磷化淀粉的合成及其与聚磷酸铵协效阻燃聚乳酸的性能研究

利用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和马来酸酐(MA)对淀粉进行改性得到磷化淀粉(DOPOMASt),通过红外光谱(FTIR)、核磁共振谱(1H-NMR)和X射线光电子能谱(XPS)确定其结构.利用DOPOMASt作为碳源,与聚磷酸铵(APP)复配后通过熔融共混制备了阻燃聚乳酸(PLA)...     

微波消解-电感耦合等离子体质谱(ICP-MS)法测定拟黑多刺蚁中11种微量元素

为准确定量拟黑多刺蚁体内的微量元素,采用微波消解法,以HNO_(3)-H_(2)O_(2)混合酸为消解体系对样品进行前处理,选择合适的同位素,以^(103)Rh为内标测定^(52)Cr、^(55)Mn、^(60)Ni、^(63)Cu、^(66)Zn、^(75)As、^(78)Se、^(88)Sr和^(114)Cd,以^(185)Re为内标测定^(202)Hg和^(208)Pb,建立了电感耦合等离子体质谱法测定拟黑多刺蚁中11种微量元素的方法。实验发现,以HNO_(3)-H_(2)O_(2)为消解体系,样品消解完全;采用KED模式消除质谱干扰,以内标法校正基体效应;通过绘制校准曲线及测定流程空白,各元素校准曲线的相关系数均大于0.999,方法检出限为0.0005~0.011 mg/kg,方法定量限为0.0016~0.033 mg/kg。对拟黑多刺蚁实际样品进行测定,各元素的相对标准偏差(RSD,n=9)在1.2%~5.5%,加标回收率为91.2%~107%;经过实验室间比对实验,相对偏差为-3.15%~2.74%;测定六个不同产地的拟黑多刺蚁样品,结果显示不同产地样品除Cd外,其他10种微量元素的含量均存在较大差异。测定结果稳定可靠,能满足拟黑多刺蚁中11种微量金属元素含量的分析检测要求。     

Modification of porous lignin with metalloporphyrin as an efficient catalyst for the synthesis of cyclic carbonates

Transition Metal Chemistry - The conversion of carbon dioxide into useful chemical raw materials is a necessary development for advancing carbon dioxide capture and storage technology. In this...     

一种检测CO32-比率荧光探针的合成及其在细胞成像中的应用

本文设计开发了一种以2,6-二甲酰基对甲苯酚为母体的新型荧光探针HMI,可用于高效识别EtOH-H₂O (8/2, v/v, HEPES 10 mM, pH =7.4)体系中的CO_3^2-。HMI在660 nm处显示发射带,加入CO_3^2-后,在600 nm的等吸收点激发时,原来在660 nm处的荧光淬灭,而以540 nm为中心的新发射带荧光显着增加,为比率型荧光探针。HMI对CO_3^2-表现出高选择性且具有较强的抗干扰能力。此外,荧光探针HMI对CO_3^2-荧光响应的检测限较低,可达到3.938×10^_-6 M。更具有意义的是,HMI探针对CO_3^2-的检测能够在实际水样中起到很好的应用,而且细胞成像研究表明,HMI可用于活体MCF-7细胞中CO_3^2-的成像。     

表面修饰多壁碳纳米管负载二氧化钛的制备及催化碳酸二甲酯与苯酚酯交换反应的性能

制备了表面修饰多壁碳纳米管负载TiO₂的催化剂,并将其应用于碳酸二甲酯与苯酚的酯交换反应. 采用X射线电子能谱、透射电子显微镜、低温N₂吸附-脱附和X射线衍射等对催化剂进行了表征. 结果表明,以低浓度的氨水（0.4%）代替去离子水作为沉淀剂时,制备的催化剂显示出更好的催化活性、分离性与重复使用性. 考察了TiO₂负载量、催化剂用量及反应时间对反应性能的影响. 在最佳反应条件下,苯酚转化率为42.5%,碳酸甲苯酯与碳酸二苯酯的总选择性达到99.9%以上. 经过4次重复使用后,催化剂的活性略有下降.     

