超分子组合流体室温磷光现象(Ⅱ)——醇对环糊精/碘代乙基联苯/溴代环己烷体系室温磷光的影响

在外部重原子微拢剂溴代环己烷存在下，β－ＣＤ／碘代乙基联苯体系可发射一定强度的室温磷光信号，若丁醇作为第四组分存在，则能显著提高体系的室温磷光发射强度。研究了该体系室温磷光发射的适宜条件和多种醇、不同环糊精及其衍生物的影响。认为β－ＣＤ／碘代乙基联苯／溴代环己烷／丁醇体系属于一种超分子组合的发光体系，醇的作用属典型的分子调控作用。β－ＣＤ／碘代乙基联苯／溴代环己烷形成主、客三元包结物，而醇则利用其羟基与ＣＤ端口羟基形成氢键，其烷基键借助于疏水相互作用力，覆盖在ＣＤ上、下端口，对外部氧向ＣＤ腔内的扩散起着隔离作用，减少了三线态氧对发光体激发三线态的猝灭，从而显著提高了体系室温磷光发射强度     

超分子组合流体室温磷光现象（Ⅱ）—醇对环糊精／碘代乙基联 …

在外部重原子微拢剂溴代环己烷存在下，β－ＣＤ／碘代乙基联苯体系可发射一定强度的室温磷光信号，若丁醇作为第四组分存在，则能显著提高体系的室温磷光发射强度。研究了该体系室温磷光发射的适宜条件和多种醇、不同环糊精及其衍生物的影响。认为β－ＣＤ／碘代乙基联苯／溴代环乙烷／丁醇体系属于一种超分子组合的发光体系，醇的作用属典型的分子调控作用。β－ＣＤ／碘代乙基联苯／溴代环乙烷形成主、客三元包结物，可醇则利用其     

液态DMF中N—14四极耦合常数的实验测定

本文利用质子的＾１３Ｃ卫星峰与＾１２Ｃ主峰的弛豫速率之差为纯的偶极偶极机制这一原理，较精确地测定了２５℃时ＤＭＦ分子的取向相关时间，结合分子中Ｎ－１４的四极弛豫时间，得到了液态ＤＭＦ分子中Ｎ－１４核的四极耦合常数为３．４２ＭＨｚ．     

环糊精—表面活性剂包结作用的研究

应用表面张力方法研究了β－环糊精（β－ＣＤ）对十二烷基苯磺酸钠（ＳＤＢＳ）的包结作用，研究了不同温度下β－ＣＤ对ＳＤＢＳ表面活性的影响以及脂肪醇加入β－ＣＤ包结ＳＤＢＳ表面活性的影响，求得了不同温度下β－ＣＤ包结ＳＤＢＳ的平衡常数Ｋ，并用＾１ＨＮＭＲ波谱探讨了包结物β－ＣＤ／ＳＤＢＳ的分子结构模型。     

SinSem分子簇的SCC—DV—Xa方法的计算研究

本文应用ＳＣＣ－ＤＶ－Ｘａ方法计算了（ＲＳｉ）４Ｓｅ６，（ＲＳｉ）２Ｓｅ３和Ｒ４Ｓｉ３Ｓｅ４（Ｒ＝ＣＨ３，Ｃ２Ｈ５，Ｐｈ）等分子簇的结合能，轨道能级，电荷分布，状态密度，分析了簇的稳定性，ＮＭＲ化学位移，紫外可见吸收和催化性能等，结果与实验相符。     

（7—甲氧基—4—亚甲基）香豆素基—单氮杂18—冠—6的合成及其？…

合成、鉴定了题示光敏离子载体（ＭＭＣ－ＭＡＣ（Ｏ５）。其中不同ｐＨ值水溶液中吸收和荧光光谱的变化,计算得该剂基态和激发态分子的酸性常数（ｐＫａ＝８．８４,ｐＫａ＾＊＝５．１１）。基于在不同溶剂中荧光光谱的变化,由Ｓｏｌｖａｃｈｒｏｍｉｃ法,借助Ａｌｃｈｅｍｙ２０００量化计算软件,估算得该分子的基态和激发态偶极矩,分别为３．１１Ｄ和８．１３Ｄ。同时发现,ＭＭＣ－ＭＡＣ（Ｏ５）水溶液除氧后其荧光强度奇     

聚异亚甲亚胺分子间氢键的形成及其对导电性能的影响

采用量子化学ＭＮＤＯ、ＣＮＤＯ／２－ＣＯ方法，探讨了聚异亚甲亚胺（ＨＣ＝Ｎ－Ｎ＝ＣＨ）ｘ分子链间Ｎ…Ｈ－Ｃ型氢键形成的可能性和氢键构成，分析了这种氢键影响高聚物导电性能的规律。     

