污泥基吸附剂对亚甲基蓝和环丙沙星的吸附性能研究

亚甲基蓝和环丙沙星是水体中2种污染物, 对生态环境有潜在危害. 本文以市政剩余活性污泥为原料, 氯化锌为活化剂热解制备污泥基吸附剂, 研究盐酸酸洗浓度、氯化锌浓度、热解温度、热解时间等对污泥基吸附剂吸附水中亚甲基蓝和环丙沙星性能的影响. 结果表明 (1)污泥基吸附剂对亚甲基蓝的吸附性能随盐酸酸洗浓度的增大而增加, 对环丙沙星的吸附性能则随盐酸酸洗浓度的增大呈先降后增趋势, 两者均在1.500mol·L-1盐酸浓度下取得最优值. (2)污泥基吸附剂对亚甲基蓝和环丙沙星的吸附性能随氯化锌浓度和热解温度的增加呈先升后降趋势, 在氯化锌浓度为4.0mol·L-1、热解温度为500℃时有最优值; 随着热解时间的延长, 污泥基吸附剂对亚甲基蓝和环丙沙星的吸附性能分别在500℃热解70min和80min时有最优值. (3)污泥基吸附剂的最佳制备条件为 氯化锌4.0mol·L-1活化2h、500℃热解70min和80min、1.500mol·L-1盐酸酸洗; 以此制得的污泥基吸附剂对亚甲基蓝和环丙沙星的去除率分别为97.7%和96.4%, 平衡吸附量分别为97.9mg·g-1和3.9mg·g-1, 且污泥基吸附剂对亚甲基蓝和环丙沙星的吸附过程均符合准二级动力学方程.     

利用MCNPX模拟研究不同中子源对有源符合中子法的影响

利用MCNPX软件建立了有源井型符合计数器(简称AWCC)测量模型，模拟了诱发中子源分别为Am-Li源和Am-Be源时AWCC测量贫化铀的中子符合计数率，研究了两种诱发中子源下AWCC测量贫化铀质量的精度。研究表明，Am-Be源引起的诱发中子符合计数率低于Am-Li源引起的诱发中子符合计数率，Am-Be源下的质量刻度曲线拟合度高于Am-Li源下的，相应的质量测量误差也小于Am-Li源下的，Am-Li源下的检验点铀质量相对误差区间为0.3%~13%，Am-Be源下的为0.1%~4.5%。使用AWCC装置测量贫化铀质量时，选取Am-Be源作为诱发中子源时相对误差更小。     

Rational Design of a Near-infrared Fluorescent Material with High Solid-state Efficiency,Aggregation-induced Emission and Live Cell Imaging Property

Near-infrared(NIR) fluorescent materials with high photoluminescent quantum yields(PLQYs) have wide application prospects. Therefore, we design and synthesize a D-A type NIR organic molecule, TPATHCNE, in which triphenylamine and thiophene are utilized as the donors and fumaronitrile is applied as the acceptor. We systematically investigate its molecular structure and photophysical property. TPATHCNE shows high T_gof 110℃ and T_d of 385℃ and displays an aggregation-induced emission(AIE) property. A narrow optical bandgap of 1.65 eV is obtained. The non-doped film of TPATHCNE exhibits a high PLQY of 40.3% with an emission peak at 732 nm, which is among the best values of NIR emitters. When TPATHCNE is applied in organic light-emitting diode(OLED), the electroluminescent peak is located at 716 nm with a maximum external quantum efficiency of 0.83%. With the potential in cell imaging, the polystyrene maleic anhydride(PMSA) modified TPATHCNE nanoparticles(NPs) emit strong fluorescence when labeling HeLa cancer cells, suggesting that TPATHCNE can be used as a fluorescent carrier for specific staining or drug delivery for cellular imaging. TPATHCNE NPs fabricated by bovine serum protein(BSA) are cultivated with mononuclear yeast cells, and the intense intracellular red fluorescence indicates that it can be adopted as a specific stain for imaging.     

Validation of a robust and rapid liquid chromatography tandem mass spectrometric method for the quantitative analysis of navitoclax

The Bcl-2 family small molecule inhibitor navitoclax is being clinically evaluated to treat multiple cancers including lymphoid malignancies and small cell lung cancer. A sensitive and reliable method was developed to quantitate navitoclax in human plasma using liquid chromatography with tandem mass spectrometry with which to perform detailed pharmacokinetic studies. Sample preparation involved protein precipitation using acetonitrile. Separation of navitoclax and the internal standard, navitoclax-d8, was achieved with a Waters Acquity UPLC BEH C₁₈ column using isocratic flow over a 3 min total analytical run time. A SCIEX 4500 triple quadrupole mass spectrometer operated in positive electrospray ionization mode was used for the detection of navitoclax. The assay range was 5–5,000 ng/ml and proved to be accurate (89.5–104.9%) and precise (CV ≤ 11%). Long-term frozen plasma stability for navitoclax at −70°C was at least 43 months. The method was applied for the measurement of total plasma concentration of navitoclax in a patient receiving a 250 mg daily oral dose.     

