Substituent effect study on δc values of the bridge group carbons in disubstituted cinnamyl aniline series

The ¹³C nuclear magnetic resonance (NMR) chemical shifts δ_c of bridge group carbons (C‐β, C‐α, and C═N) were measured in this work for a wide set of substituted cinnamyl anilines p‐XC₆H₄CH═CHCH═NC₆H₄Y‐p (X = NO₂, Cl, H, Me, MeO, or NMe₂; Y = NO₂, CN, CO₂Et, Cl, F, H, Me, MeO, or NMe₂) and were used to study the substituent effect. In the study on ¹³C NMR chemical shifts of the titled compounds with single substituent changed, for every bridge carbon δ_c, the effect of cinnamyl substituent X is opposite to that of aniline substituent Y. That is, the action of the same substituent on different aromatic rings is different from the ¹³C NMR chemical shifts, and for C‐β, C‐α, and C═N, the choice of correlation equation depends on the ratio ρ_F(Y)/ρ_R(Y). When the ratio ρ_F(Y)/ρ_R(Y) is close to 1, the chemical shifts of bridge carbons can be well correlated with the single‐parameter equation; otherwise, it is better to adopt the dual‐parameter equation for correlation, and the further the values of ρ_F(Y)/ρ_R(Y) stray from 1, the more suitable the corresponding δ_c values are to be correlated with the dual‐parameter equation. In the study on δ_c of model compounds with simultaneous variations of substituents X and Y, for δ_c(C═N), a multi‐parameter correlation equation is obtained, and the substituent cross‐interaction item Δσ² is suitable to scale the interaction between substituents; however, for δ_c(C‐α and C‐β), the substituent cross‐interaction item Δσ² is perhaps too small to be observed. The multi‐parameter correlation equations can be recommended to predict well the corresponding δ_c values of disubstituted cinnamyl anilines. Copyright © 2012 John Wiley & Sons, Ltd.     

改进的自回归过程结构变点检验

In this paper, we consider the problem of detecting for structural changes in the autoregressive processes including AR（p） process. In performing a test, we employ the conventional residual CUSUM of squares test （RCUSQ） statistic. The RCUSQ test is based on the subsampling method introduced by Jach and Kokoszka [J. Methodology and Computing in Applied Probability 25（2004）]. It is shown that under regularity conditions, the asymptotic distribution of the test statistic is the function of a standard Brownian bridge. Simulation results as to AR（1） process and an example of real data analysis are provided for illustration.     

面向桥梁长期健康监测的大数据处理技术及应用

简要介绍了桥梁长期健康监测系统的应用,总结了基于桥梁长期健康监测大数据分析技术的研究现状。介绍了基于长期健康监测大数据分析在多尺度关联性分析、异常数据挖掘和分析以及时变可靠度研究三个方面取得的研究进展。通过多尺度关联性分析对各频率组分下的桥梁应变进行了分类,确定了温度对应变的影响;发展了利用应变阈值和小波细节系数进行异常信号识别的方法;提出了局部时变可靠度的计算方法。最后,对基于云计算的桥梁健康监测服务平台的研制及应用进行了介绍和展望。     

独塔斜拉桥的环境振动试验与分析

桥梁环境振动试验具有简单方便和花费少等优点.本文以吉林市临江门大桥为工程背景,通过动力试验,研究了该桥在天然脉动荷载作用下的固有特性.采用结构分析软件ANSYS建立全桥的空间模型,计算该桥的固有特性.有限元计算结果与动力试验结果比较吻合.结果表明,环境振动响应足以识别出该桥所感兴趣的模态,可作为该桥的有限元模型修正、损伤检测、使用状态评估和健康监测的基础.     

基于静载试验钢桁梁悬索桥承载能力评估分析

早期修建的小跨径钢桁梁悬索桥大部分已接近设计年限,正确评估其承载能力是桥梁维修、加固和技术改造的基本依据.本文首先简单介绍了桥梁承载能力评估的静载试验方法.同时结合城南大桥的实例,分析了现有桥梁结构存在的主要病害及产生的原因.在充分考虑分析现场检测资料和原有设计荷载等级的基础上,建立了考虑结构损伤的有限元模型,制定了静载试验的加载方案.通过试验结果与修正后有限元模型结果的比较,评估了桥梁结构现有承载能力状况,并针对该桥提出了恢复承载能力的加固措施和建议.     

