PDOL-Based Solid Electrolyte Toward Practical Application:Opportunities and Challenges

Polymer solid-state lithium batteries(SSLB)are regarded as a promising energy storage technology to meet growing demand due to their high energy density and safety.Ion conductivity,interface stability and battery assembly process are still the main challenges to hurdle the commercialization of SSLB.As the main component of SSLB,poly(1,3-dioxolane)(PDOL)-based solid polymer electrolytes polymerized in-situ are becoming a promising candidate solid elec-trolyte,for their high ion conductivity at room temperature,good battery elec-trochemical performances,and simple assembly process.This review analyzes opportunities and challenges of PDOL electrolytes toward practical application for polymer SSLB.The focuses include exploring the polymerization mechanism of DOL,the performance of PDOL composite electrolytes,and the application of PDOL.Furthermore,we provide a perspective on future research directions that need to be emphasized for commercialization of PDOL-based electrolytes in SSLB.The exploration of these schemes facilitates a comprehensive and profound understanding of PDOL-based polymer electrolyte and provides new research ideas to boost them toward practical application in solid-state batteries.

气相色谱-三重四极杆质谱法测定染发剂中14种N-亚硝胺类化合物

建立了气相色谱-三重四极杆质谱法测定染发剂中N-亚硝基乙基异丙胺等14种N-亚硝胺类化合物含量的方法。样品采用QuEChERS法前处理,经聚乙二醇石英毛细管柱HP-INNOWAX(30 m×0.25 mm×0.25μm)程序升温分离,在多反应监测(MRM)模式下分析,含量计算为外标法。结果表明,14种亚硝胺在5~100μg/L范围内线性关系良好(r>0.998),检出限和定量下限分别为0.2~1.5μg/L和0.6~5μg/L。在25,50,100μg/kg加标水平下,染发剂基质的平均回收率为83.8%~122.8%,相对标准偏差(RSD)小于11%(n=6)。采用该方法测定市售染发产品,结果发现1批样品中含有N-甲基-N-亚硝基苯胺,含量为31μg/kg。该方法前处理简单高效,专属性强,灵敏度高,准确性好,可用于染发剂中14种亚硝胺的筛查和含量测定。

鸡PPARγ基因转录本3上游开放阅读框转录后的调控作用

过氧化物酶体增殖物激活受体γ(peroxisome proliferator-activated receptor gamma,PPARγ)是脂肪生成的关键调控因子。本实验室前期研究发现,与人和鼠等哺乳动物PPARγ基因的转录本不同,鸡PPARγ基因的多个转录本5′UTR区存在上游开放阅读框(upstream open reading frames,u ORFs)。为了揭示该u ORF转录后的调控作用,本研究构建了鸡PPARγ基因转录本3(c PPARγ3)野生型5′UTR报告基因载体psi CHECK2-c PPARγ3-5′UTR-WT和u ORF突变(u ATG突变为终止密码子TGA)的5′UTR报告基因载体psi CHECK2-c PPARγ3-5′UTR-Mut。将这两个报告基因载体分别转染永生化鸡前脂肪细胞(immortalized chicken pre-adipocytes,ICPA)和鸡胚成纤维细胞DF1,检测海肾荧光素酶报告基因h Rluc活性及其m RNA表达。荧光素酶报告基因检测结果显示,在ICPA细胞中,psi CHECK2-c PPARγ3-5′UTR-Mut的h Rluc报告基因活性极显著高于psi CHECK2-c PPARγ3-5′UTR-WT(P<0.01);在DF1细胞中,psi CHECK2-c PPARγ3-5′UTR-Mut的h Rluc报告基因活性高于psi CHECK2-c PPARγ3-5′UTR-WT,但差异不显著(P>0.05)。q RT-PCR检测h Rluc基因m RNA表达结果显示,与psi CHECK2-c PPARγ3-5′UTR-WT相比,在ICPA细胞中,psi CHECK2-c PPARγ3-5′UTR-Mut转染细胞的h Rluc基因的m RNA表达水平极显著降低(P<0.01);在DF1细胞中,psi CHECK2-c PPARγ3-5′UTR-Mut转染细胞后,h Rluc基因的m RNA表达水平也降低,但差异不显著(P>0.05)。为进一步分析该u ORF对鸡c PPARγ3的转录后调控作用,本研究又分别构建了野生型c PPARγ3真核表达载体pc DNA3.1-c PPARγ3-WT和u ORF突变的c PPARγ3真核表达载体pc DNA3.1-c PPARγ3-Mut。q RT-PCR检测c PPARγ3的m RNA表达水平,结果显示,在这两种细胞中,pc DNA3.1-c PPARγ3-Mut转染细胞的c PPARγ3 m RNA表达水平均显著低于pc DNA3.1-c PPARγ3-WT转染细胞(P<0.05),但Western blot结果显示,pc DNA3.1-c PPARγ3-Mut转染细胞的PPARγ蛋白表达水平极显著高于pc DNA3.1-c PPARγ3-WT转染细胞(P<0.01)。这些研究结果表明,5′UTR区的u ORF抑制鸡c PPARγ3的翻译。

