温度及pH敏感的树枝状高分子衍生物合成及药物控制释放研究

对合成的系列聚酰胺-胺型(PAMAM)树枝状高分子进行端基的羟基化和氯乙酰化两步修饰,使PAMAM最外层接上烷基氯.以修饰产物为引发剂,通过原子转移自由基引发甲基丙烯酸N,N-二甲氨基乙酯(DMAEMA)聚合得到树枝状PAMAM高分子衍生物,并对其结构用FTIR、1H-NMR和粒径分析进行了表征.紫外可见分光光度仪测定证实此高分子具有温度及pH敏感性.通过对小分子药物控制释放研究表明,此树枝状高分子衍生物通过环境pH值可有效地控制小分子药物的释放.     

Energy transfer rates and impact sensitivities of two classes nitramine explosives molecules

Some explosives are stable molecules with large energy barriers to chemical reaction, and in shock or impact initiation, a sizable amount of phonon energy must be converted to the molecular internal higher vibrations by multiphonon up pumping. To investigate the relationship between impact sensitivities and energy transfer rates, the number of doorway modes of explosive molecules is estimated by a simple theory in which the rate is proportional to the number of normal mode vibrations. We evaluated frequencies of normal mode vibrations of 13 explosive molecules which are CHNO nitramine-contained and have not been analyzed previously. The number of doorway modes in the regions of 200–700 cm⁻¹ was evaluated by the direct counting method. For more clear investigation of the relationship we have classified these 13 nitramine explosive molecules, by the number of nitramine group they contained, into two groups. There are eight molecules that contained one nitramine group and five molecules that contained poly-nitramine groups. It is found that the number of doorway modes shows a linearly correlation to the impact sensitivities derived from drop hammer tests. This result is in agreement with that of several previous works. Besides, it is also noted in our study that in those nitramine explosives molecules with similar molecular structure (similar number nitramine group they contained) and similar molecular weight, the correlation between the sensitivity and the number of doorway modes is higher. We found that the vibrational frequency of ω corresponds to nitro group motions of every molecule is contributed to the number of doorway modes in the regions of 200–700 cm⁻¹.     

Iterative computation of derivatives of repeated eigenvalues and the corresponding eigenvectors

Recently the authors proposed a simultaneous iteration algorithm for the computation of the partial derivatives of repeated eigenvalues and the corresponding eigenvectors of matrices depending on several real variables. This paper analyses the properties of that algorithm and extends it in several ways. The previous requirement that the repeated eigenvalue be dominant is relaxed, and the new generalized algorithm given here allows the simultaneous treatment of simple and repeated eigenvalues. Methods for accelerating convergence are examined. Numerical results support our theoretical analysis. Copyright © 2000 John Wiley & Sons, Ltd.     

A continuous adjoint formulation for the computation of topological and surface sensitivities of ducted flows

Topology optimization of fluid dynamic systems is a comparatively young optimal design technique. Its central ingredient is the computation of topological sensitivity maps. Whereas, for finite element solvers, implementations of such sensitivity maps have been accomplished in the past, this study focuses on providing this functionality within a professional finite volume computational fluid dynamics solver. On the basis of a continuous adjoint formulation, we derive the adjoint equations and the boundary conditions for typical cost functions of ducted flows and present first results for two‐ and three‐dimensional geometries. Emphasis is placed on the versatility of our approach with respect to changes in the objective function. We further demonstrate that surface sensitivity maps can also be computed with the implemented functionality and establish their connection with topological sensitivities. Copyright © 2008 John Wiley & Sons, Ltd.     

