广西大风子中2个新木脂素的NMR研究

从广西大风子的皮中分离得到两个新木脂素1和2,并通过高分辨质谱和核磁共振确定了其结构. 利用多种二维核磁共振技术,包括HSQC, HMBC, DQF-COSY 和NOESY谱,对其碳氢信号进行了全归属. 毛细管电泳分析显示1和2均为外消旋体.     

La1/3Sr2/3Fe1-xCoxO3体系中的Co替代效应研究

本文通过对La1/3Sr2/3Fe1-xCoxO3系列样品进行X射线衍射(XRD)和变温电阻率(p～T)、比热(C～T)、磁化率(M～T)等测试,研究了Co掺杂对该系列样品的晶体结构和电热磁性质的影响.结果表明,随着Co掺杂量的增加,晶胞体积单调减小;电阻中电荷有序(charge ordering,CO)的特征逐渐消失.Co含量低的样品随着温度降低发生顺磁-反铁磁(PM-AFM)转变和金属-绝缘体(M-I)转变;Co含量高的样品则在磁转变温度以下表现出团簇玻璃型短程铁磁有序行为,并且在整个测量温区内具有金属导电特性.这些证明Co掺杂引起电子的局域化效应是导致体系电磁和输运行为发生变化的主要原因.     

原位漫反射红外光谱表征钛硅分子筛TS-1催化苯乙烯氧化反应

采用高温漫反射红外光谱考察了钛硅分子筛TS-1的稳定性,发现960 cm-1吸收峰在673 K时没有变化,表明所表征的骨架钛具有一定的高温稳定性,而表征分子筛骨架振动的两个吸收峰在673 K下向低波数位移了约13 cm-1。探讨了H₂O₂吸附对TS-1分子筛骨架钛的影响,发现960 cm-1处的吸收峰在吸附H₂O₂后强度减弱,并且向高波数位移了11 cm-1;抽真空或加热,吸收峰又复原,表明骨架钛可能存在TiO结构,H₂O₂与分子筛中的TiO作用,使相应的960 cm-1吸收峰向高波数位移。原位漫反射红外光谱考察了TS-1催化苯乙烯氧化反应,谱图分析表明,苯甲醛是主要产物,TS-1催化氧化的关键是H₂O₂吸附在TS-1的骨架钛上形成活性中心。     

(μ-L1)(μ-L2)十羰基合三锇电子光谱的含时从头计算

用从头计算(ab initio)方法,在HF/CEP-4G水平上,全优化计算了Os₃(CO)₁₀(μ-L1)(μ-L2) [L1,L2=H,Cl,Br,I]簇合物的的分子几何构型,在此基础上对这些簇合物的前线轨道进行了讨论,发现对于M—M键,p轨道虽有贡献,但以s,d轨道的贡献为主,同时从Cl→I,随着桥配体原子序的增大,Os₃(CO)₁₀(μ-L)₂类簇合物的HOMO与NHOMO轨道能量依次升高,而Os₃(CO)₁₀(μ-H)(μ-L)类簇合物只有HOMO轨道能量依次升高,而Os₃(CO)₁₀(μ-L)₂类簇合物的LUMO与HOMO的能量差Δε_L-H及LUMO与NHOMO的能量差Δε_L-NH都依次变小,可以预示,簇合物的电子光谱基谱带将红移。用TDHF计算了这些簇合物的电子吸收光谱。计算结构表明,簇合物Os₃(CO)₁₀(μ-H)₂(I)的跃迁主要为π→σ*和σ→σ*,对于其他几个簇合物Os₃(CO)₁₀(μ-H)(μ-L) [L=Cl,Br,I] 和Os₃(CO)10(μ-L)₂[L=Cl,Br],电子吸收峰主要都发生在σ→σ*的跃迁。从Cl→I,随着桥配体原子序的增大,簇合物的电子光谱基谱带红移,且光谱线强度逐渐减弱。     

Pulse radiolysis studies of 2‐ and 3‐hydroxybenzyl alcohols: inhibition of dehydration of ·OH‐(hydroxybenzyl alcohols) adducts by H2PO4− ions

