Reference intervals of Cyfra21-1 and CEA in healthy adult Han Chinese population.

Objective: This study aimed to establish the reference intervals of Cyfra21-1 and CEA for the local screening populations using a chemiluminescence method. Methods: A total of 4845 healthy adults and 190 lung cancer patients were included from the First Hospital of Hebei Medical University. The levels of Cyfra21-1 and CEA were measured to establish the local reference intervals. Results: The upper limit reference intervals for Cyfra21-1 and CEA were determined as 3.19 ng/ml and 3.13 ng/ml, respectively. Notably, both Cyfra21-1 and CEA levels were found to be higher in males than in females. Additionally, both biomarkers showed an increasing trend with age.In terms of diagnostic efficacy, the receiver operating characteristic (ROC) curve areas for Cyfra21-1, CEA, and their combination in lung cancer were 0.86, 0.73, and 0.91, respectively. Conclusion: Our study revealed that the reference intervals of Cyfra21-1 and CEA in the local population differed from the established reference intervals. Furthermore, both biomarkers exhibited gender-dependent variations and demonstrated a positive correlation with age. Combining the two biomarkers showed potential for improving the diagnosis rate of lung cancer.

Breaking solvation dominance of ethylene carbonate via molecular charge engineering enables lower temperature battery.

Low temperatures severely impair the performance of lithium-ion batteries, which demand powerful electrolytes with wide liquidity ranges, facilitated ion diffusion, and lower desolvation energy. The keys lie in establishing mild interactions between Li+ and solvent molecules internally, which are hard to achieve in commercial ethylene-carbonate based electrolytes. Herein, we tailor the solvation structure with low-ε solvent-dominated coordination, and unlock ethylene-carbonate via electronegativity regulation of carbonyl oxygen. The modified electrolyte exhibits high ion conductivity (1.46 mS·cm-1) at -90 °C, and remains liquid at -110 °C. Consequently, 4.5 V graphite-based pouch cells achieve ~98% capacity over 200 cycles at -10 °C without lithium dendrite. These cells also retain ~60% of their room-temperature discharge capacity at -70 °C, and miraculously retain discharge functionality even at ~-100 °C after being fully charged at 25 °C. This strategy of disrupting solvation dominance of ethylene-carbonate through molecular charge engineering, opens new avenues for advanced electrolyte design.

A diagnostic test of real-time PCR detection in the diagnosis of clinical bloodstream infection.

BACKGROUND: Blood culture remains the standard for diagnosing bloodstream infections, but it is difficult to identify bacteria directly and timeliness. The real-time polymerase chain reaction (PCR) has the potential to fill this diagnostic gap. This study intends to explore the sensitivity and specificity of PCR in detecting bloodstream infection pathogens and to compare it with routine blood culture to explore its clinical application value. METHODS: A total of 126 patients with bloodstream infections collected from various clinical departments of The First Hospital of Hebei Medical University. The patient's sample was divided into two parts. The one for multiplex PCR detection was performed using the Pathogeno Elite Multiplex PCR kit. Another blood culture was a fully automatic blood culture system from Autobio company. RESULTS: Among the 126 patients, a total of 17 pathogens were detected by PCR and blood culture both methods. PCR detected a total of 43 positive samples and 83 negative samples. Five samples were positive with blood culture, and 81 were negative. The negative predictive value of PCR was 0.98, with a sensitivity of 0.71 and a specificity of 0.68. A total of 38 specimens were positive for PCR but negative for blood culture, and 2 samples were positive for blood culture but negative for PCR. The top 5 pathogens with PCR detection were Epstein-Barr virus (27 cases), Human herpes virus 5 (9 cases), Klebsiella pneumoniae (5 cases), Staphylococcus (5 cases), and Stenotrophomonas maltophilia (4 cases). CONCLUSIONS: PCR detection can rapidly identify more pathogens and even multi-pathogen infections. Therefore, PCR testing may improve pathogen detection in patients with suspected bloodstream infections, enabling targeted treatment of patients.

Construction of Low-Impedance and High-Passivated Interphase for Nickel-Rich Cathode by Low-Cost Boron-Containing Electrolyte Additive.

The nickel-rich cathode LiNi0.8 Co0.1 Mn0.1 O2 (NCM811) possesses the advantages of high reversible specific capacity and low cost, thus regarded as a promising cathode material for lithium-ion batteries (LIBs). However, the capacity of the NCM811 decays rapidly at high voltage due to the extremely unstable electrode/electrolyte interphase. The discharge capability at low temperature is also impaired because of the increasing interfacial impedance. Herein, a low-cost film-forming electrolyte additive with multi-function, phenylboronic acid (PBA), was employed to modify the interphasial properties of the NCM811 cathode. Theoretical calculation and experimental results showed that PBA constructed a highly conductive and steady cathode electrolyte interphase (CEI) film through preferential oxidation decomposition, which greatly improved the interfacial properties of the NCM811 cathode at room (25 °C) and low temperature (-10 °C). Specifically, the capacity retention of NCM811/Li cell was increased from 68 % to 87 % after 200 cycles with PBA additive. Moreover, the NCM811/Li cell with PBA additive delivered higher discharge capacity under -10 °C at 0.5 C (173.7 mAh g-1 vs. 111.1 mAh g-1 ). Based on the improvement of NCM811 interphasial properties by additive PBA, the capacity retention of NCM811/graphite full-cell was enhanced from 49 % to 65 % after 200 cycles.

