Highly Stable Lithium Metal Batteries Enabled by Tuning the Molecular Polarity of Diluents in Localized High-Concentration Electrolytes.

Electrolyte plays a crucial role in ensuring stable operation of lithium metal batteries (LMBs). Localized high-concentration electrolytes (LHCEs) have the potential to form a robust solid-electrolyte interphase (SEI) and mitigate Li dendrite growth, making them a highly promising electrolyte option. However, the principles governing the selection of diluents, a crucial component in LHCE, have not been clearly determined, hampering the advancement of such a type of electrolyte systems. Herein, the diluents from the perspective of molecular polarity are rationally designed and developed. A moderately fluorinated solvent, 1-(1,1,2,2-tetrafluoroethoxy)propane (TNE), is employed as a diluent to create a novel LHCE. The unique molecular structure of TNE enhances the intrinsic dipole moment, thereby altering solvent interactions and the coordination environment of Li-ions in LHCE. The achieved solvation structure not only enhances the bulk properties of LHCE, but also facilitates the formation of more stable anion-derived SEIs featured with a higher proportion of inorganic species. Consequently, the corresponding full cells of both Li||LiFePO4 and Li||LiNi0.8 Co0.1 Mn0.1 O2 cells utilizing Li thin-film anodes exhibit extended long-term stability with significantly improved average Coulombic efficiency. This work offers new insights into the functions of diluents in LHCEs and provides direction for further optimizing the LHCEs for LMBs.

Revealing the role of interfacial water and key intermediates at ruthenium surfaces in the alkaline hydrogen evolution reaction.

Ruthenium exhibits comparable or even better alkaline hydrogen evolution reaction activity than platinum, however, the mechanistic aspects are yet to be settled, which are elucidated by combining in situ Raman spectroscopy and theoretical calculations herein. We simultaneously capture dynamic spectral evidence of Ru surfaces, interfacial water, *H and *OH intermediates. Ru surfaces exist in different valence states in the reaction potential range, dissociating interfacial water differently and generating two distinct *H, resulting in different activities. The local cation tuning effect of hydrated Na+ ion water and the large work function of high-valence Ru(n+) surfaces promote interfacial water dissociation. Moreover, compared to low-valence Ru(0) surfaces, high-valence Ru(n+) surfaces have more moderate adsorption energies for interfacial water, *H, and *OH. They, therefore, facilitate the activity. Our findings demonstrate the regulation of valence state on interfacial water, intermediates, and finally the catalytic activity, which provide guidelines for the rational design of high-efficiency catalysts.

Understanding the origin of the improved sodium ion storage performance of the transition metal oxide@carbon nanocomposite anodes.

Transition metal oxide (TMO) anodes show inferior sodium ion storage performance compared with that of lithium ion storage owing to the larger radium size and heavier elemental mass of Na+ than Li+. Effective strategies are highly desired to improve the Na+ storage performance of TMOs for applications. In this work, using ZnFe2O4@xC nanocomposites as model materials for investigation, we found that by manipulating the particle sizes of the inner TMOs core and the features of outer carbon coating, the Na+ storage performance can be significantly improved. The ZnFe2O4@1C with a diameter of the inner ZnFe2O4 core of around 200 nm coated by a thin carbon layer of around 3 nm shows a specific capacity of only 120 mA h g-1. The ZnFe2O4@6.5C with a diameter of the inner ZnFe2O4 core of around 110 nm embedding in a porous interconnected carbon matrix displays a significantly improved specific capacity of 420 mA h g-1 at the same specific current. Furthermore, the latter shows an excellent cycling stability of 1000 cycles with a capacity retention of 90% of the initial 220 mA h g-1 specific capacity at 1.0 A g-1. TEM, electrochemical impedance spectroscopy, and kinetic analysis show that the inner ZnFe2O4 core with reduced particle size and the outer thicker and interconnected carbon matrix synergistically improve the active reaction sites, integrity, electric conductivity, and pseudocapacitive-controlled contribution of ZnFe2O4@xC nanocomposites, thus leading to an overall enhanced Na+ storage performance. Our findings create a universal, facile, and effective method to enhance the Na+ storage performance of the TMO@C nanomaterials.

In Situ Probe of the Hydrogen Oxidation Reaction Intermediates on PtRu a Bimetallic Catalyst Surface by Core-Shell Nanoparticle-Enhanced Raman Spectroscopy.

