CuPc/FeNC双组分催化剂协同催化硝酸盐转化为氨

氨(NH_(3))作为重要的化学品和能源储存介质,需求量与日俱增.本文旨在通过电化学硝酸根还原反应(NO_(3)^(−)RR),将NO_(3)^(−)转化为NH3,不仅解决了NO_(3)^(−)引起的环境污染问题,又可以满足对NH_(3)的迫切需求.然而,NO_(3)^(−)RR涉及多个电子和质子转移过程,其中,NO_(2)^(−)是NO_(3)^(−)活化转化和深度还原合成NH_(3)的重要中间体.酞菁铜(CuPc)能够高效地活化转化NO_(3)^(−)为NO_(2)^(−),但在低过电位时无法有效地将NO2−还原为NH3,难以获得较高的氨法拉第效率(FENH3)和分电流密度.而氮配位的铁单原子催化剂(FeNC)则有较好的NO_(2)^(−)吸附活化特性.因此,利用双组分催化剂之间的协同作用以实现高效NO_(3)^(−)RR的活性和选择性是本文的主要研究思路.本文设计了CuPc/FeNC串联催化剂,利用CuPc和FeNC对NO_(3)^(−)和NO_(2)^(−)的吸附活化能力的差异,实现了高效的协同催化转化.X射线衍射、高角环形暗场扫描透射电镜、X射线光电子能谱及X射线吸收谱结果表明,FeNC催化剂中Fe原子均匀分布于ZIF-8热解后的基底.通过将FeNC和CuPc负载于气体扩散电极,在流动电解池中完成NO_(3)^(−)RR.CuPc/FeNC催化剂在较低电势区间中能够实现接近100%的NH3法拉第效率,同时在−0.57 V vs.RHE时达到273 mA cm–2的NH3分电流密度,并且在整个电势范围内有效地抑制了NO_(2)^(–)聚集.与单组分催化剂CuPc和FeNC对比结果表明,在−0.53 V vs.RHE时,CuPc/FeNC催化剂表现出较高的FE(NH_(3))/FE(NO_(2)^(−))比值,是CuPc催化剂的50倍;同时CuPc/FeNC催化剂上NH3分电流密度是FeNC催化剂的1.5倍.进一步研究了NO_(3)^(–)RR中的串联反应机制,其中FeNC催化剂表现出较高的NO_(2)^(–)RR活性,并且有效抑制了析氢反应.此外,CuPc/FeNC催化剂和FeNC催化剂在NO_(2)^(−)RR中表现出类似的NH3分电流密度,这表明在NO_(3)^(−)RR中,CuPc/FeNC催化剂性能的提高来源于FeNC位点能够进一步还原CuPc位点产生的NO_(2)^(–).理论计算结果表明,FeNC比CuPc表现出更强的NO_(2)^(–)吸附活化能力,说明NO_(2)^(−)在FeNC上更容易进行加氢还原.NO_(3)^(−)RR反应全路径分析结果表明,对于^(*)NO_(3)还原到*NO2过程,CuPc相对于FeNC位点具有明显降低的反应自由能,说明CuPc有利于NO_(2)^(−)的生成;而FeNC位点在后续的^(*)NO_(2)还原合成^(*)NH_(3)过程中具有更低的反应自由能,这与实验结果一致.一系列非原位和原位表征证明了CuPc催化剂在高电位下存在少量金属颗粒析出,与CuPc催化剂在高电位下NH_(3)分电流密度快速增加结果一致.综上,本工作中CuPc和FeNC催化剂之间的协同作用弥补了各自的不足,通过串联反应机制,在低过电位下有效增加了NH_(3)的法拉第效率和电流密度,实现了高效的协同催化转化,为设计和合成高效催化剂提供了新思路.