S2分子X^3—Σ^—g和B^3Σ^—u态的势能函数和振动光谱特征

应用实验光谱数据，导出了Ｓ２的基态分子Ｘ３Σ－ｇ和激发态Ｂ３Σ－ｕ的ＭｕｒｅｌＳｏｒｂｉｅ势能函数，并用ＱＣＩＳＤ（Ｔ）／６－３１１Ｇ方法对基态进行了计算，结果在吸引支出现了回避相交而产生了一个浅平极大，其他部位与实验结果符合甚好。计算了Ｂ３Σ－ｕ和Ｘ３Σ－ｇ态的全部振动能级，以及激发态（Ｂ３Σ－ｕ）振动能级≤９和基态（Ｘ３Σ－ｇ）振动能级≤３０之间的Ｄｅｓｌａｎｄｒｅｓ表。给出了Ｂ３Σ－ｕ－Ｘ３Σ－ｇ跃迁Ｃｏｎｄｏｎ抛物线，各振动态的计算结果与实验值很好符合。     

1—苄基—9—氢富勒烯—60LB多层膜的制备及其光学非线性性质

利用π－Ａ等温线，小角Ｘ射线衍射和光学测量方法研究了一种取代富勒烯ＬＢ膜的结构特性。纯Ｃ６０－Ｂｅ分子以体相的形式存在于气－液界面上。氮冠分子作为隔层材料，与Ｃ６０－Ｂｅ分子相混合可以制备性能优良的ＬＢ膜。     

CH3D分子3V2泛频态高分辨红外光谱的振动分析

用最小二乘法拟合ＣＨ３Ｄ分子６４２８ｃｍ＾－１附近振动带的１３８个能级，１０个振动常数。振动分析阐明带为ＣＨ３分子Ｃ－Ｄ对称伸缩振动３Ｖ２态，并与局域模振动理论计算值进行了比较。     

单（6—S—丹磺酰基）—β—环糊精的合成及其分子识别功能初探

合成鉴定具有发光基团的环糊精衍生物，研究了该产物水溶液的荧光特性和它对客体环己醇，环己烯，溴化环己烷，以及苯甲酸系列的包结与识别作用，用修正的Ｈｉｌｄｅｂｒａｎｄ－Ｂｅｎｅｓｉ方程计算得主客化合物的包结常数和识别因子，不仅证明主客体间形成１：１包结物，且其包结常数和识别因子与客体的分子结构及疏水性等直接有关。     

Synthesis of novel bis(β‐cyclodextrin)s linked with aromatic diamine and their molecular recognition with model substrates

Novel β‐cyclodextrin (β‐CD) dimers with aromatic diamine linkers, 1,3‐(aminomethyl)‐benzylamine‐bridged bis(6‐amino‐6‐deoxy‐β‐CD) (2) , 4,4′‐diaminodiphenylmethano‐bridged bis(6‐amino‐6‐deoxy‐β‐CD) (3) , and 4,4′‐ ethylenedianiline‐bridged bis(6‐amino‐6‐deoxy‐β‐CD) (4) , were synthesized. The inclusion complexation behaviors of these compounds, together with 4,4′‐aminophenyl ethyl‐bridged bis(6‐amino‐6‐deoxy‐β‐CD) (5) , with substrates such as acridine red (AR), neutral red (NR), ammonium 8‐anilino‐1‐naphthalenesulfonate (ANS), sodium 2‐(p‐toluidinyl) naphthalenesulfonate (TNS), rhodamine B (RhB), and brilliant green (BG), were investigated by ultraviolet, fluorescence, circular dichroism, and 2D NMR spectroscopy. The results indicated that the two linked CD units cooperatively bound to a guest, and the molecular binding affinity toward substrates, especially curved guest ANS and linear guests such as NR and AR, was increased. The linker length between two CD units played a crucial role in the molecular recognition of the hosts with guest dyes. The binding constants of the hosts for AR, TNS, ANS, and RhB decreased with increasing linker length in hosts 2‐4 . Moreover, structurally similar hosts 3 and 5 exhibited very different binding behavior for the guests. Host 5 showed much higher Ks values toward positively charged guests and lower Ks toward negatively charged guests than host 3 . The 2D NMR spectra of hosts 3 and 5 with RhB were acquired to understand the binding difference between 3 and 5 . The molecular binding ability and selectivity of model substrates by these hosts were sufficiently investigated to reveal not only the cooperative contributions of the linker group and CD cavities upon inclusion complexation with dye guest molecules, but also the controlling factors for the molecular selective binding. Copyright © 2008 John Wiley & Sons, Ltd.     

