α-萜品烯马来酰亚胺基酰腙衍生物的合成及杀菌活性研究

以α-蒎烯为原料,在质子酸催化下发生Wagner-Meerwein重排得到α-萜品烯,再与马来酸酐发生Diels-Alder环加成反应得到α-萜品烯马来酸酐(3),然后与水合肼反应制备N-氨基-α-萜品烯马来酰亚胺(4).在冰醋酸催化下,4与各种取代苯甲醛反应,合成得到17个新型α-萜品烯马来酰亚胺基酰腙化合物5a～5q.初步探索了合成条件,并利用元素分析,1H NMR,13C NMR,LC-MS,FT-IR等多种手段对目标产物作了分析表征.初步的生物活性测试表明,大部分化合物具有一定的杀菌活性,其中4-羟基-3-甲氧基苯基-α-萜品烯马来酰亚胺基酰腙(5n)在浓度为50 mg/L时对苹果轮纹病菌、花生褐斑病菌和番茄早疫病菌的抑制率分别达91%,83.3%和76.7%.     

Rapid Sample Pretreatment,Identification and Determination of Active Constitutents in Water‐soluble Radix isatidis Extract via MAE,ESI‐MS and RODWs‐HPLC

In this study, we successfully studied water‐soluble extract from Radix isatidis. Optimized conditions of MAE were listed, the sample can be extracted completely in 10 minutes under microwave power of 400W and solid/liquid ratio of 1:80. Active compounds in water‐soluble extract from R. isatidis were identified with HPLC‐DAD/ESI‐MS, these compounds followed by cytidine, uridine, guanosine, (R,S)‐goitrin and adenosine. RODWs–HPLC as a new sensitive chromatography were also first proposed and investigated, we favoringly used this method for simultaneous determination of these active constitutents in water‐soluble R. isatidis extract. Chromatographic separation was performed on a Diamonsil C18 column (5 μm, 150 mm × 4.6 mm) with a mobile phase gradient consisting of methanol and water at a flow‐rate of 1.0 mL/min, detection wavelengths 240, 250, 260 and 270 nm, the retention times of the tested five compounds were about 4.2, 5.8, 11.1, 14.2 and 20.8 min respectively, the limits of detection were 15, 12, 20, 5.8 and 24 ng/mL for cytidine, uridine, guanosine, (R,S)‐goitrin and adenosine respectively, their linear ranges were between 0.045 and 350 μg/mL with correlation coefficient (R) of 0.9998‐0.9999. The relative standard deviations (RSDs) of intra‐day and inter‐day assays were 0.30‐2.36% and 0.86‐2.54% respectively. Extraction recoveries were 94.25‐106.21%. This novel analytical method was shown to be simple, low‐cost, sensitive and reliable for multiple components in complex or undeveloped materials via MAE, ESI‐MS and RODWs‐HPLC.     

Theoretical investigation on the chiral diamine-catalyzed epoxidation of cyclic enones: mechanism and effects of cocatalyst

The asymmetric epoxidation of 2-cyclohexen-1-one with aqueous H(2)O(2) as oxidant, 1,2-diaminocyclohexane as catalyst, and a Br?nsted acid trifluoroacetic acid (TFA) as cocatalyst has been studied by performing density functional theory calculations. It is confirmed that the catalyzed epoxidation proceeds via sequential nucleophilic addition and ring-closure processes involving a ketiminium intermediate. Four possible pathways associated with two Z isomers and two E isomers of ketiminium have been explored in detail. Our calculation indicates that these four pathways have high barriers and a small energy gap between two more favorable R and S pathways. We have analyzed the effects of the TFA anion and H(2)O on the activity and enantioselectivity of catalytic epoxidation. It is found that the TFA anion acts as a counterion to stabilize the transition states of the catalytic epoxidation by hydrogen-bond acceptance, leading to decreases in the barriers of the nucleophilic addition and ring-closure processes. The most significant decrease occurred in the ring-closure step of the Z-R-pathway, resulting in H-bond-induced enantioselectivity. Our calculations also show that water cooperates with TFA to further increase the reaction rate significantly.     

A hybrid finite element approach to modeling sound radiation from circular and rectangular ducts

A numerical model based on a hybrid finite element method is developed that seeks to join sound pressure fields in interior and exterior regions. The hybrid method is applied to the analysis of sound radiation from open pipes, or ducts, and uses mode matching to couple a finite element discretization of the region surrounding the open end of the duct to wave based modal expansions for adjoining interior and exterior regions. The hybrid method facilitates the analysis of ducts of arbitrary but uniform cross section as well the study of conical flanges and here a modal expansion based on spherical harmonics is applied. Predictions are benchmarked against analytic solutions for the limiting cases of flanged and unflanged circular ducts and excellent agreement between the two methods is observed. Predictions are also presented for flanged and unflanged rectangular ducts, and because the hybrid method retains the sparse banded and symmetric matrices of the traditional finite element method, it is shown that predictions can be obtained within an acceptable time frame even for a three dimensional problem.     

