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.     

坚硬顶板爆破切顶在沿空留巷中的应用研究

当煤层上方为坚硬顶板时,在工作面回采期间容易出现大面积悬顶,导致巷旁充填体出现大变形破坏,极大威胁采煤安全.为解决这一问题,以某矿1205工作面沿空留巷为工程背景,分析了爆炸围岩裂隙范围和坚硬顶板破断特征,建立了切顶卸压围岩结构力学模型,研究表明,相邻炮孔爆炸后,炮孔间裂隙互相贯穿,降低了顶板强度,同时当切顶角为15°时,巷道稳定性较好.工程实践结果表明:采用爆破切顶技术后,顶板下沉量减小了62.3%,较好地保证了围岩稳定性.     

基于XPS对硫铁矿去除SeO2-3的机理研究

硒是动植物及人体生长必需的十五种微量元素之一，具有清除体内自由基、抗氧化、增强免疫力等功能，但其安全剂量的范围却很窄。利用扫描电子显微镜（SEM）和X射线衍射仪（XRD）对湿法球磨制备的硫铁矿形貌进行了表征。SEM观测发现加乙醇助磨后的硫铁矿为粒径大小较均匀的球形颗粒团聚体，粒径范围在17～200 nm之间，平均粒径138 nm。XRD衍射图谱中的特征峰与FeS₂衍射图谱中各峰位置基本一致，因此判定硫铁矿中主要化学组分为FeS₂，且图谱中基本没有杂峰，表明制备过程中并未混入杂质，样品纯度较高。实验结果表明，该法制备的硫铁矿具有颗粒粒径小、比表面积大、反应活性高等优点。研究中利用X射线光电子能谱仪（XPS）对硫铁矿去除水体中SeO2-₃的机理进行了研究。研究结果表明, （1）在较为广泛的实验pH范围（pH 2.2～11.5），硫铁矿均能有效去除水体中SeO2-₃，去除效率（除pH值7.8以外）均达到90%以上；（2）硫铁矿与SeO2-₃发生反应后，其主要组成元素的XPS特征峰结合能有所减小，表明硫铁矿表面发生了一定化学变化；（3）酸碱环境下硫铁矿去除SeO2-₃的机理不完全相同，酸性环境下，硫铁矿对SeO2-₃的去除是单纯的氧化还原过程，即硫铁矿中被酸活化的S2-₂将SeO2-₃还原为单质Se(0)，并且酸性越强，SeO2-₃去除效果越好；碱性环境下，SeO2-₃的去除过程中氧化还原与络合反应并存，硫铁矿表面有络合态Fe(OH)SeO₃和单质Se(0)两种存在形态，且碱性越强，络合态Fe(OH)SeO₃含量越高。以上研究结果为硫铁矿去除固定水体和土壤中以SeO2-₃为代表的可变价金属阴离子提供重要理论依据和应用基础。     

算子代数上2-局部Lie三重导子的结构

设X是维数大于2的Banach空间,映射δ:B(X)→B(X)是2-局部Lie三重导子,则对所有A∈B(X)有δ(A)=[A,T]+φ(A),这里T∈B(X),φ是从B(X)到FI的齐次映射且满足对所有A,B∈B(X)有φ(A+B)=φ(A),其中B是交换子的和.     

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)....     

四方体MgO的制备及对有机染料的吸附

以六水氯化镁和六次甲基四胺为原料,采用水热法合成四方体MgO,考察其对有机染料甲基橙和亚甲基蓝的吸附行为.通过TGA-DTA、SEM、XRD、N2-sorption和FT-IR等手段表征样品.结果表明,原料浓度、温度和表面活性剂对四方体MgO结构的形成影响较小,而反应时间的延长有助于有序结构的组装.温度170℃、时间24h、MgCl2·6H2O与C6H12N4浓度比为1∶2和表面活性剂PVP是制备四方体MgO的最佳条件.在溶液浓度10mg · L-1的单一吸附实验过程中,四方体MgO对甲基橙和亚甲基蓝的去除率分别为91.3;和22.3;,吸附过程均为单层吸附且符合Langmuir等温吸附模型和伪二级吸附动力学方程.在溶液浓度40 mg·L-1、甲基橙和亚甲基蓝浓度比3∶1的混合溶液吸附过程中,四方体MgO对甲基橙和亚甲基蓝的去除率分别为80.1;和97.9;.     

纳米CeO2吸附剂的制备及对六价铬的吸附性能

吸附法是去除水中重金属离子的重要方法,开发新型吸附剂一直是研究热点.利用浸渍法和水热法制备了片状和无定形的纳米CeO2吸附剂,探讨其对六价铬的吸附性能,分析pH、吸附时间、六价铬初始浓度等因素对其吸附性能的影响,并通过循环吸附实验考察纳米CeO2吸附剂的再生能力.结果表明:厚度30 nm、直径大小约为400 nm的片状CeO2吸附剂具有更强的吸附能力和更快的吸附速率,80 min时基本达到吸附平衡;两种吸附剂的最佳吸附pH为3;吸附动力学均符合伪二级动力学方程,Langmuir模型和Freundlich模型均能很好地拟合等温吸附过程,表明纳米CeO2对六价铬的吸附以单层吸附为主.片状CeO2四次吸附-解吸实验之后吸附率稍有下降,表明片状CeO2吸附剂有较好的再生能力,因而,该片状CeO2吸附剂适用于与酸性Cr(Ⅵ)废水的处理.     

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.     

Integral closure of a quartic extension

Let R be a Noetherian unique factorization domain such that 2 and 3 are units,and let A=R[α]be a quartic extension over R by adding a rootαof an irreducible quartic polynomial p(z)=z4+az2+bz+c over R.We will compute explicitly the integral closure of A in its fraction field,which is based on a proper factorization of the coefficients and the algebraic invariants of p(z).In fact,we get the factorization by resolving the singularities of a plane curve defined by z4+a(x)z2+b(x)z+c(x)=0.The integral closure is expressed as a syzygy module and the syzygy equations are given explicitly.We compute also the ramifications of the integral closure over R.