Computational design and screening of promising energetic materials: Novel azobis(tetrazoles) with ten catenated nitrogen atoms chain

Density functional theory methods were used to study on 2 N10 compounds, 1,1′‐azobis(tetrazole) and 1,1′‐azobis(5‐methyltetrazole). We systematically investigated 10 novel substituted azobis(tetrazoles) with 10 catenated nitrogen atoms and various energetic groups (–CF₃ 1 , –C(NO₂)₃ 3 , –N₃ 5 , –NH₂ 6 , –NHNH₂ 7 , –NHNO₂ 8 , –NO₂ 9 , –OCH₃ 10 , –OH 11 , –ONO₂ 12 ). The optimized geometry, frontier molecular orbitals, electrostatic potential, Infrared and nuclear magnetic resonance spectrum were calculated for inspecting the molecular structure and stability as well as chemical reactivity. The effects of different substituents on the density, enthalpy of formation, heat of explosion, detonation velocity and pressure, and sensitivity of the azobis(tetrazole) derivatives have been investigated. Compound 9 with nitro was found to have remarkable detonation performances (D = 9.61 km/s, P = 42.14 GPa), which are close to the excellent explosive CL‐20. Results show that compounds 1 , 3 , 4 , 7 , 9 , 11, and 12 have high potential to replace RDX. It is surprising that compounds 1 , 3 , 9, and 12 possess better energetic properties than HMX. These novel substituted azobis(tetrazoles) with unique N10 structure may be promising candidates of HEDMs with outstanding performance and acceptable sensitivities.     

On the robustness of balanced fractional 2m factorial designs of resolution 2l+1 in the presence of outliers

Summary By use of the algebraic structure, we obtain a simplified expression for the outlier-insensitivity factor for balanced fractional 2^m factorial (2^m-BFF) designs of resolution 2l+1 derived from simple arrays (S-arrays), whose measure has been introduced by Ghosh and Kipnegeno (1985,J. Statist. Plann. Inference,11, 119–129). It is defined by use of the measure suggested by Box and Draper (1975,Biometrika, 62 (2), 347–352). As examples, we study the sensitivity ofA-optimal 2^m-BFF designs of resolution VII (i.e.,l=3) given by Shirakura (1976,Ann. Statist.,4, 515–531; 1977,Hiroshima Math. J.,7, 217–285). We observe that these designs are robust in the sense that they have low sensitivities. Research supported in part by Grant 59530012 (C) and 60530014 (C), Japan.     

黄土公路隧道病害治理实例研究

黄土物理力学性质相对较差,具有大孔隙、湿陷性强、强度低的特点,加之黄土区的地形地貌、地质条件比较复杂,导致黄土隧道修筑过程中病害较多。利用SIR2000型探地雷达、RSM-SY5非金属声波探测仪和BJSD-2型激光限界仪等多种方法对某黄土公路隧道病害进行了探测,探测表明隧道洞身出现环向和横向裂缝,衬砌厚度不足,局部地段存在集中涌水和渗漏水,根据探测结果对隧道病害成因进行了详细的分析。在此基础上结合黄土隧道的基本特征,有针对性地提出了锚喷加固、套衬加仰拱、套衬和下加固围岩3套病害治理方案。并利用数值模拟对隧道治理前后围岩稳定性和衬砌结构受力状态进行了分析,结果表明治理方案衬砌受力状态基本对称,结构的安全系数有较大的提高。     

Nitramines with Varying Sensitivities: Functionalized Dipyrazolyl‐ N‐nitromethanamines as Energetic Materials

1,3‐Dichloro‐2‐nitro‐2‐azapropane is an excellent precursor to dense energetic functionalized dipyrazolyl‐N‐nitromethanamines. This new family of energetic compounds was fully characterized by using ¹H, ¹³C, and ¹⁵N NMR and IR spectroscopy, differential scanning calorimetry, elemental analysis, and impact sensitivity tests. Additionally, single‐crystal X‐ray structuring was done for 3 and 5? CH₃CN, which gave insight into structural characteristics. The experimentally determined densities of 2 – 9 fall between 1.69 and 1.90 g cm^?3. Heats of formation and detonation properties were calculated by using Gaussian 03 and EXPLO5 programs, respectively. The influence of different energetic moieties on the structural and energetic properties was established theoretically.     

Chlorine‐Free Pyrotechnics: Copper(I) Iodide as a “Green” Blue‐Light Emitter

The generation of blue‐light‐emitting pyrotechnic formulations without the use of chlorine‐containing compounds is reported. Suitable blue‐light emission has been achieved through the generation of molecular emitting copper(I) iodide. The most optimal copper(I) iodide based blue‐light‐emitting formulation was found to have performances exceeding those of chlorine‐containing compositions, and was found to be insensitive to various ignition stimuli.