Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host–Guest Systems

The recognition properties of heteroditopic hemicryptophane hosts towards anions, cations, and neutral pairs, combining both cation–π and anion–π interaction sites, were investigated to probe the complexity of interfering weak intermolecular interactions. It is suggested from NMR experiments, and supported by CASSCF/CASPT2 calculations, that the binding constants of anions can be modulated by a factor of up to 100 by varying the fluorination sites on the electron‐poor aromatic rings. Interestingly, this subtle chemical modification can also reverse the sign of cooperativity in ion‐pair recognition. Wavefunction calculations highlight how short‐ and long‐range interactions interfere in this recognition process, suggesting that a disruption of anion–π interactions can occur in the presence of a co‐bound cation. Such molecules can be viewed as prototypes for examining complex processes controlled by the competition of weak interactions.     

Introducing negative charges into bis-p-phenylene crown ethers: a study of bipyridinium-based [2]pseudorotaxanes and [2]rotaxanes

This paper describes novel host-guest systems comprising viologen cations (guests) and the derivatives of bis-para-phenylene-34-crown-10 (hosts) with anionic groups COO(-) or SO(3)(-). The structure of the resulting charge-compensated host-guest complexes, their association constants and their electrochemical behaviour have been studied. In the solid state, the viologen cations thread the negatively charged crown ethers forming electroneutral zwitterion-like [2]pseudorotaxane salts; in solution this threaded geometry is preserved. The association constants of [2]pseudorotaxane salts incorporating the 1,1'-diethylviologen moiety in solution are significantly higher than those of previously reported analogues. The extrapolated association free energies in non-aqueous media exceed -40 kJ mol(-1) at 25 degrees C. This significant increase of the interaction free energy makes these compounds stable even in aqueous solutions. The association constants of [2]pseudorotaxane salts incorporating sterically more hindered 1,1'-diethyl-3,3'-dimethylviologen moieties are significantly lower. Structurally related [2]rotaxane salts, in which the oppositely charged ionic components are mechanically interlocked, have been prepared in good yields. It has been shown that [2]rotaxane salts incorporating anti-isomers of bisfunctionalised crown ethers are cycloenantiomeric. In both [2]pseudorotaxane and [2]rotaxane salts, the electrostatic interactions between the viologen moieties and the negatively charged crown ethers lead to very significant negative shifts of viologen reduction potentials up to 450 mV. The findings of the present study are valuable for the design of nanoscale molecular electronic devices.     

Molecular Recognition Properties of Biphen[4]arene

Biphen[n]arenes (n=3, 4) are a new family of macrocyclic hosts. Here, we describe the molecular recognition behavior of hydroxylated biphen[4]arene (OHBP4) for the first time. A series of cationic guests with different sizes and shapes, including quaternary ammonium salts ( 1? PF₆ and 2? PF₆), pyridinium‐based guests ( 3? 2 PF₆– 6? 2 PF₆), and cobaltocenium hexafluorophosphate ( 7? PF₆), were chosen as model guest molecules. OHBP4 exhibits good selectivity towards the 2,7‐dibutyldiazapyrenium bis(hexafluorophosphate) ( 4? 2 PF₆) axle to form a [2]pseudorotaxane‐type complex. In contrast, hydroxylated biphen[3]arene (OHBP3) cannot bind with this big guest. In addition, OHBP4 strongly interacts with adamantane derivative 2? PF₆ and cobaltocenium 7? PF₆, which have tridimensional shape and relatively large size. The association constant of the 7 ⁺?OHBP4 complex in 1:1 (v/v) [D₆]acetone/CD₂Cl₂ solution is up to 3100±300 m ^?1.     

基于非线性流形学习的人脸面部运动估计

由于人脸面部运动变化分布在一个低维非线性流形中,基于线性假设的主动外观模型采用主成分分析算法描述人脸形状的变化必然带来额外的估计误差.为降低或消除这一误差,该文提出一种改进的局部线性嵌入算法构建人脸形状-纹理空间,并将其应用于主动外观模型中.实验结果表明,不仅对于面部形变不大的人脸形状,局部线性嵌入-主动外观模型拥有更...     

