Designing and Constructing a High‐Temperature Molecular Ferroelectric by Anion and Cation Replacement in a Simple Crown Ether Clathrate

Molecular ferroelectrics have displayed a promising future since they are light‐weight, flexible, environmentally friendly and easily synthesized, compared to traditional inorganic ferroelectrics. However, how to precisely design a molecular ferroelectric from a non‐ferroelectric phase transition molecular system is still a great challenge. Here we designed and constructed a molecular ferroelectric by double regulation of the anion and cation in a simple crown ether clathrate, 4 , [K(18‐crown‐6)]⁺[PF₆]^?. By replacing K⁺ and PF₆^? with H₃O⁺ and [FeCl₄]^? respectively, we obtained a new molecular ferroelectric [H₃O(18‐crown‐6)]⁺[FeCl₄]^?, 1 . Compound 1 undergoes a para‐ferroelectric phase transition near 350 K with symmetry change from P21/n to the Pmc21 space group. X‐ray single‐crystal diffraction analysis suggests that the phase transition was mainly triggered by the displacement motion of H₃O⁺ and [FeCl₄]^? ions and twist motion of 18‐crown‐6 molecule. Strikingly, compound 1 shows high a Curie temperature (350 K), ultra‐strong second harmonic generation signals (nearly 8 times of KDP), remarkable dielectric switching effect and large spontaneous polarization. We believe that this research will pave the way to design and build high‐quality molecular ferroelectrics as well as their application in smart materials.     

Multiple Photoluminescent Processes from Pyrene Derivatives with Aggregation‐ and Mechano‐Induced Excimer Emission

Two novel pyrene‐based isocyanide gold(I) complexes have been designed and synthesized. The different structures lead to distinct and diverse photophysical properties both in solution and in the aggregate state. Multiple photoluminescence, involving monomer emission, locally excited emission and excimer emission, are observed. Notably, an excimer is formed by aggregation in solution and external mechanical stimulation in the solid state, showing aggregation‐ and mechano‐induced excimer emission.     

Water‐soluble Glucosamine‐coated AIE‐Active Fluorescent Organic Nanoparticles: Design,Synthesis and Assembly for Specific Detection of Heparin Based on Carbohydrate–Carbohydrate Interactions

Two water‐soluble carbohydrate‐coated AIE‐activate fluorescent organic nanoparticles TPE3G and TPE4G were designed and synthesized for the detection of heparin. Different from the reported strategy, we not only utilized the general detection mechanism of electrostatic interactions, but also introduced the concept of carbohydrate‐carbohydrate interactions (CCIs) to enrich the detection mechanism of heparin. TPE3G can serve as an efficient “turn‐on” probe with higher selectivity towards heparin than TPE4G . TEM studies revealed that the micro‐aggregated TPE3G was encapsulated with the heparin chain to form a complex self‐assemblied composite and emits strong fluorescence. It is believed that the results illustrated in this study provide a novel strategy based on CCls to design water‐soluble and more efficient bio‐probes for various biological and clinical applications.     

Squaraine Dyes: Interaction with Bovine Serum Albumin to Investigate Supramolecular Adducts with Aggregation‐Induced Emission (AIE) Properties

Bovine serum albumin (BSA)–squaraine supramolecular adducts with aggregation‐induced emission (AIE) properties were prepared and characterized by spectroscopic methods. While squaraine dyes showed a very low fluorescence quantum yield in water, a great enhancement in the fluorescence of the aggregated BSA adducts was achieved due to the abnormal aggregation‐induced emission properties of squaraines. The adducts formation was studied from a kinetic point of view showing unexpected structure–properties relationships.     