Plasma chitinase 3-like 1 is persistently elevated during first month after minimally invasive colorectal cancer resection

AIM: To assess blood chitinase 3-like 1(CHi3L1) levels for 2 mo after minimally invasive colorectal resection(MICR) for colorectal cancer(CRC). METHODS: CRC patients in an Institutional Review Board approved data/plasma bank who underwent elective MICR for whom preoperative(PreO p), early postoperative(PostO p), and 1 or more late PostO p samples [postoperative day(POD) 7-27] available were included. Plasma CHi3L1 levels(ng/m L) were determined in duplicate by enzyme linked immunosorbent assay. RESULTS: PreOp and PostOp plasma sample were available for 80 MICR cancer patients for the study. The median PreOp CHi3L1 level was 56.8 CI: 41.9-78.6 ng/mL(n = 80). Significantly elevated(P < 0.001) median plasma levels(ng/mL) over PreOp levels were detected on POD1(667.7 CI: 495.7, 771.7; n = 79), POD 3(132.6 CI: 95.5, 173.7; n = 76), POD7-13(96.4 CI: 67.7, 136.9; n = 62), POD14-20(101.4 CI: 80.7, 287.4; n = 22), and POD 21-27(98.1 CI: 66.8, 137.4; n = 20, P = 0.001). No significant difference in plasma levels were noted on POD27-41. CONCLUSION: Plasma CHi3L1 levels were significantly elevated for one month after MICR. Persistently elevated plasma CHi3L1 may support the growth of residual tumor and metastasis.

Plasma MMP-2 and MMP-7 levels are elevated first month after surgery and may promote growth of residual metastases

BACKGROUND MMP-2 also known as gelatinase A and MMP-7(matrilysin)are members of the zinc-dependent family of MMPs(Matrix metalloproteinase).MMP-2 and MMP-7 are remodeling enzymes that digest extracellular matrix;MMP-2 is extensively expressed during development and is upregulated at sites of tissue damage,inflammation,and in stromal cells of metastatic tumors.MMP-7 is expressed in the epithelial cells and in a variety of cancers including colon tumors.Plasma MMP-2 and MMP-7 levels were assessed before and after minimally invasive colorectal resection for cancer pathology.AIM To determine plasma MMP-2 and MMP-7 levels before and after minimally invasive colorectal resection for cancer pathology.METHODS Patients enrolled in a plasma bank for whom plasma was available were eligible.Plasma obtained from preoperative(Preop)and postoperative blood samples was used.Only colorectal cancer(CRC)patients who underwent elective minimally invasive cancer resection with preop,post-operative day(POD)1,3 and at least 1 late postop sample(POD 7-34)were included.Late samples were bundled into 7 d blocks(POD 7-13,14-20,etc.)and treated as single time points.Plasma MMP-2 and MMP-7 levels were determined via enzyme-linked immunosorbent assay in duplicate.RESULTS Total 88 minimally invasive CRC resection CRC patients were studied(right colectomy,37%;sigmoid,24%;and LAR/AR 18%).Cancer stages were:1,31%;2,30%;3,34%;and 4,5%.Mean Preop MMP-2 plasma level(ng/mL)was 179.3±40.9(n=88).Elevated mean levels were noted on POD1(214.3±51.2,n=87,P<0.001),POD3(258.0±63.9,n=80,P<0.001),POD7-13(229.9±62.3,n=65,P<0.001),POD 14-20(234.9±47.5,n=25,P<0.001),POD 21-27(237.0±63.5,n=17,P<0.001,)and POD 28-34(255.4±59.7,n=15,P<0.001).Mean Preop MMP-7 level was 3.9±1.9(n=88).No significant differences were noted on POD 1 or 3,however,significantly elevated levels were noted on POD 7-13(5.7±2.5,n=65,P<0.001),POD 14-20(5.9±2.5,n=25,P<0.001),POD 21-27(6.1±3.6,n=17,P=0.002)and on POD 28-34(6.8±3.3,n=15 P<0.001,)vs preop levels.CONCLUSION MMP-2 levels are elevated for 5 wk and MMP-7 levels elevated for weeks 2-6.The etiology of these changes in unclear,trauma and wound healing likely play a role.These changes may promote residual tumor growth and metastasis.