Theoretical insights into the host–guest interactions between [6]cycloparaphenyleneacetylene and its anthracene‐containing derivative and fullerene C70

The host–guest complexes formed with [6]cycloparaphenyleneacetylene ([6]CPPA) and its anthracene‐containing derivative ([6]CPPAs) hosts and fullerene C₇₀ guest were explored by density functional calculations. Besides two previously reported configurations in which C₇₀ guest is standing or lying in the cavity of the host, we found a new kind of configuration in which C₇₀ guest is half‐lying in the cavity of the host. More interestingly, the calculated results revealed that the fine‐tuning deformations occur readily during the formations of the complexes, suggesting that both [6]CPPA and [6]CPPAs are highly elastic host molecules. The large host–guest binding energies indicate that both two host molecules, [6]CPPA and [6]CPPAs, have excellent encapsulation ability for C₇₀ guest, and the [6]CPPAs even has much better encapsulation ability for C₇₀ than [6]CPPA. Furthermore, the host–guest interactions regions were detected and visualized in real space based on the electron density and reduced density gradient. Additionally, ¹H NMR spectra of those three different kinds of configurations mentioned earlier have been calculated with gage‐independent atomic orbital method, which may be helpful for further experimental characterizations in future. Copyright © 2014 John Wiley & Sons, Ltd.     

The guest-induced oscillation of a monolayer composed of polypeptide containing beta-cyclodextrin at the terminal

We prepared a rod-like amphiphile with a molecular recognition end group, alpha-helical and hydrophobic poly(gamma-methyl L-glutamate) (PMG) containing hydrophilic beta-cyclodextrin (CyD) as an active end group (PMG-CyD), and formed its monolayer at the n-hexane/water interface. The interfacial pressure (pi)-area (A) isotherms of the monolayer showed that alpha-helix rod of PMG-CyD could be vertically oriented at the oil/water interface, facing the hydrophilic terminal CyD group to the water phase, by increasing the interfacial concentration of the polypeptide. Under the condition 2-p-toludinyl-naphthalene-6-sulfonate (TNS), an intimate guest molecule for the CyD in water was introduced into the water phase beneath the monolayer. Within a minute the monolayer began to oscillate which could be monitored by the rhythmic response of the interfacial pressure of the monolayer. The oscillation continued over ten minutes and then terminated. The mode of the oscillation was found to change with time, i.e., the initial stage showing a periodic sharp reduction in the interfacial pressure (period I), the second stage having sharp increase in the pi value (period II), and the last stage of irregular oscillations (period III). The Fourier analysis of each period also supported the three stages during the oscillatory process. It was also found that when the alpha-helix rod of PMG-CyD lay down in the monolayer, the guest TNS did not induce any changes in the interfacial tension. This nonlinear rhythmic interfacial phenomenon was explained in terms of the periodic movement of the PMG-CyD monolayer resulting from the binding and releasing of the guest TNS across the oil/water interface. (c) 1999 American Institute of Physics.     

A study of a moleculartweezer host-guest system by a combination of quantum-chemical calculations and solid-state NMR experiments

A study of a host-guest system consisting of a naphthalene-spaced tweezer with a 1,4 dicyanobenzene guest molecule is presented. The complex is investigated using a combination of quantum-chemical calculations and solid-state NMR experiments. The advantages of such an approach are illustrated. The focus is on the calculation of (1) 1H NMR and (2) 13C NMR chemical shifts for model fragments of the solid-state structure, (3) the analysis of host-guest interactions important for molecular recognition, and (4) the investigation of the process of a guest molecule rotation. For modeling the solid-state structure, up to three host-guest units are considered and the convergence with respect to the size of the solid-state fragment is investigated.     