Reactions of ·OH/O ^.? radicals and H‐atoms as well as specific oxidants such as Cl₂^.? and N₃· radicals have been studied with 2‐ and 3‐hydroxybenzyl alcohols (2‐ and 3‐HBA) at various pH using pulse radiolysis technique. At pH 6.8, ·OH radicals were found to react quite fast with both the HBAs (k = 7.8 × 10⁹ dm³ mol^?1 s^?1 with 2‐HBA and 2 × 10⁹ dm³ mol^?1 s^?1 with 3‐HBA) mainly by adduct formation and to a minor extent by H‐abstraction from ? CH₂OH groups. ·OH‐(HBA) adduct were found to undergo decay to give phenoxyl type radicals in a pH dependent way and it was also very much dependent on buffer‐ion concentrations. It was seen that ·OH‐(2‐HBA) and ·OH‐(3‐HBA) adducts react with HPO₄^2? ions (k = 2.1 × 10⁷ and 2.8 × 10⁷ dm³ mol^?1 s^?1 at pH 6.8, respectively) giving the phenoxyl type radicals of HBAs. At the same time, this reaction is very much hindered in the presence of H₂PO ions indicating the role of phosphate ion concentration in determining the reaction pathway of ·OH adduct decay to final stable product. In the acidic region adducts were found to react with H⁺ ions. At pH 1, reaction of ·OH radicals with HBAs gave exclusively phenoxyl type radicals. Proportion of the reducing radicals formed by H‐abstraction pathway in ·OH/O ^.? reactions with HBAs was determined following electron transfer to methyl viologen. H‐atom abstraction is the major pathway in O ^.? reaction with HBAs compared to ·OH radical reaction. H‐atom reaction with 2‐ and 3‐HBA gave transient species which were found to transfer electron to methyl viologen quantitatively. Copyright © 2010 John Wiley & Sons, Ltd.     

MgF2单晶的THz光谱研究

利用THz时域光谱技术对MgF₂晶体(样品1)和MgF₂：Co晶体(样品2)在0.5—2.5 THz的吸收特性进行了研究.在0.5—2.5 THz波段，样品1吸收系数α(ν)随频率ν增加而增大，最大值为24 cm^-1.样品2的吸收系数比样品1大得多，Co掺杂使晶格吸收带边向低频移动，而且样品2在1.9 THz有吸收峰，吸收系数达到70 cm^-1，由此求出F^--Co²⁺离子键伸缩振动的键力常数K为3.40×10^-2　N/cm.这一结果表明，THz光谱分析有可能成为研究晶体化学键的一种重要手段.利用光学常数之间的关系计算了两个样品在0.5—2.5 THz的介电函数的实部ε₁(ν)，得到样品1的ε₁(ν)值在4.67至4.73之间，样品2的ε₁(ν)值在4.62至5.01之间. 关键词： THz辐射 光谱 2晶体')" href="#">MgF₂晶体     

Third-Order Optical Nonlinearity in Two-Dimensional Transition Metal Dichalcogenides

We present a detailed calculation of the linear and nonlinear optical response of four types of monolayer twodimensional (2D) transition-metal dichalcogenides (TMDCs), having the formula MX₂ with M=Mo, W and X=S, Se. The calculations are based on 6-band tight-binding model of TMDCs, and then performing a semi-classical perturbation analysis of response functions. We numerically calculate the linear χ_μν⁽¹⁾ (-ω;ω) and nonlinear surface susceptibility tensors χ_μνζη⁽³⁾(-ω_Σ; ω_r; ω_s; ω_t) with ω_Σ=ω_r+ω_s+ω_t. Both non-degenerate and degenerate cases are studied for thirdharmonic generation and nonlinear refractive index, respectively. Computational results obtained with no external fitting parameters are discussed regarding two recent reported experiments on MoS₂, and thus we can confirm the extraordinarily strong optical nonlinearity of TMDCs. As a possible application, we demonstrate generation of a π/4-rotated squeezed state by means of nonlinear response of TMDCs, in a silica micro-disk resonator covered with the 2D material. Our proposed method will enable accurate calculations of nonlinear optical response, such as four-wave mixing and highharmonic generation in 2D materials and their heterostructures, thus enabling study of novel functionalities of 2D photonic integrated circuits.     

