Analysis on First-stage Ignition of n-Heptane at Low Temperatures with a Lumped Skeletal Mechanism

Two-stage ignition exists in the low-temperature combustion process of n-heptane and the first-stage ignition also shows a negative temperature coefficient(NTC) phenomenon. To study key reactions and understand chemical principles affecting the first-stage ignition of n-heptane, a lumped skeletal mechanism with 62 species is obtained based on the detailed NUIGMech1.0 mechanism using the directed relation graph method assisted by sensitivity analysis and isomer lumping. The lumped mechanism shows good performance on ignition delay time under wide conditions. The study revealed that the temperature after the first-stage ignition is higher and a larger amount of fuel is consumed at lower initial temperatures. The temperature at the first-stage ignition is relatively insensitive to the initial temperature. Further sensitivity analysis and reaction path analysis carried out based on the lumped mechanism show that the decomposition of RO₂ to produce alkene and HO₂is the most important reaction to inhibit the first-stage ignitions. The chain branching explosion closely related to the first-stage ignition will be terminated when the rate constant for the RO₂ decomposition is larger than that of the isomerization of RO₂ to produce QOOH. The NTC behavior as well as other characteristics of the first-stage ignition can be rationalized from the competition between these two reactions.     

Effect of Manganese Valence on Specific Capacitance in Supercapacitors of Manganese Oxide Microspheres

Manganese oxides have attracted great interest in electrochemical energy storage due to high theoretical specific capacitance and abundant valence states. The multiple valence states in the redox reactions are beneficial for enhancing the electrochemical properties. Herein, three manganese microspheres were prepared by a one-pot hydrothermal method and subsequent calcination at different temperatures using carbon spheres as templates. The trivalent manganese of Mn₂O₃ exhibited multiple redox transitions of Mn³⁺/Mn²⁺ and Mn⁴⁺/Mn³⁺ during the intercalation/deintercalation of electrolyte ions. The possible redox reactions of Mn₂O₃ were proposed based on the cyclic voltammetry and differential pulse voltammogram results. Mn₂O₃ microsphere integrated the advantages of multiple redox couples and unique structure, demonstrating a high specific capacitance and long cycling stability. The symmetric Mn₂O₃//Mn₂O₃ device yielded a maximum energy density of 29.3 Wh kg⁻¹ at 250 W kg⁻¹.     

Interfacial passivation mechanism of sulfide towards quantum dot-sensitized nanocrystalline thin films

Journal of Solid State Electrochemistry - We report on the interfacial passivation mechanism in CdSe quantum dot-sensitized ZnO nanocrystalline thin film, where different sulfide semiconductors...     

TBAB包络化合物浆的管内流动再层流化现象

TBAB包络化合物浆是一种新型高密度潜热输送材料,在中央空调或区域供冷等系统中作为替代常规冷水的冷量输送媒体具有显著的节能应用前景.采用实验方法研究了A型TBAB包络化合物浆在水平直管内的层流和湍流流动特性.通过分析流动阻力随流速和固相含量等参数的变化规律,发现固相含量的增加有利于维持流动的层流趋势,在定流速条件下随着固相含量的增加流动状态会由湍流转变为层流,即出现"再层流化"现象,并且由于再层流化现象的出现,包络化合物浆的流动会出现"阻力降低区".     