竞争包结法研究β-环糊精及其衍生物对灯盏花乙素的选择键合

以酚酞作为光谱探针,采用紫外-可见光谱滴定法测定了β-环糊精(β-CD),单(6-脱氧-乙二胺)-β-环糊精(en-β-CD),单(6-脱氧-二乙基三胺)-β-环糊精(dien-β-CD),羟丙基-β-环糊精(HP-β-CD),磺丁基醚-β-环糊精(SBE-β-CD)在30℃时,pH=10.50的0.025mol/L缓冲液中与灯盏花乙素所形成超分子配合物的稳定常数。结果表明,多种弱相互作用力协同作用于环糊精的配位过程,主-客体间的尺寸匹配决定所形成配合物的稳定性,环糊精衍生物的取代基影响主体的配位能力。5种环糊精主体化合物对灯盏花乙素客体分子的包合能力大小为:β-CDSBE-β-CDen-β-CDdien-β-CDHP-β-CD。     

Detection and classification of host–guest interactions using β-cyclodextrin-decorated carbon nanotube-based chemiresistors

Carbon nanotubes (CNTs) in a chemiresistor setup have been widely explored in bio/chemical sensing. Detection of certain molecules with environmental and health related importance such as 9-anthracenecarboxylic acid, diclofenac sodium, and curcumin using electrochemical methods/unfunctionalized CNTs suffer from lack of response, high limit of detection (LOD) and poor selectivity. The key to overcome these issues is to decorate CNTs with host (receptor) molecules like β-cyclodextrin (β-CD) that interact with guest (target) molecules by host–guest complex formation. To improve guest recognition, and consequently, the sensor performance, effective immobilization of β-CD on the CNT surface using a non-covalent bridging molecule such as 3, 4, 9, 10-perylene tetracarboxylic acid (PTCA) is required. Furthermore, the selectivity can be assessed using the conductance correlation patterns of different host–guest systems in conjunction with a pattern classification tool. Our results indicate that PTCA linked β-CD-decorated CNT chemiresistors showed a good linear detection range (∼100 pM–100 nM), sensitivity (∼3 × 10⁻³–9 × 10⁻² nM⁻¹) and LOD (∼62 pM–101 nM), compared to devices without PTCA, in the detection of the guest molecules. The distinction in correlation patterns of different host–guest systems was corroborated by pattern classification yielding a classification accuracy, sensitivity, and specificity of ∼91.83%, ∼90.13%, and ∼85.39%, respectively.     

2，6—双二苯基膦吡啶银（I）配合物的光谱研究

利用电子吸收光谱和发射光谱，研究具有光致发光性能的三配位Ag(I)配合物[Ag2(μ-PNP）3](ClO4)2(PNP=2,6-双二苯基膦吡啶）的光谱性质，电子吸收光谱中约260和300nm处的肩峰吸收分别被指定为l→aπ（l代表膦的孤对电子，aπ是苯环的反键轨道）和l→π^*（π^*表示吡啶的π反键轨道）跃迁。室温下受紫外可见光激发，配合物的乙腈溶液显示了发光性质，其发射峰位于525nm，这是由配体激发态引起的。利用吸收和发射光谱，研究了配合物光物理性质在不同客体分子如AuPPh3Cl,AgCF3SO3和[Cu(CH3CN)4](ClO4)存在下光物理性质的改变情况。在配合物中，配体PNP和Ag(I)形成一个空穴，可以结合外来的离子，从而引起光物理性质的改变，这种改变，使[Ag2(μ-PNP)3](ClO4)2可以作为作为客体离子的检测探针或传感器。     

Preferential intercalation of isomeric but-2-enedioate anions into the layered double hydroxides

Intercalation of cis-but-2-enedioate anion or trans-but-2-enedioate anion into the layered double hydroxide (LDH), [Mg_0.66Al_0.34(OH)₂]Cl_0.34·0.43H₂O was carried out by the method of ion-exchange procedures. Selective reaction was observed in competitive experiments involving an equal concentration pairs of acids. The trans-but-2-enedioate anion is preferentially intercalated into the Mg-Al-LDH. The obtained intercalation compounds were characterized by X-ray diffraction, infrared and thermogravimetry techniques. The charge density on the oxygens of each of the carboxylate groups for both anions was investigated utilizing ab initio (HF/6-31G) method by G98w. From the X-ray diffraction data, the guest size and the charge density of the oxygen of the guest, the orientation of both anions between the layers was determined and the preferential intercalation mechanism was studied. These results indicate the possibility of a molecular recognition ability of LDHs.     

Molecular Recognition of 1,5 Diamino Anthraquinone by <Emphasis Type="Italic">p</Emphasis>-tert-butyl-Calix(8)arene

The molecular recognition properties of p-tert-butyl-calix(8)arene with 1,5 -diamino anthraquinone (1,5 DAAQ) were studied by using UV–Visible and Fluorescence spectroscopic techniques. The binding constant was determined by using the Benesi-Hilde brand expression. It was found that the host–guest complex was formed between 1,5 DAAQ and p-tert-butyl- calix(8)arene in the 1:2 Stoichiometry ratio.