Effect of Different Splint Thicknesses on Occlusal Function and Temporomandibular Joint Sounds:A Clinical Report

Background: Occlusal splint therapy, which is a conservative approach to treat temporomandibular disorders (TMDs) and bruxism, can change the occlusal contact of dentition. However, little is known about the variation in bite force and temporomandibular joint (TMJ) sounds. The objective of this case report is to compare the effects of different splint thicknesses constructed by vacuum lamination technology on occlusal function and TMJ sounds. Clinical Presentation: This study presents a 24-year-old male with bruxism. Four splints of different thicknesses (0.6 mm, 1 mm, 2.5 mm and 3 mm) were fabricated and tested. Then, an array of occlusal data were recorded and analyzed by the T-Scan?III system and joint vibration analysis (JVA). Conclusion: The results reveal that splints of different thicknesses manufactured by the vacuum hot-lamination apparatus may cause a change in occlusal force.

A Correlation Analysis of Postoperative Hypercoagulability and Peripheral Circulating Tumor Cells in Patients with Lung Cancer

Objective:To explore the correlation between peripheral circulating tumor cells and hypercoagulability in patients with lung cancer after surgery.Methods:From January 2017 to December 2021,89 patients with lung cancer who were treated in the Affiliated Hospital of Hebei University were selected as the research subjects,and a retrospective analysis was conducted to analyze and observe the D-dimer(DD),fibrinogen(FIB),and platelet(PLT)levels in peripheral blood,as well as detect peripheral CTC.Results:There were statistical differences in TMN staging,tumor metastasis,and lymph node metastasis in the clinical data,but there were no statistical differences in gender,smoking history,and pathological classification.After retrospective analysis and comparison of the patients,the DD(mg/ml),FIB(g/L),and PLT(×10^(9)/L)levels of the CTC positive group were 3.41±0.58,3.98±0.87,and 367.26±34.98,respectively;the CTC negative group’s DD(mg/ml),FIB(g/L),and PLT(×10^(9)/L)levels were 0.89±0.49,1.06±0.45,and 234.69±35.69,respectively,and the differences were statistically significant.The factors affecting the prognosis of patients included TMN staging and CTC;the number of CTC positives in the death group was significantly higher than that in the survival group,and there was a statistical difference between the groups.Gender,age,smoking history,pathological type,and surgical resection had no effect on the prognosis of patients.Among the enrolled patients,the survival rate was 71.91%.Conclusion:CTC-positive patients have a higher probability of hypercoagulability after surgery and are prone to tumor metastasis;thus,CTC can be used as a judgment index for the prognosis of patients.

能源催化材料的电化学合成

电催化是发展可持续洁净能源技术的基础科学,是电化学能源转换和物质转化的关键环节.精准合成催化活性纳米结构是制约很多电催化反应走向实际应用的重要挑战.与湿化学合成、固相合成和气相沉积等传统方法相比,电化学合成是一种简单、快速、廉价及可控的高效催化材料制备方法,也是一种最为直接的一体化电极制备方法.本文综述了近年来利用电化学合成方法制备高效能源催化材料的研究进展.首先,简要介绍了电沉积、阴极腐蚀、电化学去合金化、电化学置换、电化学剥离和电化学修饰等几种主要电化学合成方法的基本原理,并讨论了电化学合成中电势、电流和电解质组成等关键合成参数的影响.然后,重点讨论了电化学合成的催化材料在燃料电池、电解水、二氧化碳/一氧化碳电还原、电化学合成氨、有机分子电化学转化等重要电催化反应中的应用.这些催化材料按照形貌可分为单原子催化剂、球形纳米粒子、形貌可控的纳米粒子、二维层状/片状纳米材料和三维纳米结构等.电化学合成在制备结构明确的单原子催化剂上具有其它合成方法不可比拟的优势.与胶体化学方法相比,电化学合成的尺寸和形貌可控的纳米粒子具有表面清洁、无表面附着的有机配体以及不需要焙烧等催化剂预处理的特点.除形貌外,电化学合成还可以制备在原子尺度上具有特定几何和电子结构的催化活性纳米结构.电化学方法也是催化剂修饰和再生的一种重要途径,结合特定的电化学程序,可在连续操作条件下实现催化材料的原位再生.通过讨论代表性的催化剂案例,分析这些催化剂在电催化应用中的构效关系,阐明了电化学合成方法在催化剂理性设计和制备中的独特优势.最后,总结了当前电化学合成催化材料方面存在的问题和研究挑战,并展望了未来的发展方向.电化学合成的能源催化材料在热催化、光催化等领域的应用价值仍需进一步探索.此外,电化学合成在金属有机框架、高熵合金等新兴功能材料的制备上也具有很好的应用前景.如何利用电化学的特点并结合原位表征、大数据预测等先进实验和理论方法,更加精准、可控地合成催化活性纳米结构依然是未来该领域重要的研究机遇.

