八元瓜环与二(2-亚甲基-1,2,3,4-四氢异喹啉)的自组装模式

以用1,2,3,4-四氢喹啉和二溴乙烷合成的二(2-亚甲基-1,2,3,4-四氢异喹啉)的溴化氢酸盐为客体, 八元瓜环为主体, 利用1H NMR技术, 单晶X射线衍射方法以及理论计算等方法, 考察了两者的自组装模式. 1H NMR分析结果表明, 在溶液状态条件下, 不仅每一个八元瓜环分子同时与两个客体分子的芳环部分相互作用, 而且每一个客体分子两端的芳环部分同时与两个八元瓜环分子相互作用, 从而形成一维的自组装超分子链; 而在固体状态下, 每一个八元瓜环也可同时包结两个客体的芳环部分而形成三元的自组装结构, 但八元瓜环包结两个客体形成一独立的三元自组装结构. 利用晶体结构建立模型的计算结果说明, 模拟溶液状态比固体状态条件下的主客体包结更有利于体系能量的降低, 与主客体在溶液中1H NMR实验结果相符.     

Synthesis and inclusion properties study of some mono 6-amino ??-cyclodextrin dimers bridged by N,N-succinyldiamide linkers

Methylated and partially methylated cyclodextrin homo- and heterodimers linked by diamidosuccinic bridges were synthesised and their inclusion properties were evaluated using NMR and isothermic microcalorimetric measurements ITC. The selective binding of ligands, such as bisadamantyl derivatives, to the cavities of unprotected cyclodextrin dimers showed the equimolar formation of bidendate inclusion complexes (2:2, two ligand guest to two cavities host).     

NMR study of host–guest complexes of disulfonated derivatives of 9, 10-diphenylanthracene and corresponding endoperoxides with cyclodextrins

Disulfonated derivatives of 9,10-diphenyl anthracene (dsDPA) are known carriers of singlet oxygen. DsDPA and corresponding endoperoxides (dsDPAO₂) form host–guest complexes with native cyclodextrins (i.e. β-CD and γ-CD). The modes of host–guest interaction were studied by ¹H NMR and 2D-NMR (ROESY). Specific inclusions of phenyl groups of dsDPA/dsDPAO₂ into the cyclodextrin cavities were found for both β-CD and γ-CD. The mode of interaction depends on the size of the CD cavity and the position of the sulfonate group.     

Distribution and modification of sorption sites in amphiphilic calixarene-based solid lipid nanoparticles from hyperpolarized 129Xe NMR spectroscopy

The site distribution and accessibility in amphiphilic calixarenes-based solid lipid nanoparticles were determined as a function of lipid chain length using in situ 129Xe NMR spectroscopy with flowing hyperpolarized Xe gas. The study illustrates that host cavities in as-prepared materials are increasingly occluded by the lipid chain for compounds with chain lengths from C6 to C12 and are almost completely occluded for C14 and C16 chain lengths. Host cavities present at the surface of the particles are still accessible to small atoms (xenon) and organic molecules (methylene chloride, etc). The Xe spectra show that the accessible void space can be increased remarkably by exposure of the particle surface to suitably sized guest molecules that appear to displace the occluding hydrocarbon chains from the host cavities by competitive adsorption. This postsynthesis treatment thus modifies the state of self-assembly and improves sorption capability. The HP Xe NMR approach presented is suitable for small samples (a few milligrams) of SLNs, likely also for other biomaterials such as vesicles, model membranes, etc.     