SiNWs:Tb3+的光学稳定性及Si纳米线对其发光特性的影响

荧光纳米材料不但具备纳米材料的优势,同时还具有优异的光学性质,被广泛应用于荧光标记、离子识别、荧光免疫分析、光学成像和医学诊断等方面。因此,荧光纳米材料的制备、结构分析和荧光特性等方面的研究备受人们的关注。为了获得发光强度大、荧光量子效率高和制备过程可控的Si基荧光纳米材料,实验进一步研究了Si纳米线对样品发光特性的影响和样品的光学稳定性。首先,基于固-液-固生长机制,在反应温度为1 100 ℃、N₂气流量为1 500 sccm、生长时间为15～60 min等工艺条件下,分别以“抛光”和“金字塔”织构表面的单晶Si(100)为衬底,生长出不同长度和分布的Si纳米线;以Au或Au-Al合金膜层作为金属催化剂,生长出密度分别约为108和1010 cm-2的Si纳米线;然后,利用L4514自动控温管式加热炉,基于高温固相法,在温度为1 100 ℃、掺杂时间为60 min和N₂气流量为1 000 sccm等工艺条件下,以高纯Tb₄O₇(99.99%)粉末为稀土掺杂剂对不同Si纳米线衬底进行稀土掺杂,制备一系列的荧光纳米材料SiNWs:Tb3+样品;室温下利用Hitachi F-4600型荧光分光光度计,固定激发光波长为243 nm、激发光狭缝为2.5 nm、发射光狭缝为2.5 nm、扫描波长范围为450～650 nm、光电倍增管(photomultiplier lube, PMT)电压为600 V等参数下,测量了不同样品的光致发光特性;最后,实验测试了该荧光纳米材料的光学稳定性,如时间(0～30 d)、温度(300～500 K)、酸碱(pH 1和11)、抗光漂白(0～120 min)等稳定性以及水溶性和分散性。结果显示,在衬底为“金字塔”织构表面上、生长时间为30 min、以Au为金属催化剂等条件下制备的Si纳米线为Tb3+掺杂衬底时,SiNWs:Tb3+的绿光发射强度较大,其发光强峰值位于554 nm,属于能级5D₄→7F₅的跃迁,另外在波长为494,593和628 nm出现了三条发光谱带,它们分别属于能级5D₄→7F₆,5D₄→7F₄和5D₄→7F₃的跃迁。另外,样品展示出了优异的时间、温度、酸碱和抗光漂白等光学稳定性,同时还具有良好的水溶性和分散性。如温度升高到500 K时,光发射强度仅降低了约8.9%左右;抗光漂白能力较强,用波长为365 nm、功率为450 W的紫外光源照射120 min,样品的绿光发射强度无衰减;酸、碱稳定性好,在pH 1的强酸(HCl)溶液中120 min未见衰减,在pH 11的强碱(NaOH)溶液中15 min内衰减较小, 随后发光强度出现了缓慢下降的趋势;当60 min后,样品的发光强度变得极其微弱。分析认为,在SiNWs:Tb3+表面有一层SiO₂包覆层,而NaOH溶液容易和SiO₂发生化学反应,随着时间延长SiO₂层被破坏,故样品发光强度降低;样品溶于水中放置30 d未见沉淀物,发光亮度均匀且分散性较好。在研究了制备温度、气体流量和掺杂时间等工艺条件之后,深入研究了Si纳米线自身变化对Tb3+绿光发射的影响。该材料展示出了良好的光学稳定性、水溶性和分散性,使其作为荧光标记物具有一定的应用价值。     

温度对AZO薄膜红外辐射性能的影响

随着全球资源的减少和环境的恶化,节能减排已成为人们关注的焦点,具有保温隔热功能的低辐射玻璃成为研究的热点。提高玻璃保温隔热性能最有效的方法就是在其表面涂覆低辐射率层。原材料丰富、导电性能好、可见光透过率高等优势使得Al掺杂ZnO (AZO)薄膜成为最具潜力的低辐射率层。系统研究了温度对AZO薄膜红外辐射性能的影响,分析了变化机理。首先研究了在一定的温度下持续一段时间后,AZO薄膜的红外比辐射率的变化情况。然后研究了在变温环境中红外比辐射率的变化情况。采用直流磁控溅射法在室温下玻璃基片上沉积500 nm厚的AZO薄膜,将薄膜放到马弗炉中进行热处理,在100～400 ℃空气气氛下保温1 h,随炉冷却。采用X射线衍射仪对AZO薄膜进行物相分析,采用扫描电子显微镜观察薄膜表面形貌变化。利用四探针测试法测量AZO薄膜的电阻率,采用红外比辐射率测试仪测试薄膜红外比辐射率, 可见分光光度计测量可见光谱。测试的结果表明,薄膜热处理前后均为六角纤锌矿结构,(002)择优取向。300 ℃及以下热处理1 h后,(002)衍射峰增强,半高宽变窄,晶粒尺寸长大。随着热处理温度的升高,薄膜的电阻率先减小后增大,200 ℃热处理后的薄膜具有最小的电阻率(0.9×10-3 Ω·cm)。热处理温度升高,晶粒长大使得薄膜电阻率降低。热处理温度过高,薄膜会从空气中吸收氧,电阻率下降。薄膜的红外比辐射率变化趋势和电阻率的一致,在200 ℃热处理后获得最小值(0.48)。自由电子对红外光子有较强的反射作用,当电阻率低,自由电子浓度高的时候,更多的红外光子被反射,红外辐射作用弱,红外比辐射率小。薄膜的可见光透过率随着热处理温度的升高先减小后增大,200 ℃热处理后的薄膜的可见光透过率最小,但仍高达82%。这种变化是由于自由电子浓度变化引起的,自由电子对可见光有很强的反射作用。选取未热处理和200 ℃热处理后的样品进行变温红外比辐射率的测量,将样品放在可加热的样品台上,位置固定,在室温到350 ℃的升温和降温过程中每隔25 ℃测量一次红外比辐射率,结果表明,在室温到350 ℃的温度范围内,AZO薄膜的红外比辐射率在升温过程中随着温度的上升而增大,在降温过程中减小,经过整个升、降温过程后,薄膜的红外比辐射率增大。     

