher than those of its isomer ZJNU-12 despite their same structures, indicating that the arrangement of functional groups makes a difference to the framework stabilities against desolvation and thus to the gas adsorption properties. In addition, ZJNU-11 is also capable of selectively adsorptive separation of C2H2 and CO2 from CH4, with high C2H2/CH4 (v/v, 1/1) and CO2/CH4 (v/v, 1/1) adsorption selectivities of 36.2 and 5.9 at 298 K and 1 atm. This work not only reported a porous MOF material for highly selective C2H2/CH4 and CO2/CH4 separations, but also demonstrated that the rational arrangement of substituent groups will be favorable to improve the MOF's stabilities and thus gas adsorption properties, which needs to be taken into account upon design and construction of porous MOFs.

Combining a linear diisophthalate ligand, 5,5′-(2,3-dimethylbenzene-1,4-diyl)diisophthalic acid, with CuCl2·2H2O under different solvothermal conditions afforded two distinct copper-based metal–organic frameworks (ZJNU-96 and ZJNU-97), which were structurally characterized by various techniques. Single-crystal X-ray diffraction analyses reveal that they contain the same inorganic and organic building units but exhibit different topological structures, thus belonging to supramolecular isomers. Furthermore, gas adsorption studies show that ZJNU-96 not only exhibits better stability against desolvation than ZJNU-97 but also displays promising potential for selective adsorptive separation of C2H2 and CO2 from CH4, with C2H2 (CO2) uptake of 183.6 (88.7) cm3 (STP) g−1 and C2H2 (CO2)/CH4 (v/v, 50/50) IAST adsorption selectivity of 26.6 (5.2) at 298 K and 1 atm.