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CHEMICAL PAPERS · 2022 ·Vol. 77 ·期 1 ·259-268 · IF 2.146

Functional ionic liquids as chiral selector for visual chiral sensing and enantioselective precipitate

Ma Xiaofei,Zhang Chengchen,Cai Liangliang

This work describes a rapid and efficient method for visual chiral recognition by making use of chiral ionic liquids (CILs) based on shikimic acid and D-pipecolinic acid. Cooperation between copper (II) and appropriate solvents resulted in visual enantioselectivity responses of several amino acids and mandelic acid. All the enantiomeric distinguishment could be obtained within 3 min, depending on the difference of colour or solubility. Then, scanning electron microscopy, infrared spectroscopy, ultraviolet spectroscopy, thermogravimetric analysis and elemental analysis were employed to investigate the potential recognition mechanism. The results indicated that chiral recognition was strongly associated with the different stability between D-complex and L-complex. Furthermore, separation was achieved by treating the chiral sensor with racemic compounds. In the case of tryptophan, the proposed method provided good enantiomeric excess values (90.7% in solid phase and 63.2% in liquid phase). Graphical abstract

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JOURNAL OF NANOBIOTECHNOLOGY · 2022 ·Vol. 20 ·期 1 ·1-16 · IF 9.429

Immunotherapy for type 1 diabetes mellitus by adjuvant-free Schistosoma japonicum-egg tip-loaded asymmetric microneedle patch (STAMP)

Huang Haoming,Hu Dian,Chen Zhuo,Xu Jiarong,Xu Rengui,Gong Yusheng,Fang Zhengming,Wang Ting,Chen Wei

Background Type 1 diabetes mellitus (T1DM) is an autoimmune disease mediated by autoreactive T cells and dominated by Th1 response polarization. Insulin replacement therapy faces great challenges to this autoimmune disease, requiring highly frequent daily administration. Intriguingly, the progression of T1DM has proven to be prevented or attenuated by helminth infection or worm antigens for a relatively long term. However, the inevitable problems of low safety and poor compliance arise from infection with live worms or direct injection of antigens. Microneedles would be a promising candidate for local delivery of intact antigens, thus providing an opportunity for the clinical immunotherapy of parasitic products. Methods We developed a Schistosoma japonicum- egg tip-loaded asymmetric microneedle patch (STAMP) system, which serves as a new strategy to combat TIDM. In order to improve retention time and reduce contamination risk, a specific imperfection was introduced on the STAMP (asymmetric structure), which allows the tip to quickly separate from the base layer, improving reaction time and patient’s comfort. After loading Schistosoma japonicum- egg as the immune regulator, the effects of STAMP on blood glucose control and pancreatic pathological progression improvement were evaluated in vivo. Meanwhile, the immunoregulatory mechanism and biosafety of STAMP were confirmed by histopathology, qRT-PCR, ELISA and Flow cytometric analysis. Results Here, the newly developed STAMP was able to significantly reduce blood glucose and attenuate the pancreatic injury in T1DM mice independent of the adjuvants. The isolated Schistosoma japonicum- eggs micron slowly degraded in the skin and continuously released egg antigen for at least 2 weeks, ensuring localization and safety of antigen stimulation. This phenomenon should be attributed to the shift of Th2 immune response to reduce Th1 polarization. Conclusion Our results exhibited that STAMP could significantly regulate the blood glucose level and attenuate pancreatic pathological injury in T1DM mice by balancing the Th1/Th2 immune responses, which is independent of adjuvants. This technology opens a new window for the application of parasite products in clinical immunotherapy.

CAS / MDL: 9004-32-4
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Cell Death & Disease · 2022 ·Vol. 13 ·期 8 ·1-11 · IF 9.685

A dopamine-methacrylated hyaluronic acid hydrogel as an effective carrier for stem cells in skin regeneration therapy

Gong Meihua,Yan Fei,Yu Li,Li Furong

Adipose-derived stem cells (ADSCs) show potential in skin regeneration research. A previous study reported the failure of full-thickness skin self-repair in an injury area exceeding 4 cm in diameter. Stem cell therapies have shown promise in accelerating skin regeneration; however, the low survival rate of transplanted cells due to the lack of protection during and after transplantation leads to low efficacy. Hence, effective biomaterials for the delivery and retention of ADSCs are urgently needed for skin regeneration purposes. Here, we covalently crosslinked hyaluronic acid with methacrylic anhydride and then covalently crosslinked the product with dopamine to engineer dopamine-methacrylated hyaluronic acid (DA-MeHA). Our experiments suggested that the DA-MeHA hydrogel firmly adhered to the skin wound defect and promoted cell proliferation in vitro and skin defect regeneration in vivo. Mechanistic analyses revealed that the beneficial effect of the DA-MeHA hydrogel combined with ADSCs on skin defect repair may be closely related to the Notch signaling pathway. The ADSCs from the DA-MeHA hydrogel secrete high levels of growth factors and are thus highly efficacious for promoting skin wound healing. This DA-MeHA hydrogel may be used as an effective potential carrier for stem cells as it enhances the efficacy of ADSCs in skin regeneration.