Plasma monocyte chemotactic protein-1 remains elevated after minimally invasive colorectal cancer resection

AIM: To investigate plasma Monocyte Chemotactic Protein-1 levels preoperatively in colorectal cancer(CRC) and benign patients and postoperatively after CRC resection.METHODS: A plasma bank was screened for minimally invasive colorectal cancer resection(MICR) for CRC and benign disease(BEN) patients for whom preoperative, early postoperative, and 1 or more late postoperative samples(postoperative day 7-27) were available. Monocyte chemotactic protein-1(MCP-1) levels(pg/mL) were determined via enzyme linked immuno-absorbent assay. RESULTS: One hundred and two CRC and 86 BEN patients were studied. The CRC patient's median preoperative MCP-1 level(283.1, CI: 256.0, 294.3) was higher than the BEN group level(227.5, CI: 200.2, 245.2; P = 0.0004). Vs CRC preoperative levels, elevated MCP-1 plasma levels were found on postoperative day 1(446.3, CI: 418.0, 520.1), postoperative day 3(342.7, CI: 320.4, 377.4), postoperative day 7-13(326.5, CI: 299.4, 354.1), postoperative day 14-20(361.6, CI: 287.8, 407.9), and postoperative day 21-27(318.1, CI: 287.2, 371.6; P < 0.001 for all). CONCLUSION: Preoperative MCP-1 levels were higher in CRC patients(vs BEN). After MICR for CRC, MCP-1 levels were elevated for 1 mo and may promote angiogenesis, cancer recurrence and metastasis.

Synergistic interaction of Nb atoms anchored on g‐C_(3)N_(4) and H^(+) promoting high‐efficiency nitrogen reduction reaction

Nowadays catalytic nitrogen reduction reaction(NRR)by electrochemistry has attracted much attention because of its key role in producing the basic chemical product ammonia with low energy consumption.A stable and environmentally‐friendly single‐or multi‐atom catalyst with good performance in activity and selectivity is highly desired for NRR.From density functional theory calculations,the NRR mechanisms catalyzed by Nb monomer,dimer,trimer and tetramer anchored on graphitic carbon nitride(Nb_(x)@g‐C_(3)N_(4),x=1,2,3,4)have been deeply explored.It has been found that Nb_(3)@g‐C_(3)N_(4) exhibits the best catalytic ability among the four catalysts with the introduction of H+.A more stable intermediate(*NH_(2)+*H)can be found to reduce the huge free energy barrier of forming*NH_(3) from*NH_(2) directly in a multi‐atom system.By analyzing the density of states and projected crystal orbital Hamilton population,a synergistic effect among Nb atoms and the adsorbed H^(+)is responsible for reducing the overpotential of NRR.Furthermore,the competitive hydrogen evolution reaction is suppressed effectively.This work introduces a new insight in the reaction pathway in multi‐atoms for developing high‐efficiency NRR catalysts.

