Computational studies on two novel energetic nitrogen‐rich compounds based on tetrazolone

Two novel energetic nitrogen‐rich compounds 1,4‐diaminotetrazol‐5‐one ( DATO ) and 1,4‐dinitrotetrazol‐5‐one ( DNTO ) were proposed first and studied by quantum chemistry method with B3LYP/6‐31G* level of theory. The optimized geometry, IR predicted spectrum and thermochemical parameters, frontier molecular orbitals and molecular electrostatic potential were calculated for inspecting the electronic structure, molecular stability and chemical reactivity. The important macroscopic properties including density, enthalpy of formation, detonation parameters and impact sensitivity have been predicted as well. As a result, two designed compounds DATO and DNTO possess positive enthalpy of formation (395.79 and 342.77 kJ/mol), impressive detonation parameters (D = 8.80 km/s, P = 33.69 GPa; D = 8.89 km/s, P = 34.98 GPa) superior to the remarkable explosive RDX, acceptable sensitivities and might be promising candidates of energetic materials. Copyright © 2015 John Wiley & Sons, Ltd.     

19F-NMR进展

19F-NMR技术由于其化学位移范围大、不易出现峰重叠及灵敏度高等优点,自上个世纪50年代出现以来,在分析光学异构体,生命科学等研究中有其特殊意义.在体内核磁共振技术中,19F-NMR与其他方法相比,在不损伤样品的条件下,就可进行实时定量监测.近30年,引人氟代指示剂进行体内19F-NMR的研究,含氟生物活性物质以及含氟材料的研究受到很大的重视,19F-NMR技术及其应用发展起来.从近10年的情况来看,含氟生物活性物质的研究以及在医药、农药和具有优异性能的含氟材料的研究应用受到很大的重视,这是近期19F-NMR研究发展的一个主要特点.     

The reusability characteristics of LiF:Mg,Cu,P with a maximum intensity at 280 °C in an environment with elevated temperature

Efforts are aimed at finding a method that could serve TL dosimetric measurements in the range of low-dose but carried out in an environment with elevated temperature. The temperature at the position of the maximum intensity of LiF:Mg,Cu,P was about 280 °C when annealed at 460 °C. LiF:Mg,Cu,P with a maximum intensity at 280 °C should present good thermal stability. The TL intensity of LiF:Mg,Cu,P with a maximum intensity at 280 °C was about 54% of the standard LiF:Mg,Cu,P, it should have a minimum measurable dose in the range of micro-Gy. LiF:Mg,Cu,P with a maximum intensity at 280 °C could be re-used by the 660 °C/30 min annealing, followed by 270 °C/20 min, 240 °C/10 min and 460 °C/30 min. It's possible for LiF:Mg,Cu,P to be extended application for low dose test in an environment with elevated temperature.     

Adsorption of cyclic hydrocarbons on Pt and the interaction of the adsorbed species with hydrogen

The adsorption of six-membered hydrocarbon cycles and cyclopentane and the interaction of hydrogen with the adsorbed layer on polycrystalline Pt-foil have been studied. The work function change (Δφ) was followed by a Kelvin probe and the C/Pt peak ratio was determined by Auger electron spectroscopy. Combining these two techniques made it possible to distinguish between chemisorption via σ-bonds and π-complex formation. Benzene and toluene adsorbed first as π-complex while cyclohexane showed initially a partial aromatization and a π-complex-like bonding to the surface. Excess hydrocarbon or addition of hydrogen transformed the π-complex into σ-bonded species. Cyclopentane adsorbed via σ-bonds and showed no significant hydrogen effect.     

SiH3+O(3P)反应机理的理论研究

利用abinitio方法对SiH3+O(3P)反应进行了理论研究,在MP2/6-311+G(d,p)水平上优化得到了反应途径上的反应物、中间体、过渡态和产物的几何构型,并在QCISD(T)/6-311+G(d,p)水平上进行单点能计算.计算结果表明,SiH3+O(3P)→IM1→TS3→IM2→TS8→HOSi+H2为主反应通道,其他可能存在的次要产物有HSiOH+H、H2SiO+H和HSiO+H2.HOSi、HSiO和HSiOH(cis)还可能进一步解离生成SiO.另外,计算结果对SiH4+O(3P)反应机理中存在的争议给出了可能的解释,认为Withnall等人在实验中观察到的产物HSiOH、H2SiO和SiO并不是SiH4+O(3P)反应的直接产物,而是来自副反应SiH3+O(3P).     