低钾血症对颅脑创伤患者预后的影响

目的 探讨低钾血症在颅脑创伤患者中的发病情况及其与预后的关系。方法 2010 年6月至2013 年6 月共有168 例住院期间出现低钾血症且年龄≥18 岁的颅脑创伤患者纳入研究。依据低钾血症严重程度的不同,将患者分成轻度组（3.00mmol/L≤血钾＜3.50mmol/L）、中度组（2.50mmol/L≤血钾＜3.00mmol/L）和重度组（血钾＜2.50mmol/L）,各组均采用患者血钾的最低值进行数据分析。高钠血症和低磷血症分别被定义为血钠＞147.00mmol/L 和血磷＜0.80mmol/L。结果 受试患者的血钾在1.10~3.40mmol/L,平均2.90mmol/L。当血钾出现最低值时,与其余两组比较,重度组患者具有更高的血钠和更低的血磷水平（均P＜0.01）。与轻度组（10.5%）或中度组（25.7%）相比,重度组患者的病死率（82.1%）显著上升（均P＜0.01）。多变量逻辑回归分析结果显示,低格拉斯哥昏迷评分（OR=1.28,95%CI=1.12~1.42,P＜0.01）、低血钾（OR=5.57,95%CI=2.76~10.93,P＜0.01）、低血磷（OR=2.76,95%CI=1.11~7.25,P＜0.01）以及高血尿素氮（OR=1.16,95%CI=1.07~1.24,P＜0.01）是导致患者死亡的独立危险因素。结论 颅脑创伤患者是出现低钾血症的高危人群,重度低钾血症的患者更容易合并高钠血症和低磷血症。重度低钾血症和低磷血症是颅脑创伤患者死亡的独立危险因素。     

重度子痫前期产妇剖宫产布比卡因蛛网膜下腔阻滞麻醉适合剂量的临床研究

目的 探讨重度子痫前期产妇剖宫产重比重布比卡因蛛网膜下腔阻滞麻醉（腰麻）的适合剂量。方法 选取200例重度子痫前期产妇,ASAⅠ级或Ⅱ级,按随机数字表法分为4组,每组各50 例,相应各组鞘内注入布比卡因剂量分别为10、8、6 及4mg,并混合2.5μg 舒芬太尼。选择L3~4行腰硬联合穿刺,注药10min 后记录麻醉平面。根据结果进行Probit 回归分析,计算布比卡因腰麻的ED50和ED95。观察各组利多卡因及去氧肾上腺素的用量、肌松效果及患者麻醉满意度,观察各组术中并发症以及新生儿的Apgar 评分和脐动脉pH。结果 重度子痫前期患者腰麻剖宫产布比卡因ED50 和ED95分别为：6.51（95%CI：5.81～7.01）和8.68（95%CI：7.96～10.26）。4 组患者10min 后麻醉平面的差异均有统计学意义（均P＜0.05）。4mg 组利多卡因用量高于其他3组,差异有统计学意义（P＜0.05）。8mg 组、10mg 组去氧肾上腺素的用量高于其他两组,差异均有统计学意义（均P＜0.05）。低血压的发生率8mg 组、10mg 组高于其他两组,差异均有统计学意义（均P＜0.05）。４ 组间其他不良反应恶心、呕吐、寒战以及心动过缓发生率的差异无统计学意义（P＞0.05）。4 组胎儿娩出后1、5min Apgar 评分及脐动脉血气分析的结果差异均无统计学意义（均P＞0.05）。结论 重度子痫前期产妇剖宫产鞘内注入6mg 布比卡因混合2.5μg舒芬太尼,必要时辅以硬膜外麻醉,麻醉效果确切,血流动力学稳定,适合该类患者手术麻醉。     

Star-PDMAEMA-β-CD-Stabilized Colloidal Gold Nanoparticles: Synthesis,Characterization and pH-Controlled Assembly

Colloidal gold nanoparticles were prepared through in situ reduction in the presence of water-soluble star homopolymer with β-cyclodextrin core and poly[2-(dimethylamino) ethyl methacrylate] arms (star PDMAEMA-β-CD) at ambient temperature. In this process, star PDMAEMA-β-CD acted as both reducing agent and stabilizing agent for gold nanoparticles. More importantly, the optical properties and the morphology of star-PDMAEMA-β-CD-stabilized colloidal gold nanoparticles were sensitive to the solution pH due to structural changes of the polymer. Different assemblies can be formed by tuning the pH of the medium. Fourier transform infrared (FT-IR), UV-Vis absorption spectroscopy, transmission electron microscopy (TEM), dynamic laser light scattering (DLS) and X-ray diffraction (XRD) were used to characterize the synthetic gold nanoparticles and the pH-controlled assembly of gold nanoparticles.     

