Coumarin synthesis on π-acidic surfaces

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.     

Ratiometric mode with dyads: a breakthrough in dynamic trapping and quantification for redox regulation in living cells

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     

四边固定载流矩形薄板的磁弹性稳定性分析

本文针对四边固定载流矩形薄板,利用Mathieu方程解的稳定性,研究其在电磁场与机械荷载共同作用下的磁弹性稳定性问题。首先在载流薄板的磁弹性非线性运动方程、物理方程、几何方程、洛仑兹力表达式及电动力学方程的基础上,导出了载流薄板在电磁场与机械荷载共同作用下的磁弹性动力稳定方程,然后应用Galer-kin方法将稳定方程整理为Mathieu方程的标准形式,并将薄板的动力稳定性问题归结为对Mathieu方程的求解。利用Mathieu方程的稳定解区域与非稳定解区域的分界,即方程系数λ和η的本征值关系,得出了磁弹性问题失稳临界状态的判别方程。通过具体算例,给出了四边固定载流矩形薄板的磁弹性动力失稳临界状态与相关参量之间的关系曲线,并对计算结果及其变化规律进行了分析讨论。     

白洋淀内水体的流动特征研究

研究了风对白洋淀内水体循环流动的影响，研究指出：(1)风应力可看作是水体循环 的主要驱动力. (2)在风应力的作用下，水体表层的流动主方向与风的方向一致，下层水体 的流动方向与表层方向相逆或近似相逆. (3)表层以下水体流动复杂，次表层水平流动有明 显的双涡结构. (4)淀底地形对水体垂向流动影响很大，垂向速度变化复杂，垂向上有双涡 流动现象. 从动力学角度研究了淀内水体流动的情况.     

THERMODYNAMIC AND PARTICLE-DYNAMIC STUDIES ON SYNTHESIS OF SILICA NANOPARTICLES USING MICROWAVE-INDUCED PLASMA CVD

1. Introduction1.1 Silica nanoparticles and synthesis methods Silica (SiO2) nanoparticles are widely used in industry asan active filler for polymer reinforcement, a rheologicaladditive in fluids, a free flow agent in powders, and anagent for chemical mechanical polishing during IC (inte-grated circuit) fabrication (Sniegowski & de Boer, 2000).Silica powder is also used for producing silicon carbide(Koc & Cattamanchi, 1998) or opaque silica aerosols (Leeet al., 1995). Many methods can …     

Precise absolute positioning for a single-frequency user

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.     

Big,Strong, Neutral,Twisted, and Chiral π Acids

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.     

Photolyses of mammalian carboxy-hemoglobin studied by photoacoustic calorimetry

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.     

Silver(I)-mediated reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides:Unexpected formation of vinvl sulfones

A novel reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides was performed in the presence of silver nitrate or triflate.Conjugated vinyl sulfones as dramatic products were obtained in moderate yields and with Z-selectivity.A free radical mechanism has been proposed to account for the formation of the products.     

Effects of source opacity and expansion on two-pion Bose-Einstein correlations

We examine two-pion Bose-Einstein correlations for partially coherent particle-emitting sources within quantum statistical formalism, where the sources are treated as classical currents with chaotic and coherent components. The two-pion correlation functions of the partially coherent sources contain a phase which is sensitive to the asymmetry of the source emission function. We investigate the influence of source opacity and expansion in high energy heavy ion collisions on the phase by Monte Carlo calculati...