CAS / MDL: 85073-19-4
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Journal of Advanced Ceramics · 2022 ·Vol. 11 ·期 11 ·1735-1750 · IF 11.534

Photo-assisted charging of carbon fiber paper-supported CeO2/MnO2 heterojunction and its long-lasting capacitance enhancement in dark

Yang Weiyi,Wang Jian,Gao Shuang,Zhang Haoyu,Wang Hongyang,Li Qi

It is important to develop green and sustainable approaches to enhance electrochemical charge storage efficiencies. Herein, a two-step in-situ growth process was developed to fabricate carbon fiber paper-supported CeO 2 /MnO 2 composite (CeO 2 /MnO 2 —CFP) as a binder-free photo-electrode for the photo-assisted electrochemical charge storage. The formation of CeO 2 /MnO 2 type II heterojunction largely enhanced the separation efficiency of photo-generated charge carriers, resulting in a substantially enhanced photo-assisted charging capability of ∼20%. Furthermore, it retained a large part of its photo-enhanced capacitance (∼56%) in dark even after the illumination was off for 12 h, which could be attributed to its slow release of stored photo-generated electrons from its specific band structure to avoid their reaction with O 2 in dark. This study proposed the design principles for supercapacitors with both the photo-assisted charging capability and its long-lasting retainment in dark, which may be readily applied to other pseudocapacitive materials to better utilize solar energy.

CAS / MDL: 7757-82-6
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CATALYSIS LETTERS · 2022 ·Vol. 153 ·期 6 ·1657-1665 · IF 2.936

The Synthesis of Ionic Liquid Functionalized Polymer and its Application in the Esterification Between Methacrylic Acid and Methanol

Bian Yuhang,Liu Junyang,Zhang Guoliang,Peng Zhijian,Li Chunshan

Abstract High yield of methyl methacrylate was gained by using ionic liquid functionalized copolymer of ethylene dimethacrylate and 4-vinylbenzyl. The solid acid catalyst (VEM-ILs) was obtained through quaternary ammonization on the tetraethylenepentamine-functionalized copolymer with 1,3-propanesultone and HSO 3 CF 3 . The acid amount of VEM-ILs was 1.46 mmol/g. The surface area and pore volume of VEM-ILs were 11.1 m 2 /g and 0.04 cm 3 /g. To appraise the catalytic activity of the catalyst, the esterification between methacrylic acid and methanol was implemented. The optimized condition was as follows: 21.15 wt% catalyst dosage based on the weight of methacrylic acid, 90 °C, MAA to MeOH ratio of 1:1.5 and 3 h reaction time. Under the optimal condition, the yield of ester reached 76.5%. After four times use, the catalyst still exhibited a good catalytic effect. Graphical Abstract

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ACTA PHARMACOLOGICA SINICA · 2022 ·Vol. 44 ·期 1 ·234-243 · IF 7.169

Discovery of toxoflavin, a potent IRE1α inhibitor acting through structure-dependent oxidative inhibition

Jiang Kai-long,Liu Chang-mei,Nie Li-tong,Jiang Hai-ni,Xu Lei,Zhang Kun-zhi,Fan Li-xia,Gao An-hui,Lin Lu-ling,Wang Xiang-yu,Tan Ming-jia,Zhang Qi-qing,Zhou Yu-bo,Li Jia

Inositol-requiring enzyme 1α (IRE1α) is the most conserved endoplasmic reticulum (ER) stress sensor with two catalytic domains, kinase and RNase, in its cytosolic portion. IRE1α inhibitors have been used to improve existing clinical treatments against various cancers. In this study we identified toxoflavin (TXF) as a new-type potent small molecule IRE1α inhibitor. We used luciferase reporter systems to screen compounds that inhibited the IRE1α-XBP1s signaling pathway. As a result, TXF was found to be the most potent IRE1α RNase inhibitor with an IC 50 value of 0.226 μM. Its inhibitory potencies on IRE1α kinase and RNase were confirmed in a series of cellular and in vitro biochemical assays. Kinetic analysis showed that TXF caused time- and reducing reagent-dependent irreversible inhibition on IRE1α, implying that ROS might participate in the inhibition process. ROS scavengers decreased the inhibition of IRE1α by TXF, confirming that ROS mediated the inhibition process. Mass spectrometry analysis revealed that the thiol groups of four conserved cysteine residues (CYS-605, CYS-630, CYS-715 and CYS-951) in IRE1α were oxidized to sulfonic groups by ROS. In molecular docking experiments we affirmed the binding of TXF with IRE1α, and predicted its binding site, suggesting that the structure of TXF itself participates in the inhibition of IRE1α. Interestingly, CYS-951 was just near the docked site. In addition, the RNase IC 50 and ROS production in vitro induced by TXF and its derivatives were negative correlated ( r  = −0.872). In conclusion, this study discovers a new type of IRE1α inhibitor that targets a predicted new alternative site located in the junction between RNase domain and kinase domain, and oxidizes conserved cysteine residues of IRE1α active sites to inhibit IRE1α. TXF could be used as a small molecule tool to study IRE1α’s role in ER stress.