基于相关子空间的双峰发射线光谱特征提取与分析

低分辨率天体光谱中呈现的双峰发射线轮廓可能反映着比较珍稀的物理现象,如双活动星系核（AGNs）、双超大质量黑洞（SMBH）、喷流云与窄线区的相互作用,也可能是光谱处理过程产生的低质量特征线。双峰发射线轮廓一般由2个或2个以上的波峰构成,对该特征进行提取并分析,可作为双AGN、星系对、双黑洞等稀有天体更有效的搜寻依据,从而有助于更深入地研究星系乃至宇宙的形成与演化。提出一种新的基于相关子空间的双峰发射线特征提取与分析方法,主要工作分为以下三部分：首先利用稀疏差异因子δ度量双峰发射线光谱中属性差异程度,利用KNN方法约束参与稀疏差异因子计算的光谱范围,在此基础上,针对LAMOST低分辨率光谱给出基于相关子空间的特征提取方法;其次,为了验证稀疏差异因子σ以及KNN的输入参数k对双峰发射线光谱的适应性,选择LAMOST双峰发射线光谱样本及普通星系光谱数据,红移范围z<0.3（确保Hα,Hβ,[OⅢ]λλ4 959, 5 007,[NⅡ]λλ6 548, 6 584,[SⅡ]λλ6 717, 6 731等发射线落在LAMOST波长覆盖范围）,获得训练集光谱总数332+332（正负样本）条,并借助人眼检查分析该方法中的两个参数：k和δ阈值α对结果的影响,实验表明,当k=18,α=0.6时,相关属性分布较密集且稀疏点较少,结果比较理想;最后,对332条双峰发射线光谱特征子空间所在的波长区间、双峰红/蓝移间隔、双峰线强比等进行了理论分析、测量及人眼认证的基础上,给出了基于相关子空间的双峰发射线特征表述。此外,从双峰特征子空间上不同的发射线激发机制（[OⅢ]/[NⅡ]/[SⅡ]等禁线、Hα、Hβ等氢线）及相关特征子空间上线强关系等角度,对样本中双峰轮廓进行了分析。     

Spectral Characterization of Couplings in a Mixed Optomechanical Model *

Abstract:We study the spectrum of single-photon emission and scattering in a mixed optomechanical model which consists of both linear and quadratic optomechanical interactions. The spectra are calculated based on the exact long-time solutions of the single-photon emission and scattering processes in this system. We find that there exist some phonon sideband peaks in the spectra and there are some sub peaks around the phonon sideband peaks under proper parameter conditions. The correspondence between the spectral features and the optomechanical interactions is confirmed, and the optomechanical coupling strengths can be inferred by analyzing the resonance peaks and dips in the spectra.     

自发过程总熵判据的讨论式教学实践

将讨论式教学法的基本思想应用到物理化学的课堂教学中,对物理化学的教学难点--热力学自发过程总熵判据的适用条件问题进行了深入的讨论,最终归纳总结,得出重要结论：总熵判据只能用来判断过程的可逆性,不能直接判断过程的自发性。要想进一步判断过程的自发性质,须结合系统与环境之间交换的总功进行判断。通过讨论式教学实践,学生对热力学自发过程总熵判据的适用条件有了更加深入的理解,给后续课程的学习打下了良好的基础。