Cost-Efficient Film-Forming Additive for High-Voltage Lithium-Nickel-Manganese Oxide Cathodes.

The operating voltage of lithium-nickel-manganese oxide (LiNi0.5Mn1.5O4, LNMO) cathodes far exceeds the oxidation stability of the commercial electrolytes. The electrolytes undergo oxidation and decomposition during the charge/discharge process, resulting in the capacity fading of a high-voltage LNMO. Therefore, enhancing the interphasial stability of the high-voltage LNMO cathode is critical to promoting its commercial application. Applying a film-forming additive is one of the valid methods to solve the interphasial instability. However, most of the proposed additives are expensive, which increases the cost of the battery. In this work, a new cost-efficient film-forming electrolyte additive, 4-trifluoromethylphenylboronic acid (4TP), is adopted to enhance the long-term cycle stability of LNMO/Li cell at 4.9 V. With only 2 wt % 4TP, the capacity retention of LNMO/Li cell reaches up to 89% from 26% after 480 cycles. Moreover, 4TP is effective in increasing the rate performance of graphite anode. These results show that the 4TP additive can be applied in high-voltage LIBs, which significantly increases the manufacturing cost while improving the battery performance.

A Novel Electrolyte Additive Enables High-Voltage Operation of Nickel-Rich Oxide/Graphite Cells.

Nickel-rich oxide/graphite cells under high voltage operation provide high energy density but present short cycle life because of the parasitic electrolyte decomposition reactions. In this work, we report a novel electrolyte additive, N,O-bis(trimehylsilyl)-trifluoroacetamide (NOB), which enables nickel-rich oxide/graphite cells to operate stably under high voltage. When evaluated in a nickel-rich oxide-based full cell, LiNi0.5Co0.2Mn0.3O2 (NCM523)/graphite using a carbonate electrolyte, 1 wt % NOB provides the cell with capacity retention improved from 38% to 73% after 100 cycles at 1C under 4.5 V. It is found that NOB is able to eliminate hydrogen fluoride in the electrolyte. The radicals resulting from the interaction of NOB with the fluoride ion can be preferentially oxidized on the cathode compared with the electrolyte solvents, with its reaction products constructing N-containing interphases simultaneously on the cathode and anode, which suppress the parasitic electrolyte decomposition reactions, leading to the significantly improved cycle stability of nickel-rich oxide/graphite cells under high voltage.

Deciphering the Ethylene Carbonate-Propylene Carbonate Mystery in Li-Ion Batteries.

As one of the landmark technologies, Li-ion batteries (LIBs) have reshaped our life in the 21stcentury, but molecular-level understanding about the mechanism underneath this young chemistry is still insufficient. Despite their deceptively simple appearances with just three active components (cathode and anode separated by electrolyte), the actual processes in LIBs involve complexities at all length-scales, from Li+ migration within electrode lattices or across crystalline boundaries and interfaces to the Li+ accommodation and dislocation at potentials far away from the thermodynamic equilibria of electrolytes. Among all, the interphases situated between electrodes and electrolytes remain the most elusive component in LIBs. Interphases form because no electrolyte component (salt anion, solvent molecules) could remain thermodynamically stable at the extreme potentials where electrodes in modern LIBs operate, and their chemical ingredients come from the sacrificial decompositions of electrolyte components. The presence of an interphase on electrodes ensures reversibility of Li+ intercalation chemistry in anode and cathode at extreme potentials and defines the cycle life, power and energy densities, and even safety of the eventual LIBs device. Despite such importance and numerous investigations dedicated in the past two decades, we still cannot explain why, nor predict whether, certain electrolyte solvents can form a protective interphase to support the reversible Li+ intercalation chemistries while others destroy the electrode structure. The most representative example is the long-standing "EC-PC Disparity" and the two interphasial extremities induced therefrom: differing by only one methyl substituent, ethylene carbonate (EC) forms almost ideal interphases on the graphitic anode, thus becoming the indispensable solvent in all LIBs manufactured today, while propylene carbonate (PC) does not form any protective interphase, leading to catastrophic exfoliation of the graphitic structure. With one after another hypotheses proposed but none satisfactorily rationalizing this disparity on the molecular level, this mystery has been puzzling the battery and electrochemistry community for decades. In this Account, we attempted to decipher this mystery by reviewing the key factors that govern the interaction between the graphitic structure and the solvated Li+ right before interphase formation. Combining DFT calculation and experiments, we identified the partial desolvation of the solvated Li+ at graphite edge sites as a critical step, in which the competitive solvation of Li+ by anion and solvent molecules dictates whether an electrolyte is destined to form a protective interphase. Applying this model to the knowledge of relative Li+ solvation energy and frontier molecular orbital energy gap, it becomes theoretically possible now to predict whether a new solvent or anion would form a complex with Li+ leading to desirable interphases. Such molecular-level understanding of interphasial processes provides guiding principles to the effort of tailor-designing new electrolyte systems for more aggressive battery chemistries beyond Li-ion.

