Developing the Low-Temperature Oxidation Mechanism of Cyclopentane: An Experimental and Theoretical Study

At present, the reactivity of cyclic alkanes is estimated by comparison with acyclic hydrocarbons. Due to the difference in the structure of cycloalkanes and acycloalkanes, the thermodynamic data obtained by analogy are not applicable. In this study, a molecular beam sampling vacuum ultraviolet photoionization time-of-flight mass spectrometer (MB-VUV-PI-TOFMS) was applied to study the low-temperature oxidation of cyclopentane (CPT) at a total pressure range from 1–3 atm and low-temperature range between 500 and 800 K. Low-temperature reaction products including cyclic olefins, cyclic ethers, and highly oxygenated intermediates (e. g., ketohydroperoxide KHP, keto-dihydroperoxide KDHP, olefinic hydroperoxides OHP and ketone structure products) were observed. Further investigation of the oxidation of CPT – electronic structure calculations – were carried out at the UCCSD(T)-F12a/aug-cc-pVDZ//B3LYP/6-31+ G(d,p) level to explore the reactivity of O₂ molecules adding sequentially to cyclopentyl radicals. Experimental and theoretical observations showed that the dominant product channel in the reaction of CPT radicals with O₂ is HO₂ elimination yielding cyclopentene. The pathways of second and third O₂ addition – the dissociation of hydroperoxide – were further confirmed. The results of this study will develop the low-temperature oxidation mechanism of CPT, which can be used for future research on accurately simulating the combustion process of CPT.     

A New Quassinoid from Brucea javanica

Chemistry of Natural Compounds - A new quassinoid, dehydrobruceantinol B (1), was isolated from the seeds of Brucea javanica, together with two known compounds, bruceantinol (2) and bruceine A (3)....     

桉树杂交种与其亲本的近红外光谱判别

研究桉树控制授粉后目标性状的基因作用方式是探索其基因重组规律的重要内容。常规的数量统计分析精度往往不高,而DNA分析的专业要求高,且费时费力。该研究利用近红外光谱(NIRs)研究不同基因型桉树杂交种、亲本及杂交种与亲本间近红外光谱信息的关系,探索NIRs用于桉树杂交种与其亲本判别的可行性和准确性。以控制授粉的桉树亲本及其杂交F1代材料为对象,每种基因型从各自田间试验分别选取10个单株,采集树冠中上部新鲜健康叶片。用手持式近红外仪Phazir Rx(1624)采集桉树杂交种与其亲本叶片的NIRs信息。每单株选10片完全生理成熟的健康叶片,避开叶脉扫描其正面光谱5次,以50条NIRs信息的均值代表单个叶片的NIRs信息,最终每个基因型获得10条NIRs信息。对原始NIRs采用二阶多项式S.G一阶导数预处理。预处理后的NIRs用于多元统计分析,首先对桉树杂交亲本和子代样本进行主成分分析(PCA),直观展示不同基因型的分类情况。然后运用簇类独立软模式(SIMCA)和偏最小二乘判别分析(PLS-DA)两种有监督的判别模式验证NIRs用于桉树杂交种与其亲本树种的分类判别效果。PCA结果显示,不同的亲本间、杂交种间及杂交种与亲本间样本的主因子得分可以清晰地将各基因型分开。SIMCA模式判别分析中,桉树杂交种样本到亲本PCA模型的样本距离显示,待判别样本能够形成单独的聚类,且能直观反映两者的遗传相似。PLS-DA判别结果显示,桉树杂交亲本的PLS模型能通过预测其杂交子代的响应变量将其与亲本准确分开。结果表明,桉树叶片的NIRs信息可以准确地反映桉树杂交子代遗传信息的传递规律,NIRs判别模型可以准确地将各种基因型予以区分。因此,NIRs信息不仅可用于桉树杂交种和纯种的定性判别,还可以分析桉树基因重组过程中加性遗传效应的大小,从而为桉树遗传基础分析及其育种改良研究提供理论支撑。     

Organocatalytic asymmetric chlorinative dearomatization of naphthols

An organocatalytic asymmetric chlorinative dearomatization of naphthols was realized for the first time, providing chiral naphthalenones with a Cl-containing all-substituted stereocenter in excellent yields and enantioselectivity (up to 97% yield and 96% ee). The reaction features mild reaction conditions, good tolerance of diverse functional groups and simple reaction operation.     

红外动态场景生成装置空间分辨率的测试

建立了一套基于刀口灰度图红外探测的实验装置,对红外场景生成器的空间分辨率进行了测试。首先通过被测红外场景生成器产生带有刀口标志的红外图像,然后利用红外热像仪采集红外场景生成器所成的红外图像,通过对采集到的红外热图的数据处理,实现了对红外场景生成器空间分辨率的测量。测得的红外场景生成器的空间分辨率为5lp/mm,标准误差为0.04。     

新型4-羟色胺类化合物的合成及生物活性

以4-羟基吲哚为原料,经吲哚环4位乙酰基化、3位亲电取代、酰胺化和还原加氢等反应合成目标化合物7.通过核磁共振氢谱及碳谱对化合物进行结构表征,并对目标化合物进行体外抗氧化生物活性测试.初步生物活性测试结果表明,化合物7a,7b,7c和7d对DPPH·均有很强的清除作用(清除率为85.25%~90.73%),7e,7f,7g,7h作用较差;目标化合物与Vc相比,对·OH的清除作用稍差,最高清除率25.66%(Vc的最高清除率为34.67),但各化合物整体水平相当;在清除O-2·能力上化合物7a,7d,7g,7h最大清除率(分别为19.34,35.35,27.93和31.74)均强于同等浓度的Vc(17.58).     

用标准件对梯度磁场定标

就标准厚度卡片在霍尔传感器的定标方面的应用作了有益的探讨。在纵向测量微小长度时,霍尔片处于磁场边缘位置,其对磁场的梯度更大,即灵敏度更高,且靠中心位置的线性更好。