垂直于界面V型缺口尖端的应力奇异性及其应用

基于双材料垂直于界面V型缺口理论,给出了单一材料和双材料裂纹问题、V型缺口问题应力强度因子的统一定义,得到了应力外推法计算双材料K_I的公式,数值算例验证了本文方法的有效性.以双材料单向拉伸和三点弯曲模型为对象,深入研究了双材料中弹性模量、泊松比、缺口深度、缺口张角对缺口尖端奇异应力场的影响,获得了一定范围内各种参数变化对缺口尖端奇异应力场的影响规律,为异体材料形成的V型缺口在应力断料中的应用提供了必要的参考依据.     

两层液体Bénard-Marangoni对流的实验研究

采用粒子图像测速技术(PIV)对两层流体B(en)ard-Marangoni对流进行了实验研究.研究了各种不同厚度比下的临界对流模式,同时研究了在温差变大时向超临界对流模式转化过程.实验结果表明,界面张力对各种对流模式的形成和转变具有重要的作用.     

检验人工听骨力学性质的解析方法

传导性耳聋多由鼓膜或听骨链病变所致,人工中耳已在临床上广泛应用于传导性耳聋治疗.根据人工中耳结构试验和力学假设,用变分原理建立在任意时刻$t$点,人工鼓膜受迫振动位移与激发声压的关系,推导控制方程. 采用分离变量法及贝塞尔函数对方程求解,得到鼓膜和听骨位移的解析解. 通过与文献试验数据比较,感觉曲线形状与走势基本一致,证明了该方程是正确的,能够反映声音的传导机制. 利用方程计算得到:质量小的材料传音效果好于质量大的;顶盘面积一定时,质量为某一特定值时传音效果更佳; 该结果与相关文献的试验结果相符合. 研究表明: 该方程对于人工中耳数据的获得非常方便,并且能够优化人工听骨材料,特别是对质量的控制能达到科学的效果,避免测量因素及其他因素的干扰.该方法为耳生物力学的研究及应用提供了新的视点.      

A combination of energy method and spectral analysis for study of equations of gas motion

There have been extensive studies on the large time behavior of solutions to systems on gas motions, such as the Navier-Stokes equations and the Boltzmann equation. Recently, an approach is introduced by combining the energy method and the spectral analysis to the study of the optimal rates of convergence to the asymptotic profiles. In this paper, we will first illustrate this method by using some simple model and then we will present some recent results on the Navier-Stokes equations and the Boltzmann equation. Precisely, we prove the stability of the non-trivial steady state for the Navier-Stokes equations with potential forces and also obtain the optimal rate of convergence of solutions toward the steady state. The same issue was also studied for the Boltzmann equation in the presence of the general time-space dependent forces. It is expected that this approach can also be applied to other dissipative systems in fluid dynamics and kinetic models such as the model system of radiating gas and the Vlasov-Poisson-Boltzmann system.      

Stochastic modeling of unresolved scales in complex systems

Model uncertainties or simulation uncertainties occur in mathematical modeling of multiscale complex systems, since some mechanisms or scales are not represented (i.e., ‘unresolved’) due to a lack in our understanding of these mechanisms or limitations in computational power. The impact of these unresolved scales on the resolved scales needs to be parameterized or taken into account. A stochastic scheme is devised to take the effects of unresolved scales into account, in the context of solving nonlinear partial differential equations. An example is presented to demonstrate this strategy. Dedicated to Professor Peter E. Kloeden on the occasion of his 60th birthday     

生物酶法制备1, 3-甘油二酯

近年来的研究表明,食用含有1,3-甘油二酯（1,3-DAG）的油脂可以降低脂肪积累、防止体重增加。但是天然存在的1,3-DAG很少,所以1,3-DAG的制备尤显重要。相对于化学法,生物酶法合成1,3-DAG具有反应条件温和、环境友好、产品质量好等优点,故近年来利用酶法合成1,3-DAG越来越受到关注。本文综述了国内外生物酶法制备1,3-DAG的相关研究进展,并指出降低酶的生产成本、延长酶的使用寿命等措施有助于促进生物酶法工业化生产1,3-DAG。