Reversible Adaptation to Photoinduced Shape Switching by Oligomer–Macrocycle Interconversion with Component Selection in a Three‐State Constitutional Dynamic System

Light irradiation of the molecular photoswitch 1 ‐E causes isomerization into the 1 ‐Z configuration stabilized by an internal hydrogen bond. 1 ‐E bears aldehyde groups allowing for dynamic covalent reaction with linear diamines. On photoinduced E/Z shape switching of 1 in presence of diamines, the system undergoes interconversion between two states, a non‐cyclic oligomeric one and a macrocyclic one, corresponding respectively to the E and Z configurations of 1 . With a mixture of linear α,ω‐diamines, 1 ‐E yields non‐selective dynamic oligomers by random incorporation of diamine components. Photoswitching to the 1 ‐Z form leads to constitutional adaptation with preferential formation of the macrocycle incorporating the best suited diamine, H₂N(CH₂)₇NH₂. In presence of metal cations, the E form switches from its unbound W shape to its coordinated U shape and yields the macrocycle resulting from the selective incorporation of the diamine H₂NCH₂CH₂OCH₂CH₂NH₂ that contains an additional O coordination site. Taken together, the results obtained describe constitutional adaptation in a triple state system: an oligomeric one and two different macrocyclic ones generated in response to two orthogonal agents, a physical stimulus, light, or a chemical effector, metal cations. These three states present, towards the incorporation of diamine components, respectively no selection, photoselection and metalloselection.     

Measurement of the Refractive Index and Estimate of the Order Parameter in Oriented Liquid Crystals

The refractive indices of a cholesteric liquid crystal, cholesteryl dodecyl carbonate (CDC), and a smectic liquid crystal, p-n-octoxybenzilidene-p-n-butylaniline (OOBBA), have been measured as a function of temperature in the transition temperature regions. The measurements were made on oriented liquid crystals with an Abbe refractometer. By combining the data on ordinary and extraordinary refractive indices, the relative order parameter, α_aS/α, is plotted as a function of temperature. The behavior of the order parameter near the cholesteric to isotropic transition of CDC is similar to a nematic liquid crystal, whereas, the order parameter in OOBBA shows only a slight temperature variation like many solids.     

Coating curly carbon nanotubes with monocrystalline Zn(BO2)2 and the mechanism of straightening the tubes

We overgrew single-crystalline Zn(BO₂)₂ coatings on carbon nanotubes (CNTs) for the first time. Scanning electron microscopy and transmission electron microscopy analyses revealed that the carbon nanotube-zinc borate composite rods are from tens to hundreds of nm in diameter. It is notable that the original curly tubes were straightened by the monocrystalline coatings. In addition, the crystal nucleation and growth on the surface of CNT were explained. We set a two-dimensional model, which is based on our experimental result, to qualitatively explain the mechanism of straightening the curly tubes by coating them with single-crystals.     

Dynamic polymer membranes displaying tunable transport properties on constitutional exchange

Functional dynamic polymers, “dynamers”, are used to design new membrane materials. Our efforts involve the synthesis and the fabrication of dynamic thin-layer supported solid membrane films. The transport performances of (permeability, selectivity and partition coefficients) are evaluated by using the solution-diffusion model. The membrane performances designed to transport ionic salts NaCl and KCl depend and are based on encoded molecular features of the monomeric subcomponents. Thanks to the possibility to combine the structural and functional features of different monomers, the heteropolymeric membrane materials can exhibit very different properties from their original homopolymeric components. In the examples developed here, this strategy revealed itself as a versatile way for the synthesis of new membranes presenting different permeabilities and preserving their selectivity (SK_+/Na₊∼1.4)$(S_{{\text{K}}^{+}/\text{N}{\text{a}}^{+}}\sim 1.4)$.     

A broadband ADEQUATE pulse sequence using chirp pulses

Recently, we have introduced the ADEQUATE pulse sequence as a sensitive method to observe ¹³C,¹³C correlations in natural products. This kind of experiment suffers from offset‐dependent effects of the 180°(¹³C) pulses. Here we describe an application of smoothed chirp pulses in the ADEQUATE pulse sequence which allows ¹³C,¹³C correlations to be run without any offset dependences. This experiment is called chirp ADEQUATE and was applied to δ‐valerolactone and cholesteryl acetate. This modification will allow a general application of the ADEQUATE pulse sequence. Copyright © 2002 John Wiley & Sons, Ltd.     