Sodiation as a tool for enhancing the diagnostic value of MALDI‐TOF/TOF‐MS spectra of complex astaxanthin ester mixtures from Haematococcus pluvialis

The microalga Haematococcus pluvialis produces the pigment astaxanthin mainly in esterified form with a multitude of fatty acids, which results in a complex mixture of carotenol mono‐ and diesters. For rapid fingerprinting of these esters, matrix‐assisted laser desorption ionization time of flight mass spectrometry (MALDI‐TOF/TOF‐MS) might be an alternative to traditional chromatographic separation combined with MS. Investigation of ionization and fragmentation of astaxanthin mono‐ and diester palmitate standards in MALDI‐TOF/TOF‐MS showed that sodium adduct parent masses [M + Na]⁺ gave much simpler MS² spectra than radical / protonated [M]^+● / [M + H]⁺ parents. [M + Na]⁺ fragments yielded diagnostic polyene‐specific eliminations and fatty acid neutral losses, whereas [M]^+● / [M + H]⁺ fragmentation resulted in a multitude of non‐diagnostic daughters. For diesters, a benzonium fragment, formed by polyene elimination, was required for identification of the second fatty acid attached to the astaxanthin backbone. Parents were forced into [M + Na]⁺ ionization by addition of sodium acetate, and best signal‐to‐noise ratios were obtained in the 0.1 to 1.0 mM range. This method was applied to fingerprinting astaxanthin esters in a crude H. pluvialis extract. Prior to MALDI‐TOF/TOF‐MS, the extract was fractionated by normal phase Flash chromatography to obtain fractions enriched in mono‐ and diesters and to remove pheophytin a, which compromised monoester signals. All 12 types of all‐trans esterified esters found in LC were identified with MALDI‐TOF/TOF‐MS, with the exception of two minor monoesters. Copyright © 2013 John Wiley & Sons, Ltd.     

The thermodynamic method for selecting oxygen carriers used for chemical looping air separation

Chemical looping air separation (CLAS) has been suggested as a new and energy saving method for producing oxygen from air. The selection of suitable oxygen carriers is the key issue for CLAS system. This paper shows a comprehensive thermodynamic method for selecting oxygen carriers used for CLAS through studying the properties of 34 different oxygen releasing reactions referring to 18 elements at different temperatures. The research mainly includes analysis of oxygen releasing capacity by calculating the Gibbs free energy change (ΔG) and the equilibrium partial pressure of oxygen of the reduction or oxidation reaction at different temperatures. Oxygen content and transport capacity were calculated. The spontaneous reaction temperatures for oxygen releasing reactions were presented to determine the operating temperatures. Also, the minimum demand of the steam for the reduction reaction was discussed. On the basis of the comprehensive thermodynamic study, the oxide systems of CrO₂/Cr₂O₃, PbO₂/Pb₃O₄, PbO₂/PbO, Pb₃O₄/PbO, MnO₂/Mn₂O₃, and Ag₂O/Ag have been found suitable for the CLAS process in low temperatures (500–800 K). The systems of PdO₂/PdO, PdO₂/Pd, PdO/Pd, MnO₂/MnO, and MnO₂/Mn₃O₄ were suitable for medium temperatures (800–1100 K) CLAS process. And Co₃O₄/CoO, CuO/Cu₂O, Mn₂O₃/Mn₃O₄, and OsO₂/Os systems only worked successfully in high temperatures (1100–1400 K). In addition, the CaO₂/CaO system was not suitable for CLAS because of the reaction with steam. The various binders such as SiO₂, TiO₂, Al₂O₃, Y₂O₃, ZrO₂, and YSZ which have been used for CLC could also be the supports for CLAS oxygen carriers.