重氮化制备钯(0)催化剂及其用于合成芳香胺研究

以2,3-二氨基萘为配体,K_2PdCl_4为金属前驱体,经重氮化制备出一种Pd(0)纳米催化剂(Pd-NPs),其结构经TEM、 XPS、 XRD、 EA和ICP-OES表征,并将催化剂应用于芳香醛类化合物直接还原胺化反应中.在常温常压下以苯甲醛为底物,水为溶剂,H_2为还原剂,探究了胺源、溶剂pH、催化剂用量、反应时间等变量对芳香伯胺产率的影响.实验结果表明芳香伯胺产率高达99%,且该催化剂能多次使用而不失活.     

Carbon dots/Bi_2WO_6 composite with compensatory photo-electronic effect for overall water photo-splitting at normal pressure

Overall water photo-splitting is a prospective ideal pathway to produce ultra-clean H_2 energy by semiconductors.However,the band structure of many semiconductors cannot satisfy the requirement of H_2 and O_2 production at the same time.Herein,we illustrate that carbon dots(CDs)/Bi_2 WO_6 photocatalyst with compensatory photo-electronic effect has enhanced activity for overall water photo-splitting without any sacrificial agent.In this complex photocatalytic system,the photo-potential provided by CDs makes the CDs/Bi_2 WO6(C-BWO) composite could satisfy the band structure conditions for overall water photo-splitting.The C-BWO composite(3 wt% CDs content) exhibits optimized hydrogen evolution(oxygen evolution) of 0.28 μmol/h(0.12 μmol/h) with an approximate 2:1(H_2:O_2) stoichiometry at normal pressure.We further employed the in-situ transient photovoltage(TPV) technique to study the photoelectron extraction and the interface charge transfer kinetics of this composite catalyst.     

超高效液相色谱-大气压化学电离-三重四极杆质谱联用法快速测定食品中苯并[a]芘

建立了快速检测食品中苯并[a]芘的超高效液相色谱-三重四极杆质谱联用(UPLC-MS/MS)分析方法。样品用正己烷提取后,经分子印迹固相萃取柱净化,以甲醇和水作为流动相进行梯度洗脱,在XBridge BEH C18柱上实现分离,大气压化学电离(APCI)-三重四极杆质谱正离子MRM方式检测,以苯并[a]芘-d12作为内标的稳定同位素稀释法定量。方法的线性范围为0.07~50μg/kg,定量限为0.07μg/kg。平均加标回收率为86%~104%,相对标准偏差为2.3%~14%。该方法灵敏、准确,适用于食品中苯并[a]芘的测定,已应用于实际样品的检查。     

基于常温无外压的转移印刷技术构筑半球状多级Ag基底

基于自组装技术制备了3种不同粒径的聚苯乙烯微球阵列,并翻制了与微球阵列互补的软模板.基于室温无外压的转移印刷技术制备了聚甲基丙烯酸甲酯半球形微纳阵列,然后基于原位光还原技术在聚甲基丙烯酸甲酯半球表面制备Ag纳米颗粒,构筑了拉曼增强的半球状多级Ag基底.转移印刷技术的关键是利用软模板自身的低表面能和表面羟基化的图案化材料与亲水基底界面间的氢键作用力.     

考虑底部隆起的浅埋隧道围岩压力计算分析

针对浅埋隧道开挖后底部隆起变形现象,应用极限分析上限法构造了考虑底部隆起变形的围岩压力计算模型,结合线性Mohr-Coulomb准则等推导出极限围岩压力的理论表达式。通过约束条件将围岩压力的计算转化为数学中的最优化问题,编制程序进行了优化计算。将计算结果与工程实测数据及文献计算结果进行了对比,验证了当前方法的可靠性。同时,指出在运用极限分析法处理浅埋隧道围岩压力问题过程中应将隧道底部一同考虑,对隧道底部支护会对整个围岩压力产生影响,有助于隧道结构的整体稳定。研究可以为浅埋隧道的开挖、支护提供一定的理论指导.     

侵入气体沿井筒的上升规律研究

地层气体侵入井筒后形成气液两相流动体系,气体沿井筒向上滑脱运移,随着所受压力的降低其发展变化过程会很快,如果不及时处理就会演变为井涌、井喷,甚至井喷失控.因此,准确的预测侵入气体沿井筒的上升规律,有助于认识气侵发展过程,同时为现场采取井控措施提供理论依据,有效避免井下复杂事故.基于侵入气体沿井筒运动的力学特性,建立了气体的上升速度模型,模型模拟分析表明:地层渗透率越高、机械钻速越快、单位时间内侵入井筒的气体量越多、气体上升速度越快,井底压力波动越大;施加一定的井口回压可以有效抑制气体的膨胀运移.     

Viscosity based droplet size controlling in negative pressure driven droplets generator for large‐scale particle synthesis

The poor control and regulation of droplets limit the applications of negative pressure driven droplet generator (NPDDG). Here, we present a simple method to control droplet size in NPDDG via varying the oil viscosity. Depending on the infinite intersolubility of high viscous mineral oil and low viscous hexadecane, we obtain a series of oils with kinematic viscosities linearly varied from 4.2 to 194.6 mm²/s. By using these oils as continuous phases, monodisperse droplets are fabricated with controllable size in NPDDG. This viscosity‐based droplet regulation method is effective, reliable, and compatible with scale‐up processes. Compared with droplet generator driven by positive pressure, the presented method can fabricate hydrogel particles massively, without complicated multilayer chip structure and complex fluid controlling, which may extend the potential of NPDDG in droplets based high‐throughput assay or large‐scale materials synthesis.     

APCI as an innovative ionization mode compared with EI and CI for the analysis of a large range of organophosphate esters using GC‐MS/MS

Organophosphate esters (OPEs) are chemical compounds incorporated into materials as flame‐proof and/or plasticizing agents. In this work, 13 non‐halogenated and 5 halogenated OPEs were studied. Their mass spectra were interpreted and compared in terms of fragmentation patterns and dominant ions via various ionization techniques [electron ionization (EI) and chemical ionization (CI) under vacuum and corona discharge atmospheric pressure chemical ionization (APCI)] on gas chromatography coupled to mass spectrometry (GC‐MS). The novelty of this paper relies on the investigation of APCI technique for the analysis of OPEs via favored protonation mechanism, where the mass spectra were mostly dominated by the quasi‐molecular ion [M + H]⁺. The EI mass spectra were dominated by ions such as [H₄PO₄]⁺, [M–R]⁺, [M–Cl]⁺, and [M–Br]⁺, and for some non‐halogenated aryl OPEs, [M]^+● was also observed. The CI mass spectra in positive mode were dominated by [M + H]⁺ and sometimes by [M–R]⁺, while in negative mode, [M–R]⁻ and more particularly [X]^‐ and [X₂]^‐● were mainly observed for the halogenated OPEs. Both EI and APCI techniques showed promising results for further development of instrumental method operating in selective reaction monitoring mode. Instrumental detection limits by using APCI mode were 2.5 to 25 times lower than using EI mode for the non‐brominated OPEs, while they were determined at 50‐100 times lower by the APCI mode than by the EI mode, for the two brominated OPEs. The method was applied to fish samples, and monitored transitions by using APCI mode showed higher specificity but lower stability compared with EI mode. The sensitivity in terms of signal‐to‐noise ratio varying from one compound to another. Copyright © 2016 John Wiley & Sons, Ltd.