空间目标的联合矩阵束极点估计

极点作为谐振区雷达目标的最主要电磁特性,具有很大的空间目标识别前景。但是在使用频域观测数据提取目标极点时,存在虚假极点和估计精度问题。针对上述问题,首先通过加窗和截断改进了后时响应信号的获取流程,抑制了虚假极点影响;然后采用最小描述长度法（MDL）估计极点个数,避免了定阶错误引起的虚假极点;最后采用联合矩阵束法估计极点,有效减少了单角度数据估计极点时存在的遗漏极点和虚假极点问题。FEKO软件验证表明,所提算法具有更高的精度和抗噪能力。     

抽油机悬点载荷计算图版的数学模拟

美国石油学会公式是计算抽油机悬点载荷常用的公式之一,在该公式中,有两个无因次参数需要人工读图才能够查出。利用图像识别技术读取图版曲线上的数据点,对曲线进行数学模拟,使其能方便地应用于工程计算之中。     

Mixing Layers in Sink Flow: Effect of Length of Flight on Mixing in a Channel Downstream

We have experimentally and analytically studied transport of a passive scalar in the wake of a thin flat plate located at the centerline of a planar contraction with flat walls. The constant Launder parameter in the contraction, K = 6.25 ×10^− 6, was twice the value required for a turbulent boundary layer to relaminarize. In addition to the mixing analysis inside the contraction, layer mixing is also investigated downstream, where the flow continues inside a constant cross-section channel. In order to generate the passive scalar, the airflow above the plate was heated and the temperature stratification in the wake was traced by measuring the temperature field using constant current anemometry. Using different plate lengths, we found that the degree of mixing, obtained at a given position in the straight channel, is a function of the distance from the plate trailing edge to the contraction outlet. For a plate which does not protrude into the straight channel, we demonstrate the existence of an optimal trailing edge-contraction outlet distance that results in the lowest possible degree of mixing at a given downstream position in the straight channel. This finding is also supported by a semi-empirical relationship based on our developed self-similar solution for mixing layers in planar contractions.     

Four‐State Molecular Shuttling of [2]Rotaxanes in Response to Acid/Base and Alkali‐Metal Cation Stimuli

In this study, we synthesized [2]rotaxanes possessing three recognition sites—a dialkylammonium, an alkylarylamine, and a tetra(ethylene glycol) stations—in their dumbbell‐like axle component and dibenzo[24]crown‐8 (DB24C8) as their macrocyclic component. These [2]rotaxanes behaved as four‐state molecular shuttles: i) under acidic conditions, the DB24C8 unit encircled both the dialkylammonium and alkylarylammonium stations; ii) under neutral conditions, the dialkylammonium unit was the predominant station for the DB24C8 component; iii) under basic conditions, when both ammonium centers were deprotonated, the alkylarylamine unit became a suitable station for the DB24C8 component; and iv) under basic conditions in the presence of an alkali‐metal cation, the tetra(ethylene glycol) unit recognized the DB24C8 component through cooperative binding of the alkali‐metal ion. In addition, we observed that the [2]rotaxanes exhibited selective recognition for metal cations. These shuttling motions of the macrocyclic component proceeded reversibly.     

基于三角小波的弹性薄板高精度分析方法

采用同时具有三角函数良好逼近特性和小波多分辨率与局部特性的Hermite插值型三角小波,基于二维张量积三角小波,推导了求解各种不同边界条件下的矩形弹性薄板的弯曲、振动和屈曲问题的统一列式,同时给出了两种提高计算精度的方法一升阶法和多分辨率法。数值算例表明,三角小波法求解弹性薄板的弯曲、振动和屈曲问题时,能方便地处理各类边界条件,计算效果良好;自振特性分析更具优势,升阶法和多分辨率法能有效地提高分析精度。     

pH‐Controlled Molecular Switches and the Substrate‐Directed Self‐Assembly of Molecular Capsules with a Calix[4]pyrrole Derivative

10α,20α‐Bis(4‐nitrophenyl)calix[4]pyrrole ( 1 ) forms 1:1 complexes with anions of selected aromatic hydroxy acids in which the host orientation within the guest is controlled by a change in the pH value. Some bis‐anionic guests, including those obtained from 4‐hydroxybenzoic acid, 1,4‐ and 1,3‐benzenedicarboxylic acids, induce the self‐assembly of molecular capsules involving two molecules of the receptor. ¹H NMR data and solid‐state structures of the 1:1 complex of 1 with p‐C₆H₄(COOH)(COO^?)⁺NMe₄ and the 2:1 capsule [( 1 )₂m‐C₆H₄(COO^?)₂(⁺NMe₄)₂] provide structural details in solution and in the solid state.