[Synthesis of 4-palmitoyl-sinomenine and its anti-inflammation activity].

OBJECTIVE: To synthesize the derivatives of sinomenine, 4-palmitoyl-sinomenine, and explore its therapeutic effect on lipopolysaccharide (LPS)-induced endotoxemia. METHODS: A highly efficient synthesis of sinomenine derivatives called 4-palmitoyl-sinomenine was made with a molecule of palmitic acid substitutions at C-16 position of ring A. One hour before endotoxemia induction by i.p. injection of 10 mg/kg LPS, high-dose treatment mice (n=5/group) received an i.p. injection of 5 mg/kg sinomenine or 4-palmitoyl-sinomenine while the low-dose treatment mice (n=5/group) received 2.5 mg/kg sinomenine or 4-palmitoyl-sinomenine. Untreated group and normal control group received normal saline. And their survival was monitored hourly for 24 hours. Examination of cytotoxicity of 4-palmitoyl-sinomenine on RAW264.7 cells was conducted at a concentration range of 1 to 125 µmol/L using MTT assay. RAW264.7 cells were exposed to 4-palmitoyl-sinomenine (0, 1, 2, 5, 10 µmol/L) for 24 hours, and then treated with LPS (1 µg/mL) for 6 hours. Then RAW264.7 cells were collected and the mRNA level of IL-6 was detected by real-time quantitative PCR(qRT-PCR). RESULTS: Sinomenine derivatives were successfully synthesized to get 4-palmitoyl-sinomenine. The survival percentage of 4-palmitoyl-sinomenine treatment groups was higher than that of sinomenine treatment groups at the same treatment concentration. The 4-palmitoyl-sinomenine inhibited RAW264.7 cell proliferation and IL-6 gene transcription. CONCLUSION: The 4-palmitoyl-sinomenine has an anti-inflammation probably through inhibiting the proliferation of RAW264.7 cells and decreasing the inflammatory gene expression and inflammatory cytokine release.

Oxidation induced decomposition of ethylene carbonate from DFT calculations--importance of explicitly treating surrounding solvent.

The oxidation induced reactions of the common lithium battery electrolyte solvent ethylene carbonate (EC) have been investigated for EC(2) using density functional theory and for selected reaction paths using Møller-Plesset perturbation theory (MP4). The importance of explicitly treating at least one solvent molecule interacting with EC during oxidation (removal of an electron) on the EC oxidation potential and decomposition reactions was shown by comparing oxidation of EC and EC(2). Accuracy of DFT results was evaluated by comparing with MP4 and G4 values for oxidation of EC. The polarized continuum model (PCM) was used to implicitly include the rest of the surrounding solvent. The oxidation potentials of EC(2) and EC(4) were found to be significantly lower than the intrinsic oxidation potential of an isolated EC and also lower than the oxidation potential of EC-BF(4)(-). The exothermic proton abstraction from the ethylene group of EC by the carbonyl group of another EC was responsible for the decreased oxidative stability of EC(2) and EC(4) compared to EC. The most exothermic path with the smallest barrier for EC(2) oxidation yielded CO(2) and an ethanol radical cation. The reaction paths with the higher barrier yielded oligo(ethylene carbonate) suggesting a pathway for the experimentally observed poly(ethylene carbonate) formation of EC-based electrolytes at cathode surfaces.

Theoretical investigations on oxidative stability of solvents and oxidative decomposition mechanism of ethylene carbonate for lithium ion battery use.

The electrochemical oxidative stability of solvent molecules used for lithium ion battery, ethylene carbonate (EC), propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate in the forms of simple molecule and coordination with anion PF(6)(-), is compared by using density functional theory at the level of B3LYP/6-311++G (d, p) in gas phase. EC is found to be the most stable against oxidation in its simple molecule. However, due to its highest dielectric constant among all the solvent molecules, EC coordinates with PF(6)(-) most strongly and reaches cathode most easily, resulting in its preferential oxidation on cathode. Detailed oxidative decomposition mechanism of EC is investigated using the same level. Radical cation EC(*+) is generated after one electron oxidation reaction of EC and there are five possible pathways for the decomposition of EC(*+) forming CO(2), CO, and various radical cations. The formation of CO is more difficult than CO(2) during the initial decomposition of EC(*+) due to the high activation energy. The radical cations are reduced and terminated by gaining one electron from anode or solvent molecules, forming aldehyde and oligomers of alkyl carbonates including 2-methyl-1,3-dioxolane, 1,3,6-trioxocan-2-one, 1,4,6,9-tetraoxaspiro[4.4]nonane, and 1,4,6,8,11-pentaoxaspiro[4.6]undecan-7-one. The calculation in this paper gives a detailed explanation on the experimental findings that have been reported in literatures and clarifies the mechanism on the oxidative decomposition of EC.