用于二氧化碳电催化还原的电解器研究进展

可再生能源驱动的二氧化碳电催化还原反应(CO_(2)RR)是实现CO_(2)高效转化和利用的有效途径。电解器的理性设计对于提高CO_(2)RR性能及其工业放大应用具有重要意义。电解器构型及其操作条件在很大程度上决定了电极附近的局部反应环境,从而调变催化性能。本文深度剖析了三种CO_(2)电解器(H型电解池、流动电解池和膜电极电解池)的研究进展和现状,结合文献报道,在电流密度、法拉第效率、能量效率和稳定性等四个关键性能参数上比较和讨论了不同电解器构型的优缺点及其对CO_(2)RR性能的影响。面向实际应用的CO_(2)RR研究应该把工业级电流密度作为提高其它三个指标的前提。尽管目前还存在一些问题和挑战,膜电极电解器被认为是最具工业应用前景的技术方案。本文最后提出了一些可能的研究策略和机遇,展望了该领域的未来发展趋势。

Effects of 5-hydroxytryptamine Receptor on the Reaction of the Lower Esophageal Sphincter Under the Electrical Field Stimulation

In the first and second parts of this study,5-hydroxytryptamine(5HT)receptors,including 5-HT3 and 5-HT4 with the highest expression level,were found in clasp and sling fibres of the lower esophageal sphincter(LES).Specific 5-HT3 and 5-HT4 receptor agonists can induce the contraction effect of clasp and sling fibres of the LES while specific 5-HT7 receptor agonists showed no effects.In the study of this part,the in-vitro muscle tension measurement technology and EFS methods were used to detect the effect of the selective 5-HT receptor antagonist on the clasp and sling fibres of the in-vitro LES under the electrical field stimulation(EFS),and further to ensure the effect of 5-HT receptor in the LES neuroregulatory pathway,and deeply explore the effect of 5-HT receptor in the systolic and diastolic function regulation of the LES.

Effect of 5-hydroxytryptamine Receptor in the Lower Esophageal Sphincter Regulation Mechanism

As a neurotransmitter and avascular active substance,the 5-hydroxytryptamine(5-HT,serotonin)is widely distributed in the central nervous system and surrounding tissues.The 5-HT can play its role by acting on its corresponding 5-HT receptor.Nowadays,the 5-HT receptor can be classified into seven,according to different signal transduction method of receptors,the 5-HT3 receptor belongs to the ligandgated ion channels,while other six 5-HT receptors are involved into the G protein-coupled receptors and play the biological role by binding to specific G protein-coupled receptors(GPCRs)on the surface of the cell membrane.The 5-HT plays an important role in the brain-gut information transmission and studies showed that the physiological stimulations like having meals,and pathological stimulations like ischemia and stress could promote the release of the 5-HT.In the gastrointestinal tract,the 5-HT is closely related to gastrointestinal sensitivity,gastrointestinal movement and secretion regulation,as well as many gastrointestinal dysfunction disorders,such as gastrointestinal power and visceral sensitivity abnormality and abnormalities of brain-gut axis.

Observation on the Effect of Spontaneous Ventilation Single-Port Thoracoscopy and Conventional Thoracoscopy on T Lymphocyte Subsets and Inflammatory Factors in Patients with Non-Small Cell Lung Cancer

