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1.
Catalysis with anion–π interactions is emerging as an important topic in supramolecular chemistry. Among the reactions explored so far on π-acidic surfaces, coumarin synthesis stands out as a cascade process with several coupled anionic transition states. Increasing π-acidity has been shown in a different context to increase transition-state stabilisation and thus catalytic activity. In this report, we explore the possible use of macrocycles to accelerate coumarin synthesis between two π-acidic surfaces. To our disappointment, we found that compared to monomeric π-acids, coumarin synthesis within divalent macrocycles is clearly slower. Hindered access to an overly confined active site within the macrocycles could possibly account for this loss in activity, but several other explanations are certainly possible. However, operational coumarin synthesis on monomeric π-acidic surfaces is shown to tolerate structural modifications. Best results are obtained with structures that aim for proximity without obstructing transition-state stabilisation on the π-acidic surface.  相似文献   
2.
Redox-based post-translational modification of protein thiols has become an attractive strategy in cellular homeostasis and cell signaling.Due to the reductive end of the redox buffer network,the vicinal dithiol-containing proteins(VDPs)maintains an appropriate oxidation-reduction state of proteins through the reversible transformation from vicinal dithiols to disulfide,which is responsible for a variety of  相似文献   
3.
An efficient and mild synthesis of 2-(guaiazulen-1-yl)furans,starting from easily accessible 1-(3-aryl-2-cyanopropenoyl) guaiazulenes,tributylphosphine and acyl chlorides,is described.The strategy employs the intramolecular Wittig protocol as a key step to append the crticial furan ring,leading to the highly functional furans in good yields.  相似文献   
4.
给出了Markov链中任一状态集的逗留时间或击中时间的分布(混合指数分布),以及其分布的各阶微分与Q-矩阵之间的约束方程组.利用该约束关系及环形链结构的先验信息,采用Markov链反演方法证明了:对于有限状态环形Markov链,其Q-矩阵能由其中任意两个相邻状态的逗留时间和击中时间分布唯一决定,并给出了相应的算法.  相似文献   
5.
A new strategy to realize precise absolute positioning for a single-frequency user is presented. In the presented strategy, the receiver clock and ambiguities are removed using the satelliteand epoch-differenced (SDED) algorithm. As a further development of the SDED algorithm, a regional augmentation network is used to generate the SDED atmospheric delays at the user. The weakened mathematic property due to the epoch-differenced operation is improved by adding the generated atmospheric delays and applying the robust estimation. To test the new approach, the 24-h data at 5 Continuous Operation Reference Station (CORS) stations in Shanghai is processed. The results show a more than 96% success rate, defined as the case where three directions achieve the desired positioning accuracy of 10 cm, when the observation is longer than 20 min. The 20-min static results show that the new method can reach an accuracy of 3.42, 4.76 and 9.26 cm in the North, East and Up directions, respectively. An experiment was carried out to assess the kinematic positioning. The results show that the kinematic positioning accuracy is 4.11, 5.31 and 4.05 cm in the north-south, east-west and height directions,respectively.  相似文献   
6.
General synthetic access to expanded π‐acidic surfaces of variable size, topology, chirality, and π acidity is reported. The availability of π surfaces with these characteristics is essential to develop the functional relevance of anion–π interactions with regard to molecular recognition, translocation, and transformation. The problem is that, with expanded π surfaces, the impact of electron‐withdrawing substituents decreases and the high π acidity needed for strong anion–π interactions can be more difficult to obtain. To overcome this problem, it is herein proposed to build large surfaces from smaller fragments and connect these fragments with bridges that are composed only of single atoms. Two central surfaces for powerful anion–π interactions, namely, perfluoroarenes and naphthalenediimides (NDIs), were selected as fragments and coupled with through sulfide bridges. Their oxidation to sulfoxides and sulfones, as well as fluorine substitution in the peripheral rings, provides access to the full chemical space of relevant π acidities. According to cyclic voltammetry, LUMO levels range from ?3.96 to ?4.72 eV. With sulfoxide bridges, stereogenic centers are introduced to further enrich the intrinsic planar chirality of the expanded surfaces. The stereoisomers were separated by chiral HPLC and characterized by X‐ray crystallography. Their topologies range from chairs to π boats, and the latter are reminiscent of the cation–π boxes in operational neuronal receptors. With pentafluorophenyl acceptors, the π acidity of NDIs with two sulfoxide groups in the core reaches ?4.45 eV, whereas two sulfone moieties give a value of ?4.72 eV, which is as low as with four ethyl sulfone groups, that is, a π superacid near the limit of existence. Beyond anion–π interactions, these conceptually innovative π‐acidic surfaces are also of interest as electron transporters in conductive materials.  相似文献   
7.
常耀龙  任光霞  王彤威  孟旭 《应用声学》2015,23(7):2308-2310
某型引进装备雷达高频舱部位数字电路随着使用年限的增长,使用频率的增多,故障率逐年增高,已严重制约装备功能的发挥;针对原有备件必须在所属装备测试的验证方式,对装备本身消耗大、验证手段单一,无法满足维修保障需求的问题,开发了基于实物数据采集、分析、测试于一体的自动测试系统,有效地解决了装备作为唯一验证手段的现状,同时大大提高了测试验证的工作效率及验证的准确性,对装备整体功能以及局部功能的检测产生很大的作用,实用性强,适于推广应用。  相似文献   
8.
The enthalpy and conformational volume changes in the photolyses of carboxy-hemoglobin (HbCO) of human, bovine, pig, horse and rabbit are investigated by photoacoustic calorimetry. Considering the time scales of the exciting laser pulse and the receiving ultrasound transducers (PVDF films and PZT ceramics), as well as the reaction lifetimes in the photolysis processes of HbCO, the measured results are related to the geminate recombination and tertiary relaxation in photolyses of HbCO. Moreover, the quantum yields of the five mammals are also measured by laser pump-probe technique. The results show that the dynamic parameters, such as enthalpy and conformational volume changes, differ between the processes of the geminate recombination and tertiary relaxation. Also, the dynamic parameters differ among the five mammals although some of them may be consistent with each other.  相似文献   
9.
Shape optimization of the caudal fin of the three-dimensional self-propelled swimming fish,to increase the swimming efficiency and the swimming speed and control the motion direction more easily,is investigated by combining optimization algorithms,unsteady computational fluid dynamics and dynamic control in this study.The 3D computational fluid dynamics package contains the immersed boundary method,volume of fluid method,the adaptive multi-grid finite volume method and the control strategy of fish swimming.Through shape optimizations of various swimming speeds,the results show that the optimal caudal fins of different swimming modes are not exactly the same shape.However,the optimal fish of high swimming speed,whose caudal fin shape is similar to the crescent,also have higher efficiency and better maneuverability than the other optimal bionic fish at low and moderate swimming speeds.Finally,the mechanisms of vorticity creation of different optimal bionic fish are studied by using boundary vorticity-flux theory,and three-dimensional wake structures of self-propelled swimming of these fish are comparatively analyzed.The study of vortex dynamics reveals the nature of efficient swimming of the 3D bionic fish with the lunate caudal fin.  相似文献   
10.
Gauss和与广义Kloosterman和的几个新的恒等式   总被引:5,自引:1,他引:4  
主要应用Gauss和的性质和解析方法来研究Gauss和与广义Kloosterman和之间的关系,并且给出了几个有趣的恒等式.  相似文献   
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