双塔联体分幅斜拉桥塔结构模型实验索力测试结果分析

以甬江特大斜拉桥为工程背景,对其整个联塔结构进行室内模型试验研究.针对模型试验中加载斜拉索的布置位置、数量及索力的确定,提出了最少索数的索力优化方法,编制了相应的数值程序.在满足预期目标的前提下,以最少斜拉索数量为原则,确定了试验中斜拉索的优化布置及相应的优化索力及各级加载索力,对优化索力和试验中的测试索力进行比较分析,结果表明索力优化方法可行,两联塔之间索力相互影响较小.     

Carpet Beater Molecules: Synthesis and Characterization of Functional Hexa-peri-benzocoronene–Alkyne Coupling Products

Within the scope of this paper, nine π-expanded mono-substituted 5,8,11,14,17-pentakis-(tert-butyl)-hexa-peri-hexabenzocoronenes (HBC) are introduced. 2-Iodo-5,8,11,14,17-pentakis-(tert-butyl)-hexa-peri-hexabenzocoronene served as precursor and was reacted with ethynyltrimethylsilane in a Sonogashira coupling reaction. The acetylene unit is used as a linker and can undergo another Sonogashira coupling reaction combining different phenyl coupling partners with the HBC core. The electron-withdrawing groups such as nitrile, pyridine and carbonyl species (aldehyde, methylester, carboxylic acid) as well as the three quinoxaline based species (diphenylquinoxaline, dibenzo[a,c]phenazine, phenanthro[4’,5’-a,b,c]phenazine) serve as substitution moieties. Their influence on the optoelectronic properties were investigated by UV/Vis absorption spectroscopy demonstrating a maximum redshift of 7 nm compared to starting compound 2-Iodo-5,8,11,14,17-pentakis-(tert-butyl) HBC. As for the phenanthro[4’,5’-a,b,c]phenazine substituted HBC a dramatic decrease in the intensity of the absorption of the UV/Vis spectrum was observed. The fluorescence spectroscopy pointed out that the dibenzo[a,c]phenazine and phenanthro[4’,5’-a,b,c]phenazine substitution changed the spectra to one broad peak departing from the characteristic HBC-like emission pattern.     

A micro-investigation on water bridge effects for unsaturated granular materials with constant water content by discrete element method

The most common state of surface soil is unsaturated. Changes in water content will substantially impact its strength, leading to geological and engineering catastrophes. This paper used LIGGGHTS software to simulate the water bridge effect of unsaturated granular materials with constant water content and verify the rationality of the simplification of the stress-force-fabric (SFF) relationship. The results showed that the capillary force was not isotropic, which was different from the previous study, thus it cannot be overlooked in the simplification of the SFF relationship. Moreover, the influence of water content on the macroscopic mechanical behavior of unsaturated granular materials was interpreted through the evolutions of coordination number, interparticle force, fabric and force anisotropy, and other microscopic parameters. Compared to the literature, we found that different water bridge models would not change the characteristics of the solid skeleton.     

双缆悬索桥空缆状态主缆抗滑安全性研究

为指导双缆悬索桥上下缆垂跨比的取值，明确双缆悬索桥施工阶段主缆抗滑稳定性，提出一种主缆在施工阶段空缆状态下的抗滑安全系数计算方法。基于上缆变下缆的主缆布置方式，通过双缆悬索桥成桥状态反推空缆状态主缆垂度，根据空缆状态下主缆线形为悬链线计算中塔塔顶鞍座处缆力及包角，并据此计算空缆状态抗滑安全系数。建立多塔悬索桥有限元模型对提出的公式进行验证，分析成桥状态上下缆垂跨比和桥梁跨度的取值对空缆到成桥状态主缆垂度变化以及抗滑安全系数的影响。结果表明，采用本文公式计算的双缆悬索桥空缆状态下抗滑安全系数精度较高；上下缆垂跨比对空缆状态主缆抗滑安全性影响较大，抗滑安全系数随着上下缆垂跨比差值的增大迅速减小；空缆状态主缆抗滑安全系数受跨度影响不大，其随跨度增大略有提高。在实际的双缆悬索桥初步设计过程中应考虑施工阶段主缆抗滑稳定性，选择适宜的上下缆垂跨比，采取措施提高施工阶段主缆抗滑安全性。