Objective:To explore the effects of two types of surgical approaches,spontaneous ventilation single-port thoracoscopy and conventional thoracoscopy,on T lymphocyte subsets and inflammatory factors in patients with non-small cell lung cancer.Methods:Fifty-eight patients with non-small cell lung cancer who underwent surgery in the Affiliated Hospital of Hebei University from January 2020 to December 2021 were selected as the study subjects.All of them underwent standard lobectomy and lymph node dissection.Among them,32 patients who underwent spontaneous ventilation single-port thoracoscopy were included in the study group,while 26 patients who underwent conventional thoracoscopy were included in the control group.The perioperative related indices,lung function,immune factor levels,and inflammatory factor levels were compared between the two groups.Results:In the study group,the perioperative incision length,intraoperative blood loss,operation time,and number of lymph node dissections were 4.28±2.01,77.89±12.02,87.21±16.11,and 20.69±4.45,respectively.In the control group,the perioperative incision length,intraoperative blood loss,operation time,and number of lymph node dissections were 6.32±2.45,84.98±16.98,95.88±14.89,and 21.45±4.36,respectively.There was no statistical difference between the study group and the control group in the number of lymph node dissections and intraoperative blood loss;the lung function in the study group was significantly better than that in the control group;the levels of T cell subsets CD4+,CD8+,CD4+/CD8+,CD16+CD56+of the study group were 46.36±5.87,30.98±4.12,1.19±0.23,and 17.41±6.25,respectively,while those in the control group were 35.78±4.12,34.14±3.87,1.04±0.24,and 12.45±5.56,respectively;the levels of immunoglobulin IgG,IgM,and IgA of the study group were 10.45±2.14,1.21±0.24,and 1.26±0.25,respectively,while those of the control group were 8.78±1.78,1.06±0.12,and 1.06±0.26,respectively,with statistical differences;the levels of CRP,IL-6,IL-8,and TNF-αof the control group were 21.87±4.26,98.01±9.58,111.03±9.96,and 123.05±9.77,respectively,while those of the study group were 19.47±3.89,89.12±8.96,104.32±9.12,and 112.98±9.16,respectively,in which the comparison was statistically significant.Conclusion:In the surgical treatment of non-small cell lung cancer,spontaneous ventilation single-port thoracoscopic surgery has several advantages,which include less trauma and bleeding.It reduces the impact of surgical trauma on the immune function of the body,improves the postoperative lung function and inflammatory stress of the body,as well as accelerates the recovery of patients.It is an alternative to open lung lobectomy for the treatment of lung cancer.

Analysis and Comparison of the Effect of Preserving Spontaneous Breathing Without Intubation and Endotracheal Intubation with One Lung Ventilation in Single-hole Thoracoscopic Bulla Suture

Objective:To explore the situation of patients and the compare the effect between two methods,which are preserving spontaneous breathing without intubation and endotracheal intubation with one lung ventilation in the single-hole thoracoscopic bulla suture.Method:42 patients who received single-hole thoracoscopic pulmonary bullae suture in our hospital from January 2020 to December 2021 were selected as the study subjects,including 19 patients who underwent endotracheal intubation and one lung ventilation as the control group and 23 patients who underwent single-hole thoracoscopic pulmonary bullae suture without intubation as the study group.The relevant indexes,postoperative general conditions,complications and pneumothorax recurrence of the two groups were analyzed and observed.Results:In the control group,the scores of anesthesia time(points),resuscitation time(points),surgical visual field score(points),surgical time(points),and surgical bleeding volume(points)were 20.8±4.6,19.9±7.9,1.7±0.5,44.9±7.9,and 11.4±2.4 respectively.In the study group,the scores of anesthesia time(points),resuscitation time(points),surgical visual field score(points),surgical time(points),and scores of surgical bleeding(points)were 17.9±4.3,15.4±3.4,1.9±0.4,48.4±7.1,10.9±2.2,respectively.There was no statistical difference in surgical visual field score,surgical time and surgical bleeding whereas there was a statistical difference between anesthesia time and resuscitation time.In the control group after operation,VAS score at 6 hours after operation,SaO_(2)(%)after operation,PaCO_(2)(mmHg)after operation,drainage volume(ML)after operation,feeding time(H)after operation,retention time of thoracic tube after operation(H),WBC(109)on the first day after operation,hospitalization time(d),and total hospitalization cost(RMB 1000)were 2.1±0.7,98.2±1.4,42.4±4.9,139.1±23.1,6.9±1.6,37.1±5.4,7.9±2.1,6.6±1.3,and 2.6±0.3 respectively.As for the study group,the VAS score at 6 hours after operation,SaO_(2)(%)after operation,PaCO_(2)(mmHg)after operation,drainage volume(ML)after operation,feeding time(H)after operation,retention time of thoracic tube after operation(H),WBC(109)on the first day after operation,hospitalization time(d),and total hospitalization cost(RMB 1000)were 1.9±0.4,97.9±1.2,42.8±5.1,151.8±21.9,4.3±1.4,15.3±2.6,5.2±2.3,4.2±1.2,and 1.8±0.4 respectively.Among them,there were no significant differences in visual analog scale(VAS)score at 6 hours after operation,SaO_(2) after operation and PaCO_(2) after operation between the two groups,but there were significant differences in other factors.The complication rate of the control group was 36.84%,which was significantly higher than that of the study group(4.35%),with statistical difference.The recurrence rate of the control group was 21.05%,which was not significantly different from that of the study group(4.35%).Conclusion:The single-hole thoracoscopic bullae suture without intubation can reduce the anesthesia time and resuscitation time of patients,reduce the hospitalization cost of patients,reduce the treatment burden,shorten the first feeding time,and reduce the complication rate of patients.Therefore,it is worthy of clinical promotion.

