α－萘甲酰呋喃甲酰甲烷的合成及谱学性质的研究

本文用Ｃｌａｉｓｅｎ缩合反应合成了未见文献报道的一种新的β－二酮，α－萘甲酰呋喃甲酰甲烷（α－ＮＦＭ），考察了该化合物的红外光谱、质谱及核磁共振氢谱。确定其存在着互变异构。     

氧化钨薄膜微型电化学器件的研究

本文论述了WO_3薄膜氢离子敏器件的结构、原理、制备技术和测试分析。利用WO_3薄膜在H+溶液中由绝缘转化为导电特性,成功地研制成氢离子敏器件。这是一种简易而经济的微型pH敏器件技术。     

超高效液相色谱-三重四极杆质谱法测定血浆和尿液中马桑亭和马桑宁

建立了超高效液相色谱-三重四极杆质谱联用技术测定血浆和尿液中马桑中毒标志物马桑亭和马桑宁的方法。血浆和尿液样品经固相支持液液萃取法提取净化后，溶于15%（v/v）甲醇水溶液中，以Cortecs C₁₈色谱柱（100 mm×2.1 mm，1.6 μm）作为分析柱进行分离，电喷雾负离子多反应监测（MRM）模式下检测，以氟苯尼考作为内标物，基质工作曲线内标法定量。血浆和尿液中马桑亭和马桑宁的平均加标回收率为86.2%~110%，相对标准偏差为5.1%~14.6%（n=6），血浆中马桑亭和马桑宁的检出限（S/N=3）分别为0.01 μg/L和0.1 μg/L，尿液中马桑亭和马桑宁的检出限分别为0.03 μg/L和0.3 μg/L。本法简单、灵敏、准确，可用于血浆和尿液中马桑亭和马桑宁的中毒检测。     

CuCrAl和CuCrZr低温液相合成甲醇催化剂的研究

 用络合共沉淀法制备了CuCrAl和CuCrZr复合氧化物液相合成甲醇催化剂，其比表面分别达到119和116m2／g．在5．0～5．5MPa和383K条件下，分别用间歇式和流动式反应釜考察了催化剂的活性和稳定性．结果表明：CuCrAl和CuCrZr的活性均明显高于CuCr；CuCrAl的活性略高于CuCrZr，但甲酸甲酯（MF）的选择性明显低于CuCrZr；两者在12h内未见活性明显下降．甲醇钠在反应过程中部分转化为甲酸钠和NaOH．CuCrAl和CuCrZr有较高的氢解活性可抑制甲醇钠与MF生成甲酸钠，从而有较低的甲酸钠浓度．但是，Al2O3和ZrO2的酸性有利于甲醇脱水，引起甲醇钠水解生成NaOH．溶剂对CuCr基催化剂的活性和选择性有明显影响．对反应机理进行了讨论．     

Calibration of the complex matrix effects on the sampling of polycyclic aromatic hydrocarbons in milk samples using solid phase microextraction

Solid phase microextraction (SPME), a simple, fast and promising sampling technique, has been widely used for complex sample analysis. However, complex matrices could modify the absorption property of coatings as well as the uptake kinetics of analytes, eventually biasing the quantification results. In the current study, we demonstrated the feasibility of a developed calibration method for the analysis of polycyclic aromatic hydrocarbons (PAHs) in complex milk samples. Effects of the complex matrices on the SPME sampling process and the sampling conditions were investigated. Results showed that short exposure time (pre-equilibrium SPME, PE-SPME) could increase the lifetime of coatings, and the complex matrices in milk samples could significantly influence the sampling kinetics of SPME. In addition, the optimized sampling time, temperature and dilution factor for PAHs were 10 min, 85 °C and 20, respectively. The obtained LODs and LOQs of all the PAHs were 0.1–0.8 ng/mL and 1.4–4.7 ng/mL, respectively. Furthermore, the accuracy of the proposed PE-SPME method for milk sampling was validated by the recoveries of the studied compounds in two concentration levels, which ranged from 75% to 110% for all the compounds. Finally, the proposed method was applied to the screening of PAHs in milk samples.     

免疫亲和柱净化-超高效液相色谱-三重四极杆质谱法高灵敏测定尿液和血浆中3种鹅膏毒肽

建立了超高效液相色谱-三重四极杆质谱高灵敏测定尿液和血浆中α-鹅膏毒肽、β-鹅膏毒肽和γ-鹅膏毒肽的方法。经过免疫亲和柱净化,尿液样品浓缩20倍、血浆样品浓缩10倍,以Kinetex Biphenyl色谱柱(100 mm×2.1 mm, 1.7 μm)作为分析柱,甲醇-0.005%(v/v)甲酸水溶液作为流动相进行梯度洗脱分离,电喷雾电离、负离子、多反应监测模式下检测,外标法定量。3种鹅膏毒肽的线性范围为0.1~200 ng/mL,相关系数(r)>0.999。尿液和血浆中3种鹅膏毒肽的基质效应和提取回收率分别为92%~108%和90%~103%,变异系数均小于13%。尿液中3种鹅膏毒肽的准确度为-9.4%~8.0%,重复性和中间精度分别为3.0%~14%和3.5%~18%,当取样量为2.00 mL时,方法的检出限均为0.002 ng/mL;血浆中3种鹅膏毒肽的准确度为-13%~8.0%,重复性和中间精度分别为3.9%~9.7%和5.5%~12%,当取样量为1.00 mL时,方法的检出限均为0.004 ng/mL。该法操作简单、灵敏、准确,已在中毒患者摄入野生蘑菇后138 h的尿液中检出0.0067 ng/mL α-鹅膏毒肽和0.0059 ng/mL β-鹅膏毒肽。该法已成功解决中毒患者尿液和血浆中超痕量鹅膏毒肽的检测难题,对于疑似中毒病人的早诊断、早治疗、降低死亡率都具有非常重要意义,也为今后开展此类毒素毒理作用及机体代谢规律的研究提供了可靠的技术支撑。     

Radiolysis products and degradation mechanism studies on di-1-methyl heptyl methyl phosphonate

Di-1-methyl heptyl methyl phosphonate (DMHMP) is a promising alternative extractant for Th-U fuel reprocessing, in which the irradiation stability of extractant should be systematically studied. In this paper, the radiolysis products of DMHMP were analyzed qualitatively and quantitatively with gas and ion chromatograph, the possible radiolysis mechanism of DMHMP was also concluded. Moreover, the effect of structure on the radiolysis products and irradiation stability of neutral organophosphorus compound extractant was also discussed.

     

Estimation of IIR Systems with Binary-Valued Observations*

Estimation and control problems with binary-valued observations exist widely in practical systems. However, most of the related works are devoted to finite impulse response (FIR for short) systems, and the theoretical problem of infinite impulse response (IIR for short) systems has been less explored. To study the estimation problems of IIR systems with binary-valued observations, the authors introduce a projected recursive estimation algorithm and analyse its global convergence properties, by using the stochastic Lyapunov function methods and the limit theory on double array martingales. It is shown that the estimation algorithm has similar convergence results as those for FIR systems under a weakest possible non-persistent excitation condition. Moreover, the upper bound for the accumulated regret of adaptive prediction is also established without resorting to any excitation condition.     

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。