CAS / MDL: 11089-65-9
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JOURNAL OF SOLID STATE ELECTROCHEMISTRY · 2022 ·Vol. 26 ·期 10 ·2219-2229 · IF 2.747

The preparation of schwertmannites/mesoporous carbons and its application in simultaneous determination of paracetamol and dopamine

Kang Xianyu,Qiao Xingxing,Zhao Jingchuang,Li Yancai,Lü Jian

In this work, mesoporous carbons (MCs) were synthesized by a template method, and the schwertmannites (Schs) were prepared by a calcination method. They were mixed uniformly by ultrasound and obtained the Schs/MCs nanocomposites. The Schs/MCs/GCE can be used to detect paracetamol (PA) and dopamine (DA) simultaneously. Under the best terms, it exhibits wide linear range of 1.0 to 300 µM for PA and 1.0 to 400 µM for DA. The determination limits are 0.33 µM for PA and 0.24 µM for DA ( S / N  = 3), respectively. Besides, the sensor is expected to be used for detect PA and DA in pharmaceutical samples.

CAS / MDL: 7664-38-2
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Nature Biomedical Engineering · 2021 ·Vol. 6 ·期 1 ·32-43 · IF 25.671

Biomaterial-mediated modulation of oral microbiota synergizes with PD-1 blockade in mice with oral squamous cell carcinoma

Zheng Di-Wei,Deng Wei-Wei,Song Wen-Fang,Wu Cong-Cong,Liu Jie,Hong Sheng,Zhuang Ze-Nan,Cheng Han,Sun Zhi-Jun,Zhang Xian-Zheng

Because a host’s immune system is affected by host–microbiota interactions, means of modulating the microbiota could be leveraged to augment the effectiveness of cancer therapies. Here we report that patients with oral squamous cell carcinoma (OSCC) whose tumours contained higher levels of bacteria of the genus Peptostreptococcus had higher probability of long-term survival. We then show that in mice with murine OSCC tumours injected with oral microbiota from patients with OSCCs, antitumour responses were enhanced by the subcutaneous delivery of an adhesive hydrogel incorporating silver nanoparticles (which inhibited the growth of bacteria competing with Peptostreptococcus ) alongside the intratumoural delivery of the bacterium P. anaerobius (which upregulated the levels of Peptostreptococcus ). We also show that in mice with subcutaneous or orthotopic murine OSCC tumours, combination therapy with the two components (nanoparticle-incorporating hydrogel and exogenous P. anaerobius ) synergized with checkpoint inhibition with programmed death-1. Our findings suggest that biomaterials can be designed to modulate human microbiota to augment antitumour immune responses.

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Nano Research · 2021 ·Vol. 15 ·期 2 ·1087-1093 · IF 8.897

One-dimensional iridium-based nanowires for efficient water electrooxidation and beyond

Li Leigang,Wang Pengtang,Cheng Zifang,Shao Qi,Huang Xiaoqing

The sluggish reaction kinetics of oxygen evolution reaction (OER) has largely lowered the efficiency of electrochemical water splitting. Ir represents one of the state-of-the-art electrocatalysts for promoting OER especially in acidic electrolytes. However, it remains a formidable challenge to synthesize high-quality one-dimensional (1D) Ir-based nanostructures for improved electrocatalytic performance. Herein, a template-assisted synthesis method is reported wherein 1D porous Ir-Te nanowires (Ir-Te NWs) are synthesized with Te NWs serving as the template. The Ir-Te NWs exhibit highly enhanced OER performance compared to commercial IrO 2 and Ir/C. In detail, the overpotentials to reach 10 mA·cm −2 are 248 and 284 mV in 1 M KOH and 0.5 M H 2 SO 4 , respectively, much lower than those of commercial catalysts. The Ir-Te NWs also show smaller Tafel slopes than commercial IrO 2 and Ir/C, signifying faster reaction kinetics. Besides, much more durable OER activity can be maintained for Ir-Te NWs with negligible decay during 25 and 20 h stability tests in 1 M KOH and 0.5 M H 2 SO 4 , respectively. Further analysis indicates that the significantly improved OER performance of Ir-Te NWs could be ascribed to the larger electrochemical surface area and smaller electrical resistance. More significantly, the templated synthesis of Ir-Te NWs can be facilely extended to the fabrication of other metal-Te NWs including Ru-Te, Rh-Te and Pt-Te NWs. The design and synthesis of 1D metal-based NWs in this work provide important inspiration for the synthesis of diversified 1D metallic nanostructures with distinctly enhanced catalytic performance and beyond.