Analysis of Recurrence and Influencing Factors of Spontaneous Pneumothorax After Thoracoscopic Surgery

This study was conducted to explore the factors that are influencing the recurrence of spontaneous pneumothorax after thoracoscopic surgery.Around 110 patients with spontaneous pneumothorax who underwent thoracoscopic bullectomy in Hebei Hospital from May 2017 to May 2021 were included in this study.The patients were divided into the recurrence group(15 cases)and the non-recurrence group(95 cases),and the influences of gender,age,smoking history,height,weight,operation time,the weight of the excised tissue,number of excised pulmonary bullae,postoperative chest tube maintenance time,duration of air leakage,and length of hospital stay on the recurrence of spontaneous pneumothorax after thoracoscopic surgery were investigated.This study found that the height/weight,operation time,duration of air leakage,number of pulmonary bullae removed,weight of the removed tissue,postoperative chest tube maintenance time,and duration of hospital stay in the recurrence group was 3.2±0.4,50.9±1.2,2.1±0.4,1.6±0.2,4.2±1.3,2.4±1.5 and 7.2±1.5,respectively.Meanwhile,the recurrence group was 2.6±0.3,50.8±1.3,1.3±0.2,1.8±0.9,4.4±1.2,4.1±1.7 and 6.9±1.6,respectively.After comparing the relevant factors between the recurrence group and the non-recurrence group,it was found that there was comparability between age,height/weight,duration of air leakage and postoperative chest tube maintenance time,where these factors were shown to affect the recurrence of spontaneous pneumothorax after thoracoscopic surgery,while gender,smoking,operation time,number of resected bullae,weight of resected tissue and length of hospital stay had no effect on recurrence after spontaneous pneumothoracoscopic surgery.In short,thoracoscopic bullectomy is the best clinical treatment for spontaneous pneumothorax,however the occurrence of recurrence of spontaneous pneumothorax after the operation,which is mainly influenced by the patient’s height/weight,postoperative air leakage duration,and chest tube maintenance time.Therefore,it is essential to pay attention to the surgical treatment of the patients,and fully identify the related factors of postoperative recurrence,thereby the follow-up clinical treatment can be carried out effectively.

CO2 electrolysis at industrial current densities using anion exchange membrane based electrolyzers

Significant progress on electrocatalytic CO2 reduction reaction (CO2RR) has been achieved in recent years.However,the research and development of electrolyzer device for CO2RR is scarce.Here we use anion exchange membrane to develop zerogap electrolyzers for CO2RR.The electrochemical properties of the electrolyzers with Pd/C and Cu cathodes are investigated.The Pd/C cathode shows a current density of 200 mA cm^-2with CO Faradaic efficiency of 98%and energy efficiency of 48.8%,while the Cu cathode shows a current density of 350 mA cm^-2with total CO2RR Faradaic efficiency of 81.9%and energy efficiency of 30.5%.This work provides a promising demonstration of CO2 electrolyzer using anion exchange membrane for CO2 electrolysis at industrial current densities.