发展高效的不对称Suzuki-Miyaura偶联反应及其合成应用

为解决不对称Suzuki-Miyaura交叉偶联反应中活性和选择性问题,我们设计并发展了一系列结构刚性的手性联芳基单膦配体.在发展高活性的大位阻交叉偶联反应方面,成功地实现了邻位四取代芳基芳基之间的Suzuki-Miyaura交叉偶联,并发展了官能团化的大位阻交叉偶联,在邻位二取代芳基溴苯与二级烷基硼酸之间的大位阻芳基烷基交叉偶联中也取得进展.在发展高立体选择性的交叉偶联反应方面,我们采用手性大位阻单膦配体和底物间次级作用相结合的设计理念,利用苯并噁唑啉酮辅基和芳基间的π-π作用,成功地发展了高立体选择性的邻位酰基化芳基芳基间不对称Suzuki-Miyaura偶联;利用极性基团双(2-氧代-3-噁唑烷基)次磷酰基(BOP)辅基和芳基间的极性π作用,成功地实现了应用性强的邻位氧基取代芳基芳基间高效不对称Suzuki-Miyaura偶联.最后我们首次将高效的不对称SuzukiMiyaura偶联方法学应用于天然产物合成,完成了手性联芳基天然产物Korupensamine A和Korupensamine B的高效不对称合成,并完成天然产物Michellamine B的立体选择性全合成.     

Red-emitting salicylaldehyde Schiff base with AIE behaviour and large Stokes shift

Three salicylaldehyde Schiff base (SSB) with AIE behavior were designed and facilely synthesized through a condensation reaction. In solid and aggregation states, these SSB dyes exhibited yellow to red emission with large Stokes shift. One of SSB dyes could specifically stain lipid droplets in living cells.     

Characterization of a Stable Adaptive Calibration Model Using Near-Infrared Spectroscopy and Partial Least Squares with a Kalman Filter

The calibration model of near-infrared (NIR) spectra established using the Kalman filter-partial least square (partial least squares combined with a Kalman filter) method can be adapted to outdated equipment, environmental changes, external samples, and other applications. However, the variance of the measurement noise estimation for NIR spectrum measurements cannot be easily obtained using Kalman filter-partial least squares; therefore, the variance in the measurement noise is often assumed to be zero for the Kalman filter-partial least square calibration model, which affects the stability of the model. In this study, the measured input and output data were used effectively, and the gamma test method for estimating the measurement noise variance was used to improve the stability of the Kalman filter-partial least square calibration model. First, an accurate estimation of the measurement noise variance was obtained, and accurate modeling was then performed using Kalman filter-partial least squares. Finally, 600 abandoned drilling fluid samples were used to confirm the validity of the proposed method. The Kalman filter-partial least square and gamma test-Kalman filter-partial least square methods are compared. Testing of external samples 401–600 demonstrated that the stability of the Kalman filter-partial least square model decreased. The root mean square error of the prediction of the Kalman filter-partial least square model was 27.135, which was worse than that of the gamma test-Kalman filter-partial least square model (20.307). The validation results show that the proposed method has better stability in tracking the evolution of the NIR spectrometer’s measurement state.     

Enhanced Photodynamic Therapy by Reduced Levels of Intracellular Glutathione Obtained By Employing a Nano‐MOF with CuII as the Active Center

In photodynamic therapy (PDT), the level of reactive oxygen species (ROS) produced in the cell directly determines the therapeutic effect. Improvement in ROS concentration can be realized by reducing the glutathione (GSH) level or increasing the amount of photosensitizer. However, excessive amounts photosensitizer may cause side effects. Therefore, the development of photosensitizers that reduce GSH levels through synergistically improving ROS concentration in order to strengthen the efficacy of PDT for tumor is important. We report a nano‐metal–organic framework (Cu^II‐metalated nano‐MOF {CuL‐[AlOH]₂}_n (MOF‐2, H₆L=mesotetrakis(4‐carboxylphenyl)porphyrin)) based on Cu^II as the active center for PDT. This MOF‐2 is readily taken up by breast cancer cells, and high levels of ROS are generated under light irradiation. Meanwhile, intracellular GSH is considerably decreased owing to absorption on MOF‐2; this synergistically increases ROS concentration and accelerates apoptosis, thereby enhancing the effect of PDT. Notably, based on the direct adsorption of GSH, MOF‐2 showed a comparable effect with the commercial antitumor drug camptothecin in a mouse breast cancer model. This work provides strong evidence for MOF‐2 as a promising new PDT candidate and anticancer drug.     

对流层大气过氧自由基实地测量的技术进展及其在化学机理研究中的应用

大气过氧自由基化学是对流层大气化学的重要组成部分,对于理解大气氧化性、光化学臭氧和二次有机气溶胶生成等核心科学问题具有重要意义。基于实地测量,准确掌握大气过氧自由基的浓度水平、进行相关化学行为分析以及实测结果模拟分析一直是大气过氧自由基化学研究的重点和难点。本文总结了大气过氧自由基实地测量的技术方法,回顾了涉及大气过氧自由基的大型实地观测实验,分析了已有观测实验中大气过氧自由基的浓度水平和差异,归纳了实地测量数据在化学机理研究中的应用,讨论了模拟分析实地测量结果中的主要科学发现。最后,提出该领域中尚存在的问题及可能的重点研究方向。