紫外光谱法快速测定生物质乙醇/水水解液中糠醛和5-羟甲基糠醛含量

木质纤维类生物质水解过程中产生的可溶性木素、呋喃类化合物在紫外波长范围内均有吸收峰,且吸收峰相互叠加。研究提出了一种基于紫外光谱法快速测定生物质水解液中糠醛(F)和5-羟甲基糠醛(5-HMF)混合物(M)的方法。研究发现,M中5-HMF的含量百分率(W_(5-HMF))和最大吸收波长(λ_(max))存在良好的线性关系,R2=0.998 4。进一步研究表明M中W_(5-HMF)不变时,混合物浓度(cM)和吸光度值(A)之间也存在良好的线性关系,R2在0.998 6~1.000 0之间,且重现性均良好。因此,基于A,cM及λ_(max),W_(5-HMF)之间的良好线性关系,可以准确地检测出F和5-HMF的含量,其相对偏差、回收率及RSD分别为5.6%和3.7%,89%~96%,0.21%~0.85%。该方法简单、快捷、准确,适应于乙醇法精炼木质纤维类生物质水解液中F和5-HMF混合物的测定。     

Rapid and high-capacity ultrasonic assisted adsorption of ternary toxic anionic dyes onto MOF-5-activated carbon: Artificial neural networks,partial least squares,desirability function and isotherm and kinetic study

The present paper focused on the ultrasonic assisted simultaneous removal of fast green (FG), eosin Y (EY) and quinine yellow (QY) from aqueous media following using MOF-5 as a metal organic framework and activated carbon hybrid (AC-MOF-5). The structure and morphology of AC-MOF-5 was identified by SEM, FTIR and XRD analysis. The interactive and main effects of variables such as pH, initial dyes concentration (mg L⁻¹), adsorbent dosage (mg) and sonication time (min) on removal percentage were studied by central composite design (CCD), subsequent desirability function (DF) permit to achieved real variable experimental condition. Optimized values were found 7.06, 5.68, 7.59 and 5.04 mg L⁻¹, 0.02 g and 2.55 min for pH, FG, EY and QY concentration, adsorbent dosage and sonication time, respectively. Under this conditions removal percentage were obtained 98.1%, 98.1% and 91.91% for FG, EY and QY, respectively. Two models, namely partial least squares (PLS) and multi-layer artificial neural network (ANN) model were used for building up to construct an empirical model to predict the dyes under study removal behavior. The obtained results show that ANN and PLS model is a powerful tool for prediction of under-study dyes adsorption by AC-MOF-5. The evaluation and estimation of equilibrium data from traditional isotherm models display that the Langmuir model indicated the best fit to the equilibrium data with maximum adsorption capacity of 21.230, 20.242 and 18.621 mg g⁻¹, for FG, EY and QY, respectively, while the adsorption rate efficiently follows the pseudo-second-order model.     

High heat generation ability in AC magnetic field for nano-sized magnetic Y3Fe5O12 powder prepared by bead milling

Nano-sized magnetic Y₃Fe₅O₁₂ ferrite having a high heat generation ability in an AC magnetic field was prepared by bead milling. A commercial powder sample (non-milled sample) of ca. 2.9 μm in particle size did not show any temperature enhancement in the AC magnetic field. The heat generation ability in the AC magnetic field improved with a decrease in the average crystallite size for the bead-milled Y₃Fe₅O₁₂ ferrites. The highest heat ability in the AC magnetic field was for the fine Y₃Fe₅O₁₂ powder with a 15-nm crystallite size (the samples were milled for 4 h using 0.1 mm? beads). The heat generation ability of the excessively milled Y₃Fe₅O₁₂ samples decreased. The main reason for the high heat generation property of the milled samples was ascribed to an increase in the Néel relaxation of the superparamagnetic material. The heat generation ability was not influenced by the concentration of the ferrite powder. For the samples milled for 4 h using 0.1 mm? beads, the heat generation ability (W g⁻¹) was estimated using a 3.58×10⁻⁴ fH² frequency (f/kHz) and the magnetic field (H/kA m⁻¹), which is the highest reported value of superparamagnetic materials.     

Spinel lithium titanate (Li4Ti5O12) as novel anode material for room-temperature sodium-ion battery

This is the first time that a novel anode material, spinel Li₄Ti₅O₁₂ which is well known as a “zero-strain” anode material for lithium storage, has been introduced for sodium-ion battery. The Li₄Ti₅O₁₂ shows an average Na storage voltage of about 1.0 V and a reversible capacity of about 145 mAh/g, thereby making it a promising anode for sodium-ion battery. E_x-situ X-ray diffraction (XRD) is used to investigate the structure change in the Na insertion/deinsertion process. Based on this, a possible Na storage mechanism is proposed.     

可信计算模式下P2P匿名通信系统设计

为了提高P2P匿名通信系统的安全性与可信性,需要对P2P匿名通信系统进行设计。当前使用的匿名通信系统,无法在用户节点匿名的情况下,保证P2P匿名通信系统匿名节点的可信性。因此,提出一种基于可信计算模式的P2P匿名通信系统设计方法。该系统的硬件部分分为系统登录模块、通信模块、数据模块、可信计算模块4大模块,模块之间相互合作,形成一个完整的匿名通信系统,匿名通信系统软件设计部分通过建立可信计算的联接,实现在匿名通道中进行数据传递,并对待传递的数据进行层次性打包加密,同时采用可信度计算对匿名通信系统中节点、匿名通道进行计算,形成安全可信的匿名传递通道。实验仿真证明,该方法在保证该系统数据传递的效率的同时提高了匿名通信系统的安全性与可靠性。