In situ monitoring of the evolution of intermediates and catalysts during hydrogen oxidation reaction (HOR) processes and elucidating the reaction mechanism are crucial in catalysis and energy science. However, spectroscopic information on trace intermediates on catalyst surfaces is challenging to obtain due to the complexity of interfacial environments and lack of in situ techniques. Herein, core-shell nanoparticle-enhanced Raman spectroscopy was employed to probe alkaline HOR processes on representative PtRu surfaces. Direct spectroscopic evidence of an OHad intermediate and RuOx (Ru(+3)/Ru(+4)) surface oxides is simultaneously obtained, verifying that Ru doping onto Pt promotes OHad adsorption on the RuOx surface to react with Had adsorption on the Pt surface to form H2O. In situ Raman, XPS, and DFT results reveal that RuOx coverage tunes the electronic structure of PtRuOx to optimize the adsorption energy of OHad on catalyst surfaces, leading to an improvement in HOR activity. Our findings provide mechanistic guidelines for the rational design of HOR catalysts with high activity.

Label-free SERS strategy for rapid detection of capsaicin for identification of waste oils.

Identification of waste oils is challenging in the field of food safety due to the lack of common markers and straightforward analytical methods. Herein, we developed a novel label-free surface-enhanced Raman spectroscopy (SERS) strategy to identify waste oils using Ag nanoparticles solution (Ag NPs sol.) as a SERS substrate to significantly enhance the Raman signal of capsaicin marker molecule usually contained in the waste oils. The enhanced signal was directly detected by a portable Raman spectrometer with the limit of detection (LOD) of 2.9 µg L-1 within 10 min. Concentration-dependent SERS investigation showed the linear relationship between the SERS signal intensity of the characteristic peaks and the concentrations of capsaicin in the range of 10-2500 µg L-1 and the correlation coefficient was 0.9895. Our findings show the sensitivity, accessibility, and reliability of this method for the rapid identification of waste oils and furthermore for the practical applications in the field of food safety.

Rapid and Simple Analysis of the Human Pepsin Secondary Structure Using a Portable Raman Spectrometer.

Human pepsin is a digestive protease that plays an important role in the human digestive system. The secondary structure of human pepsin determines its bioactivity. Therefore, an in-depth understanding of human pepsin secondary structure changes is particularly important for the further improvement of the efficiency of human pepsin biological function. However, the complexity and diversity of the human pepsin secondary structure make its analysis difficult. Herein, a convenient method has been developed to quickly detect the secondary structure of human pepsin using a portable Raman spectrometer. According to the change of surface-enhanced Raman spectroscopy (SERS) signal intensity and activity of human pepsin at different pH values, we analyze the change of the human pepsin secondary structure. The results show that the content of the ß-sheet gradually increased with the increase in the pH in the active range, which is in good agreement with circular dichroism (CD) measurements. The change of the secondary structure improves the sensitivity of human pepsin SERS detection. Meanwhile, human pepsin is a commonly used disease marker for the noninvasive diagnosis of gastroesophageal reflux disease (GERD); the detection limit of human pepsin we obtained is 2 µg/mL by the abovementioned method. The real clinical detection scenario is also simulated by spiking pepsin solution in saliva, and the standard recovery rate is 80.7-92.3%. These results show the great prospect of our method in studying the protein secondary structure and furthermore promote the application of SERS in clinical diagnosis.

[Effect of RYBP Gene Silencing on Sensitivity of HL-60 Cells to Chemotherapeutic Drugs].

OBJECTIVE: To investigate the effect of RYBP gene on sensitivity of HL-60 cells to chemotherapy drugs by using RNA interference. METHODS: Plasmid expressing RYBP specific shRNA was constructed and then was used to establish the RYBP knockdown stable HL-60 cell line. Q-PCR and Western blot were used to confirm the efficacy of RYBP gene silencing at mRNA and protein level respectively; then the DNA ladder and Annexin V labeled flow cytometry were used to detect cell apoptosis; CCK-8 was used detect the sensitivity of HL-60 cells to the chemotherapeutic drug cytarabine or daunorubicin. RESULTS: The lentiviral-RYBP-shRNA vector was succesfully and effectively inhibit the expression of RYBP at mRNA and protein in HL-60 cells. It was found that without chemotherapy drug treatment the apoptosis rate of RYBP shRNA group was lower than that of the empty vector control group (NC group). When treated with cytarabine, the apoptosis rate and inhibitive rate of RYBP shRNA group were lower than those of NC group. Besides, when treated with daunorubicin, the apoptosis rate of RYBP shRNA group was lower than that of NC group, while the inhibitive rate had no significant difference. CONCLUSIONS: RYBP gene silencing can inhibitive the apoptosis of HL-60 cells and significantly reduce the sensitivity to cytarabine, but this gene silencing can't affect the sensitivity to daunorubicin.