Simulation of temperature-modulated DSC of transitions represented by abrupt changes in heat capacity

Computer simulations have been applied to elucidate the response of a sample to temperaturemodulated differential scanning calorimetry (tm-DSC) during transitions. Two cases have been simulated; a latent heat without supercooling (represented by an abrupt heat capacity pulse with perfect reversibility) and a latent heat with perfect supercooling or large hysteresis (an abrupt heat capacity change without reversibility, i.e. the change in heat capacity is seen on heating, but not on cooling). Because the simulation was applied to these well-characterized phenomena, the results are useful to reveal actual sample thermal responses during transitions. The non-reversible component was observed in both cases and has no distinct difference. Higher harmonics due to non-linearity of the transitions were also observed. Furthermore, by inspecting thermal response of the sample and the essential feature of tm-DSC, a new method of data analysis has been devised.     

静电悬浮技术研究进展

利用静电悬浮技术可使各种材料处于稳定的悬浮无容器状态,达到深过冷,并对材料的熔凝过程进行实时观测.文章介绍了静电悬浮技术的机理及其在材料科学研究中的应用,并展望了它的发展方向.     

钽-钨合金动态响应特性研究

用冶金技术与冲击波物理实验相结合的方法,研究了钽 钨合金不同初始状态和不同钨含量时的材料动态响应特性,给出了Ta12W 合金材料的动态断裂强度、Hugoniot 弹性极限、屈服强度以及理想弹 塑性本构关系中包含的其它本构参量。     

Cryo-scanning electron microscopic study on freezing behavior of xylem ray parenchyma cells in hardwood species

Differential thermal analysis (DTA) has indicated that xylem ray parenchyma cells (XRPCs) of hardwood species adapt to freezing of apoplastic water either by deep supercooling or by extracellular freezing, depending upon the species. DTA studies indicated that moderately cold hardy hardwood species exhibiting deep supercooling in the XRPCs were limited in latitudinal distribution within the −40°C isotherm, while very hardy hardwood species exhibiting extracellular freezing could distribute in colder areas beyond the −40°C isotherm. Predictions based on the results of DTA, however, indicate that XRPCs exhibiting extracellular freezing may appear not only in very hardy woody species native to cold areas beyond the −40°C isotherm but also in less hardy hardwood species native to tropical and subtropical zones as well as in a small number of moderately hardy hardwood species native to warm temperate zones. Cryo-scanning electron microscopic (cryo-SEM) studies on the freezing behavior of XRPCs have revealed some errors in DTA. These errors are originated mainly due to the overlap between exotherms produced by freezing of water in apoplastic spaces (high temperature exotherms, HTEs) and exotherms produced by freezing of intracellular water of XRPCs by breakdown of deep supercooling (low temperature exotherms, LTEs), as well as to the shortage of LTEs produced by intracellular freezing of XRPCs. In addition, DTA results are significantly affected by cooling rates employed. Further, cryo-SEM observations, which revealed the true freezing behavior of XRPCs, changed the previous knowledge of freezing behavior of XRPCs that had been obtained by freeze-substitution and transmission electron microscopic studies. Cryo-SEM results, in association with results obtained from DTA that were reconfirmed or changed by observation using a cryo-SEM, revealed a clear tendency of the freezing behavior of XRPCs in hardwood species to change with changes in the temperature in the growing conditions, including both latitudinal and seasonal temperature changes. In latitudinal temperature changes, XRPCs in less hardy hardwood species native to tropical and subtropical zones exhibited deep supercooling to −10°C, XRPCs in moderately hardy hardwood species native to temperate zones exhibited a gradual increase in the supercooling ability to −40°C from warm toward cool temperate zones, and XRPCs in very hardy hardwood species native to boreal forests exhibited extracellular freezing via an intermediate form of freezing behavior between deep supercooling and extracellular freezing. In seasonal temperature changes, XRPCs in hardwood species native to temperate zones changed their supercooling ability from a relatively low degree in summer to a high degree in winter. XRPCs in hardwood species native to boreal forests changed their freezing behavior from deep supercooling to −10°C in summer to extracellular freezing in winter. These results indicate that the freezing behavior of XRPCs in hardwood species tends to shift gradually from supercooling of −10°C, to a gradual increase in the deep supercooling ability to −40°C or less, and finally to extracellular freezing as a result of cold acclimation in response to both latitudinal and seasonal temperature changes. It is thought that these temperature-dependent changes in the freezing behavior of XRPCs in hardwood species are mainly controlled by changes in cell wall properties, although no distinct changes were detected by electron microscopic observations in cell wall organization between hardwood species or between seasons. Evidence of temperature-dependent changes in the freezing behavior of XRPCs in hardwood species provided by the results of studies using a cryo-SEM has indicated the need for further investigation to clarify cold acclimation-induced cell wall changes at the sub-electron microscopic level in order to understand the mechanisms of freezing adaptation.