CAS / MDL: 7790-58-1
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Nature Sustainability · 2021 ·Vol. 5 ·期 3 ·205-213 · IF 19.346

A non-flammable hydrous organic electrolyte for sustainable zinc batteries

Han Daliang,Cui Changjun,Zhang Kangyu,Wang Zhenxing,Gao Jiachen,Guo Yong,Zhang Zhicheng,Wu Shichao,Yin Lichang,Weng Zhe,Kang Feiyu,Yang Quan-Hong

Aqueous zinc (Zn) batteries have long been considered a potentially more sustainable alternative to lithium-ion batteries because of their better environmental compatibility, enhanced safety and cost advantage. However, in the presence of an aqueous electrolyte, the Zn anode is poised to undergo dendrite failure, corrosion and hydrogen evolution, all of which resonate with each other leading to fast performance degradation. Here, in a break from the current aqueous battery path, we report a low-cost hydrous organic electrolyte involving a hydrated Zn(BF 4 ) 2 salt and an ethylene glycol solvent, which not only promotes the in situ formation of a favourable ZnF 2 passivation layer to protect Zn from dendrite growth and side reactions but also embraces excellent non-flammability. Remarkably, the present Zn anode sustains a long-term cycling over 4,000 h at a current density of 0.5 mA cm −2 with a high Coulombic efficiency of 99.4% and shows an areal capacity as high as 5 mAh cm − 2 . Equally intriguingly, the electrolyte can run across a wide temperature range from −30 °C to 40 °C without seriously compromising performance. The Zn//V 2 O 5 full cells with our electrolyte also perform much better in terms of capacity retention than a device with an aqueous ZnSO 4 electrolyte. Our findings suggest a promising direction for developing electrolyte solutions for practical Zn batteries which combine safety, performance and sustainability.

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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2021 ·Vol. 414 ·期 4 ·1553-1561 · IF 4.157

Aptamer functionalized and reduced graphene oxide hybridized porous polymers SPE coupled with LC–MS for adsorption and detection of human α-thrombin

Zhang Wenjuan,Hu Haoyun,Ruan Guihua,Huang Yipeng,Du Fuyou,Chen Zhengyi

In this study, reduced graphene oxide (rGO) hybridized high internal phase emulsions were developed and polymerized as porous carriers for aptamer (5’/5AmMC6/-AGT CCG TGG TAG GGC AGG TTG GGG TGA CT-3’) modification to enrich human α-thrombin from serum. The structure and properties of the materials were confirmed by scanning electron microscope (SEM), Fourier transform infrared spectroscope (FT-IR), and X-ray photoelectron spectra (XPS). The adsorption ability and selectivity were studied and the thrombin was detected with liquid chromatography-mass spectrometry (LC–MS). The adsorption of thrombin onto the sorbent was achieved within 30 min and the desorption was realized using 5.0 mL of acetonitrile/water (80/20, v/v). The thrombin was quantified by LC–MS according to its characteristic peptide sequence of ELLESYIDGR. Graphical abstract

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Science China-Technological Sciences · 2021 ·Vol. 65 ·期 1 ·179-190 · IF 3.572

An Azo-PDMS-based wearable UV sensor with the optimized photo response mode for dual sensing and synchronous detection

Qi YuHao,Zheng JunPing

A wearable UV sensor is designed to realize UV detection and a warning effect on people’s excessive UV exposure. It is noteworthy that the photoelectric system and supporting material of the most conventional sensor are separated. The unstable connection between the two components and the complicated construction method makes the sensor susceptible to external motion interference and prone to failure. Herein, we developed a unique photo response mode of the UV sensor based on a novel photo responsive material. An azobenzene-containing polydimethylsiloxane (Azo-PDMS) film was prepared as the outer layer of the sensor. It integrated the functions of photo response source, support and protection, which realized the direct contact and rapid response to the UV light source. Carbon nanotube (CNT), wrapped in the middle of Azo-PDMS films as an inner layer, transformed the photomechanical response signal into the photoelectric signal. The photo response mode endows the sensor with excellent anti-motion interference capabilities and a true sense of UV-strain synchronous monitoring performance, which is of great significance to the practical application of wearable devices. In addition, based on the excellent properties of Azo-PDMS, the sensor can also protect the human body from UV damage, self-repair after fracture, and realize personalized customization through 3D printing. It makes a breakthrough in the design and construction of wearable UV sensors and paves a new way to optimize sensor photo response modes.

CAS / MDL: 109-99-9
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