[Expression of histone demethylase lysine specific demethylase 1 in acute leukemia and its clinical significance].

The aim of this study was to investigate the expression of histone demethylase lysine specific demethylase1 (LSD1) in patients with acute leukemia (AL) and its clinical significance. LSD1 protein expression level was detected by semi-quantitative Western blot in HL-60 and SHI-1 leukemia cell line, in bone marrow mononuclear cells of acute AL patients with different condition [new diagnosis, complete remission (CR) and relapse] and in patients with non malignant hematopathy (control). Clinical data of AL patient followed up was collected. The relationship of LSD1 expression level with clinical prognosis was analyzed. The results showed that in HL-60 and SHI-1 leukemia cell line, LSD1 expression was strong positive, relative amount (LSD1/ß-actin gray level rate) was 4.647 ± 3.840 and 1.628 ± 0.185 (n = 4) respectively. In 72 AL patients, LSD1 expression levels were quite different. LSD1 positive rate was 56.9% (41/72), average relative amount was 1.053 ± 1.976. In 17 controls, LSD1 positive rate was 0%, relative amount was 0.004 ± 0.012. The LSD1 positive rate in newly diagnosed AML or ALL group (90.4%, 77.8%) and refractory/relapse AML or ALL group (100%, 100%) was higher than that in AML or ALL CR group (4.7%, 0%) (p = 0.000), relative amount of LSD1 showed no statistically difference between newly diagnosed AML and ALL groups (1.177 ± 1.646, 1.275 ± 1.845) or refractory/relapse group (2.050 ± 2.470, 4.107 ± 3.676) and CR group (0.029 ± 0.033, 0.019 ± 0.024) (p > 0.05). In all AL patients, LSD1 positive rate in newly diagnosed (84.6%) and refractory/relapse groups (100%) was higher than that in CR group (3.8%). LSD1 relative amount in newly diagnosed group (1.274 ± 1.760), refractory/relapse group (3.359 ± 3.319) and CR group (0.027 ± 0.031) was higher than that in control group (p < 0.01), and in refractory/relapse group was higher than that in newly diagnosed group and CR group (p < 0.01), in newly diagnosed group was higher than that in CR group (p < 0.01). It is concluded that overexpression of LSD1 is correlated with refractory or relapse in AL. LSD1 expression level can reflect disease status of AL patients and may be a predictive biomarker for unfavourable prognosis of AL.

Surface-enhanced Raman spectroscopy: substrate-related issues.

After over 30 years of development, surface-enhanced Raman spectroscopy (SERS) is now facing a very important stage in its history. The explosive development of nanoscience and nanotechnology has assisted the rapid development of SERS, especially during the last 5 years. Further development of surface-enhanced Raman spectroscopy is mainly limited by the reproducible preparation of clean and highly surface enhanced Raman scattering (SERS) active substrates. This review deals with some substrate-related issues. Various methods will be introduced for preparing SERS substrates of Ag and Au for analytical purposes, from SERS substrates prepared by electrochemical or vacuum methods, to well-dispersed Au or Ag nanoparticle sols, to nanoparticle thin film substrates, and finally to ordered nanostructured substrates. Emphasis is placed on the analysis of the advantages and weaknesses of different methods in preparing SERS substrates. Closely related to the application of SERS in the analysis of trace sample and unknown systems, the existing cleaning methods for SERS substrates are analyzed and a combined chemical adsorption and electrochemical oxidation method is proposed to eliminate the interference of contaminants. A defocusing method is proposed to deal with the laser-induced sample decomposition problem frequently met in SERS measurement to obtain strong signals. The existing methods to estimate the surface enhancement factor, a criterion to characterize the SERS activity of a substrate, are analyzed and some guidelines are proposed to obtain the correct enhancement factor.

[Distribution behaviors of phenanthrene to humic fractions in natural soil].