新型暂堵酸化用自降解暂堵剂的制备及现场应用

针对传统暂堵酸化用暂堵剂颗粒耐酸性差、降解性差和除堵工艺复杂等问题，本研究通过水溶液自由基聚合法制备了一种新型的自降解暂堵剂CQZDJ。考察了单体加量、交联剂加量、引发剂加量对CQZDJ凝胶强度和降解性的影响；通过FT-IR、TGA、SEM对其结构进行表征；并对其降解机理进行了探讨；最后在长8区块的环平81-8实验井进行了现场实践。结果表明：CQZDJ凝胶强度及降解时间与单体加量、交联剂加量、引发剂加量成正比关系，且降解时间可控；降解性实验表明CQZDJ在(1%~10%)HCl溶液、水、（2%~10%）NaCl溶液中均可在4 d内完全降解，具备良好的降解性能，对地层伤害小；SEM照片显示CQZDJ的降解过程是从初始三维网状结构逐渐崩解为层状结构，最终降解为无规则线性小分子链的过程；暂堵后现场流压上升6.3 MPa，日产油由3.87 t/d增产至5.22 t/d，实现了储层的有效改造，增产效果显著。      

热解吸反压低温等离子体电离源质谱检测食品中的邻苯二甲酸酯EI北大核心CSCD

基于低温等离子体设计并实现了一套热解吸反压低温等离子体电离(TD-iLTPI)装置。TD-iLTPI装置由热解吸模块和电离源模块集成在一个π型四通管上组成,进样探针取得样品后插入热解吸模块使其气化,之后随载气进入电离区域被电离。iLTPI内部的针电极接交流电,外部的环形电极接地,电极连接方式与LTP相反。该文对热解吸反压低温等离子体电离源进行了参数的优化,并与三重四极杆质谱联用检测了12种代表性的邻苯二甲酸酯,同时考察了TD-iLTPI-MS的分析性能,并对含有邻苯二甲酸酯的实际样品进行了检测。结果表明,邻苯二甲酸丁苄酯(BBP)的标准曲线具有良好的线性相关系数(R;=0.9958),加标回收率为89.7%~116.8%,相对标准偏差为4.5%~8.2%,对邻苯二甲酸酯的检出限也远低于其他敞开式离子源。对白酒、果汁、面包、奶酪和黄油中的邻苯二甲酸酯进行了快速筛查,并定量检测了果汁中的邻苯二甲酸丁苄酯。     

基于快速神经网络架构搜索的鲁棒图像水印网络算法

为解决深度学习在图像水印算法中计算量大且模型冗余的问题，提高图像水印算法在抵抗噪声、旋转和剪裁等攻击时的鲁棒性，提出基于快速神经网络架构搜索（neural architecture search，NAS）的鲁棒图像水印网络算法。通过多项式分布学习快速神经网络架构搜索算法，在预设的搜索空间中搜索最优网络结构，进行图像水印的高效嵌入与鲁棒提取。首先，将子网络中线性连接的全卷积层设置为独立的神经单元结构，并参数化表示结构单元内节点的连接，预先设定结构单元内每个神经元操作的搜索空间；其次，在完成一个批次的数据集训练后，依据神经元操作中的被采样次数和平均损失函数值动态更新概率；最后，重新训练搜索完成的网络。水印网络模型的参数量较原始网络模型缩减了92%以上，大大缩短了模型训练时间。由于搜索得到的网络结构更为紧凑，本文算法具有较高的时间性能和较好的实验效果，在隐藏图像时，对空域信息的依赖比原始网络更少。对改进前后的2个网络进行了大量鲁棒性实验，对比发现，本文算法在CIFAR-10数据集上对抵抗椒盐噪声和旋转、移除像素行（列）等攻击优势显著；在ImageNet数据集上对抵抗椒盐高斯噪声、旋转、中值滤波、高斯滤波、JPEG压缩、裁剪等攻击优势显著，特别是对随机移除行（列）和椒盐噪声有较强的鲁棒性。     

Ultrahigh Loading Copper Single Atom Catalyst for Palladium-free Wacker Oxidation

Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by ¹⁸O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.