One-pot synthesis of Ag-rich AgPd alloy nanoactiniae and their enhanced electrocatalytic activity toward oxygen reduction

The electro-catalytic properties can be effectively optimized by designing bimetallic alloy nanoparticles with high-content less-active metal to enhance the competence of more-active noble metal. Herein, a one-pot hydrothermal approach is demonstrated for the controllable synthesis of Ag-rich Ag_9Pd_1 alloy nanoactiniae with obviously enhanced electro-catalytic activity(2.23 mA cm^(-2) at 0.85 V) and stability for oxygen reduction reaction. In alkaline solution, the ORR onset potential and half-wave potential of the Ag_9Pd_1 alloy nanoactiniae can reach a value of 1.02 V and 0.89 V, respectively, which origin from strong ligand and ensemble effects between Pd element and Ag element. The nanocrystals are uniformly alloyed, displaying a Ag_9Pd_1 combination, as displayed by an assembly of X-ray diffraction(XRD) spectrum,energy dispersive X-ray(EDX) analysis, and cyclic voltammetry(CV). This concept of tuning bimetallic alloy nanocrystals with low concentrations of more precious metal may be a promising approach to be applicable to a wide range of alloy nanocrystals.

Conformational change-modulated spin transport at single-molecule level in carbon systems

Controlling the spin transport at the single-molecule level,especially without the use of ferromagnetic contacts,becomes a focus of research in spintronics.Inspired by the progress on atomic-level molecular synthesis,through firstprinciples calculations,we investigate the spin-dependent electronic transport of graphene nanoflakes with side-bonded functional groups,contacted by atomic carbon chain electrodes.It is found that,by rotating the functional group,the spin polarization of the transmission at the Fermi level could be switched between completely polarized and unpolarized states.Moreover,the transition between spin-up and spin-down polarized states can also be achieved,operating as a dual-spin filter.Further analysis shows that,it is the spin-dependent shift of density of states,caused by the rotation,that triggers the shift of transmission peaks,and then results in the variation of spin polarization.Such a feature is found to be robust to the length of the nanoflake and the electrode material,showing great application potential.Those findings may throw light on the development of spintronic devices.

Different noncollinear magnetizations on two edges of zigzag graphene nanoribbons

Based on density functional theory and non-equilibrium Green’s function method,we studied noncollinear magnetism and spin transport in a 180°domain wall made of zigzag graphene nanoribbon(ZGNR)with different noncollinear magnetic profiles on the top and bottom edges.Our results show that a helical domain wall on the top(bottom)edge and an abrupt domain wall on the bottom(top)edge can survive in the ZGNR.This indicates that such characteristic magnetization distribution can be obtained by some means,e.g.,the introduction of impurity on one edge.Compared to a wide ZGNR,a narrow ZGNR presents obvious coupling between the two edges which changes the magnetization and transmission greatly.As for the above-mentioned distinct magnetic profile,the spin transport is blocked in the abrupt domain wall due to strong spin flip scattering while remains unaffected in the helical domain wall due to the spin mixing effect.We deduce a formula of the transmission for various magnetic profiles of the ZGNRs.A new result based on this formula is that the transmission at the Fermi level can be zero,one,and two by tuning the edge magnetization.Our results provide insights into the noncollinear spin transport of the ZGNR-based devices.

New highly specific anti-BnASY polyclonal antibody prepara-tion and application in immunofluorescence assay

ASY （asynaptic） is a synaptonemal complex （SC） related protein in plant mei- osis. Some ASYs in plants have been cloned and functional determined. ASY in Brassica napus has not been sequenced and functional certificated. Here, we first cloned ASY gene in Brassica napus （BnASY） and inserted it into vector pET-32a for expression fusion protein BnASY-6His in Escherichia coli BL21 （DE3）. Purified fusion protein was used to produce polyclonal antibody. Specificity and application of polyclonal antibody was examined by Western blot and immunofluorescence assay. Results showed that BnASY-6His recombi-nant protein and anti-BnASY antibody were successfully obtained. Polyclonal anti-BnASY antibody had high specificity. Results of immunofluorescence showed that ASY signals appeared at leptotene stage, faded away gradually at pachytene stage and almost disap-peared at diplonema stage. In this study, highly specific polyclonal antibody was success-fully acquired and used for immunofluorescence assay in plant cells. It will contribute to functional research of ASY in B. napus.We thank Zhigang Li for providing pET-32a vector and Escherichia coli BL21 pLysS strains.