After adsorption of phenanthrene by the natural soil under different concentrations initially added, the soil sample was extracted for humic acid fraction (including humic acid and fulvic acid), and the sorption amount of phenanthrene in humin fraction was calculated to investigate the adsorption/distribution kinetics in two soil organic fractions and the corresponding influence of original phenanthrene concentration. The experimental data were fitted using Freundlich equation. The results show that, distribution of phenanthrene in the soil exhibited a multi-stage property, i.e., from a first fast sorption to a breakthrough at about 48 h, then followed by a slow sorption procedure. In the fast sorption stage (before 48 h), there was an up-to-down fluctuation of phenanthrene sorption ratio (sorption amount/added amount) in humic acid fraction, possibly due to surface sorption by minerals and competitive sorption by humin fraction. In the slow sorption stage, variations in sorption ratio in humic acid fraction was very small, and the influence of original concentration of phenanthrene was slight; while for humin fraction, the sorption ratio of phenanthrene at lower initial concentration was significantly higher than at higher one, in addition, the sorption ratio showed a gradually increasing trend, indicated humin fraction as the main domain in charge of the slow sorption. The fitting results of model parameters demonstrated that, sorption nonlinearity of phenanthrene in the natural soil increased in the following order: humic acid fraction< whole soil< humin fraction, and enhanced gradually. Different characteristics of humic acid and humin fractions in the multi-stage kinetics of phenanthrene sorption/distribution further reflected the effects of heterogenerity of soil organic fractions on nonlinear sorption behaviors.

[Effect of different cytokine combinations on the expression of CD49d and CXCR4 and ex vivo expansion of umbilical cord blood mononuclear cells].

This study was purposed to explore the effect of different cytokine combinations on the expansion of the mononuclear cells drived from umbilical cord blood (CB) ex vivo and expression of CXCR4 and CD49d on CD34+ cells after expansion. Human fresh CB mononuclear cells were cultured in serum-free and stroma-free medium containing different combinations of cytokine for 7 days. At day o and 7, the total cells were counted, CD34+ cells and CD34+CXCR4+, CD34+CD49d+ cells were assayed by flow cytometry, and CFU were determined. According to the different combinations of cytokine, experiments were divided into four groups: control, SF group (SCF + FL), SFT group (SCF + FL + TPO) and SFT6 group (SCF + FL + TPO + IL-6). The results showed that the SF (SF group) combination supported only low expansion of total cells, CD34+ cells and CFU. The addition of TPO in SF group restored UCB stem/progenitors expansion to a higher level than that in SF group, while there was no difference between groups SFT and SFT6 (P > 0.05). The cytokine combinations in groups SF, SFT and SFT6 all could upregulate the expression levels of CD49d and CXCR4 on expanded cord blood CD34+ cells, but there were no significant differences between groups SF, SFT and SFT6 (P > 0.05). It is concluded that SCF + FL has no strong synergistic effects on primitive hematopoietic cells. TPO plays an important role in enhancing expansion of umbilical cord blood hematopoietic cells, while IL-6 only shows a neutral effect on it. SCF + FL + TPO combination not only promotes progenitor cells expansion but also upregulates the expression of CD49d and CXCR4 on CD34+ cells from cord blood.

Distribution and characteristics of organic micropollutants in surface sediments from Bohai Sea.

Spatial distribution and compositional characteristics of PAHs, DDTs and PCBs in surface sediments from Bohai Sea were investigated. Proportion of LMW PAHs at Jinzhou Bay was significant, due probably to the petrogenic sources from neighboring oil wells and plants, while HMW PAHs were dominant in the other sea areas, inferred pyrogenic origins mainly from coal or petroleum combustion. The average ERL quotient for the PAH species in Qinhuangdao and Liaodong Bay indicated relatively stronger potential ecological risk. The concentration ratios of DDT to metabolites (DDD + DDE) exceeded 1.0 in the coastal areas of Qinhuangdao, Liaodong Bay and Bohai Bay, demonstrated some recent inputs of DDT nearby, and DDD as the major degradation product. The concentrations of PCBs were generally low, however, the contents of DDTs were greater than the ERL guidelines in the coastal areas of Qinhuangdao, Liaodong Bay and Bohai Bay, and suggested the potential ecological risk.

[Influence of water soluble organic carbon on determination of adsorption coefficient of phenanthrene].

Organic carbon normalized sorption coefficient of phenanthrene in soils was determined in a batch experiment. The influence of the presence of dissolved organic carbon (DOC) on sorption coefficient was also investigated. The results demonstrated that, the DOC dissolved from the soil would enhance the water solubility of phenanthrene and change the sorption behavior of phenanthrene between soil and water, consequently leading to an underestimation of sorption coefficient. When the binding coefficient of DOC and phenanthrene (K(doc)) from the literatures was adopted for correction of measured data, a better estimation of sorption coefficient could be achieved. In this study, lgK(oc) and lgK(Foc) were 4.35 and 7.01, respectively. Comparison between the uncorrected/corrected lgK(oc) and the literature data could partially reflect the deviation caused by the influence from various concentrations of DOC may occur in many sorption studies in water-soil system. It was significant to compare the sorption coefficient derived from different studies considering this influence.