MgO-decorated carbon nanotubes for CO2 adsorption: first principles calculations

The global greenhouse effect makes it urgent to deal with the increasing greenhouse gases.In this paper the performance of MgO-decorated carbon nanotubes for CO 2 adsorption is investigated through first principles calculations.The results show that the MgO-decorated carbon nanotubes can adsorb CO 2 well and are relatively insensitive to O 2 and N 2 at the same time.The binding energy arrives at 1.18 eV for the single-MgO-decorated carbon nanotube adsorbing one CO 2 molecule,while the corresponding values for O 2 and N 2 are 0.55 eV and 0.06 eV,respectively.In addition,multi-molecule adsorption is also proved to be very satisfactory.These results indicate that MgO-decorated carbon nanotubes have great potential applications in industrial and environmental processes.     

Formation energies and electronic structures of native point defects in potassium dihydrogen phosphate

The formation energies and the equilibrium concentration of vacancies,interstitial H,K,P,O and antisite structural defects with P and K in KH 2 PO 4 (KDP) crystals are investigated by ab initio total-energy calculations.The formation energy of interstitial H is calculated to be about 2.06 eV and we suggest that it may be the dominant defect in KDP crystal.The formation energy of an O vacancy (5.25 eV) is much higher than that of interstitial O (0.60 eV).Optical absorption centres can be induced by defects of O vacancies,interstitial O and interstitial H.We suggest that these defects may be responsible for the lowering of the damage threshold of the KDP.A K vacancy defect may increase the ionic conductivity and therefore the laser-induced damage threshold decreases.     

Hydrogeochemical modeling for groundwater management in arid and semiarid regions using MODFLOW and MT3DMS: A case study of the Jeffara of Medenine coastal aquifer,South-Eastern Tunisia

The study of water quality and the quantification of reserves and their variations according to natural and anthropogenic forcing is necessary to establish an adequate management plan for groundwater resources. For this purpose, a modeling approach is a useful tool that allows, after calibration phase and verification of simulation, and under different scenarios of forcing and operational changes, to estimate and control the groundwater quantity and quality. The main objective of this study is to collect all available data in a model that simulates the Jeffara of Medenine coastal aquifer system functioning. To achieve this goal, a conceptual model was constructed based on previous studies and hydrogeological investigations. The regional groundwater numerical flow model for the Jeffara aquifer was developed using MODFLOW working under steady-state and transient conditions. Groundwater elevations measured from the piezometric wells distributed throughout the study area in 1973 were selected as the target water levels for steady state (head) model calibration. A transient simulation was undertaken for the 42 years from 1973 to 2015. The historical transient model calibration was satisfactory, consistent with the continuous piezometric decline in response to the increase in groundwater abstraction. The developed numerical model was used to study the system's behavior over the next 35 years under various constraints. Two scenarios for potential groundwater extraction for the period 2015–2050 are presented. The predictive simulations show the effect of the increase of the exploitation on the piezometric levels. To study the phenomenon of salinization, which is one of the most severe and widespread groundwater contamination problems, especially in coastal regions, a solute transport model has been constructed by using MT3DMS software coupled with the groundwater flow model. The best calibration results are obtained when the connection with the overlying superficial aquifer is considered suggesting that groundwater contamination originates from this aquifer. Recommendations for water resource managers

• The results of this study show that Groundwater resources of Jeffara of Medenine coastal aquifer in Tunisia are under immense pressure from multiple stresses.
• The water resources manager must consider the impact of economic and demographic development in groundwater management to avoid the intrusion of saline water.
• The results obtained presented some reference information that can serve as a basis for water resources planning.
• The model runs to provide information that managers can use to regulate and adequately control the Jeffara of Medenine water resources.