Absorption mechanism of carbon-nanotube paper- titanium dioxide as a multifunctional barrier material for lithium-sulfur batteries

Lithium-sulfur batteries attract much interest as energy storage devices for their low cost, high specific capacity, and energy density. However, the insulating properties of sulfur and high solubility of lithium polysulfides decrease the utilization of active materials by the battery resulting in poor cycling performance. Herein, we design a multifunctional carbon-nanotube paper/titanium-dioxide barrier which effectively reduces active material loss and suppresses the diffusion of lithium polysulfides to the anode, thereby improving the cycling stability of lithium-sulfur batteries. Using this barrier, an activated carbon/sulfur cathode with 70% sulfur content delivers stable cycling performance and high Coulombic efficiency （-99%） over 250 cycles at a current rate of 0.5 C. The improved electrochemical performance is attributed to the synergistic effects of the carbon nanotube paper and titanium dioxide, involving the physical barrier, chemical adsorption from the binding formation of Ti-S and S-O, and other interactions unique to the titanium dioxide and sulfur species.

Non-metallic electronic regulation in CuCo oxy-/thio-spinel as advanced oxygen evolution electrocatalysts

Developing cost-effective and high-performance oxygen evolution reaction(OER)electrocatalysts has become the intense research on pursuing emerging renewable energy conversion,in which exploring and investigating the intrinsic nature of efficient and stable Cu Co spinel catalysts toward OER in alkaline media is highly desirable.Herein,Cu1–xCo2+xO4oxy-spinel nanoflakes are fabricated by a facile hydrothermal method with the oxidation of ammonia water.In the same condition,Cu1–xCo2+xS4thio-spinel nanospheres are formed without oxidation.In OER process,the as-obtained Cu1–xCo2+xO4nanoflakes and Cu1–xCo2+xS4nanospheres possess the anodic overpotential of 267 and 297 m V in alkaline media to drive the current density of 10 m A/cm^2,respectively,outperforming the state-of-the-art noble metal catalyst of RuO2.X-ray photoelectron spectroscopy analysis exhibits the higher ratio value of Co(Ⅲ)/Co(Ⅱ)in Cu1–xCo2+xO4than that in Cu1–xCo2+xS4,suggesting that the stronglyelectronegative oxygen efficiently predominates in regulating valence states of Co active sites in spinel structures.Remarkably,density functional theory simulation further reveals that the increased valence state of Co could accelerate the electron exchange between catalysts and oxygen adsorbates during electrocatalysis,thus contributing to the higher OER activity of Cu1–xCo2+xO4catalysts.This work provides deep insight regarding the significance of non-metal element(O and S)in Cu Co spinel structure catalysts,as well as presents a promising approach to exploit higher performance and grasp the mechanism of various non-noblemetal spinel catalysts for water oxidation.

Ultrathin oxide controlled photocurrent generation through a metal–insulator–semiconductor heterojunction

Recent advances in nanoscale lasers,amplifiers,and nonlinear optical converters have demonstrated the unprecedented potential of metal–insulator–semiconductor(MIS)structures as a versatile platform to realize integrated photonics at the nanoscale.While the electric field enhancement and confinement have been discussed intensively in MIS based plasmonic structures,little is known about the carrier redistribution across the heterojunction and photocurrent transport through the oxide.Herein,we investigate the photo-generated charge transport through a single Cd Se microbelt-Al_(2)O_(3)-Ag heterojunction with oxide thickness varying from 3 nm to 5 nm.Combining photocurrent measurements with finite element simulations on electron(hole)redistribution across the heterojunction,we are able to explain the loss compensation observed in hybrid plasmonic waveguides at substantially reduced pump intensity based on MIS geometry compared to its photonic counterpart.We also demonstrate that the MIS configuration offers a low-dark-current photodetection scheme,which can be further exploited for photodetection applications.