[In vitro expansion of cord blood mononuclear cells supported by fetal bone marrow stromal cells and cytokines].

This study was aimed to explore the role of human fetal bone marrow stromal cells (FBMSC) in combination with exogenous cytokines in supporting the in vitro expansion of cord blood mononuclear cells and the expression of CXCR4(+) and CD49d(+) in CD34(+) cells. Mononuclear cells (MNC) separated from cord blood (CB) were cultured in a serum-free support culture system with FBMSC or exogenous cytokines or both of them. On day 0, 6, 10 and 14, total cells were counted, CD34(+), CD34(+)CXCR4(+) and CD34(+)CD49d(+) cells were quantitated by FACS, and hematopoietic progenitor cells were assessed by semisolid culture assay. The results showed that after culturing for 14 days, CD34(+) cells, CD34(+)CXCR4(+) cells, CD34(+) CD49d(+) cells and colony forming unit (CFU) were significantly increased (P < 0.05). Compared with other groups, expansion multiple of CD34(+), CD34(+)CXCR4(+), CD34(+)CD49d(+) cells and CFU were higher than that in FBMSC and cytokine group (P < 0.05). It is concluded that the culture system used in this study can not only support the expansion of CB MNCs but also increase the number of hematopoietic stem and progenitor cells which has chemokine and adhesion capacity. This culture system may be a feasible way for in vitro culture of cord blood cells.

[Influence of neferine and erythromycin on cellular GSH concentration in K562/A02 cell line].

OBJECTIVE: To investigate the reversal effect of multidrug resistance (MDR) mediated by glutathione (GSH) detoxifcation system in K562/A02 cell line by neferine and erythromycin. METHODS: Cellular GSH concentration was examined by biochemical analyses with DTNB. RESULTS: Cellular GSH concentration in K562/A02 cell line [(137.34 +/- 33.10) mg/mgprot] was higher than that in K562 cell line [(73.38+/-10.02) mg/mgprot] (P < 0.05), and 1.87-fold greater in K562/A02 cell line compared with that in K562 cell line. Cellular GSH concentration in K562/A02 cell line treated with Nef10 mg/L, EM100 mg/L, Nef10 mg/L + EM100 mg/L, and VRP5 mg/L for 2 days [(69.01 +/- 15.99) mg/mgprot, (70.57 +/- 11.93) mg/mgprot, (65.74 +/- 13.37) mg/mgprot, and (70.86 +/- 16.16) mg/mgprot, respectively] decreased than that in K562/A02 cell line without drugs (P < 0. 05). CONCLUSION: Increase of cellular GSH concentration was one of the MDR mechanisms in K562/A02 cell line. Decrease of cellular GSH concentration may be one of the MDR reversal mechanisms in K562/A02 cell line by neferine and erythromycin.

[Expression of multidrug resistance P-170 and MRP and their correlation with clinical drug resistance in acute leukemia].

OBJECTIVE: To investigate the relevance between the expression of P-170 and MRP and clinical drug resistance in acute leukemia. METHODS: The expression of P-170 and MRP in mononuclear cells of bone marrows was analyzed by the immunohistochemical technique in 72 acute leukemia patients. RESULTS: The expression of P-170 was positive in 46 and negative in 26 of the 72 post-chemotherapy acute leukemia patients. The therapeutic effect of the P-170 positive expression patients was significantly poorer than that of the negative expression patients (P < 0.01). The expression of MRP was positive in 39 and negative in 33 of the 72 post-chemotherapy acute leukemia patients. The therapeutic effect of the MRP positive expression patients was significantly poorer than that in the negative expression patients (P < 0.01). The expression of P-170 and MRP had a significant concordance (Kappa = 0.427, P < 0.01). The sensitivity of P-170 and MRP which were analyzed simultaneously was 97.5%, which was higher than that of P-170 (90%) or MRP (77.5%) analyzed respectively in drug resistance patients. CONCLUSION: The expression of P-170 and/or MRP was significantly related with drug resistance in clinical chemotherapy. The therapeutic effect was significantly poorer in P-170 and/or MRP positive expression patients than that in negative expression patients. These data suggest that P-170 and MRP analyzed simultaneously can improve the value of diagnosis and prognosis in patients with drug resistance leukemia.