Dendronized copolymers functionalized with crown ethers and their reversible modification through host–guest interaction

Crown ether‐functionalized dendronized copolymers with an alternating structure were synthesized by free radical copolymerization of styrene derivatives pendent with Percec‐type polyether dendron of two generations and maleimide pendent with dibenzo[24]crown‐8 (24C8). Novel dendronized copolymers bearing tremendous host molecular cavities have been characterized by ¹H NMR, ¹³C NMR spectroscopy, static light scattering (SLS), and differential scanning calorimetry (DSC) analysis as well as atomic force microscopy (AFM) techniques. Host–guest interactions between 24C8 units dispersed along the dendronized copolymers and organic ammonium salts of pyrene, anthracene, and phenol have been explored. These molecular recognition processes can be monitored by ¹H NMR spectroscopy and fluorescence excitation spectroscopy. These results showed that the supramolecular polymer systems are acid–base controllable, demonstrating that dendronized copolymers may be modified reversibly via host–guest interaction. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Structural and Dynamical Properties of n-Alkane Molecules in Clathrate Phase of Syndiotactic Polystyrene

Syndiotactic polystyrene (sPS) forms a clathrate phase with a variety of compounds. Not only rigid molecules but also flexible molecules can be stored in the cavities of the clathrate phase. To clarify the adjustment mechanism of a flexible guest molecule to the sPS clathrate system, the host and guest structures were investigated by means of solid-state ¹³C NMR and Raman spectroscopy, and X-ray diffractometry for the sPS clathrates with a series of n-alkanes from n-hexane to n-decane. Although the 010 spacing of the host sPS lattice expanded slightly on going from n-hexane to n-heptane, it decreased markedly at n-octane and then increased gradually with the chain length of guest n-alkane. The conformational change of guest n-alkane molecules was involved in this anomalous change in the 010 spacing. Majority of the n-hexane and n-heptane molecules took extended chain structures in the clathrates, whereas all longer n-alkanes took bent chain structures. The mean-square displacement of hydrogen atoms in the clathrates was estimated by quasielastic neutron scattering experiments. It was confirmed that the host lattice contraction suppressed thermal motion of the clathrate system.     

A fluorescent, shape-persistent dendritic host with photoswitchable guest encapsulation and intramolecular energy transfer

A fluorescent and photoresponsive host based on rigid polyphenylene dendrimers (PPDs) has been synthesized. The key building block for the divergent dendrimer buildup is a complex tetracyclone 12 containing azobenzenyl, pyridyl, and ethynyl entities. The rigidity of polyphenylenes is of crucial importance for a site-specific placement of different functions: eight azobenzene (AB) moieties into the rigid scaffold, a fluorescent perylenetetracarboxdiimide (PDI) into the core, and eight pyridin functions into the interior cavities. AB moieties of host-1 undergo reversible cis-trans photoisomerization and are photostable, as confirmed by various techniques: UV-vis, (1)H NMR, size exclusion chromatography, and fluorescence correlation (FCS). In this system, AB moieties act as photoswitchable hinges and enable control over (i) molecular size, (ii) intramolecular energy transfer between AB and PDI, and (iii) encapsulation and release of guest molecules. The presence of PDI allows not only following the effect of cis-trans photoisomerization on molecular size with highly sensitive FCS but also monitoring the efficiency of the intramolecular energy transfer process (from AB to PDI) by time-resolved optical spectroscopy. Pyridyl functions were incorporated to facilitate guest uptake via hydrogen bonds between the host and guests. Also, we have demonstrated that the photoswitchability of the host can be utilized to actively encapsulate guest molecules into its interior cavities. This novel, light-driven encapsulation mechanism could enable the design of new drug delivery systems.     

Highly organized spherical hosts that bind organic guests in aqueous solution with micromolar affinity: microcalorimetry studies

Two novel closed-shell hemicarcerand-like hosts with spherical cavities of 11 A diameter that are soluble in aqueous solution were constructed. The binding of xylenes, aryl ethers, polyaromatic compounds, ferrocene derivatives, and bicyclic aliphatic compounds were examined by NMR spectroscopy and microcalorimetry. NMR binding studies indicated that binding depended upon guest hydrophobicity and shape. No binding was detected for guests in which a charge must be desolvated as part of inclusion or for guests that can not fit within the cavity of the host. Three complexes 2.naphthalene, 2.p-xylene, and 2.ferrocene were isolated and found to be indefinitely stable in the solid phase and in aqueous solution. The binding constants for these complexes are estimated to be greater than 10(8) M-1. Thirteen guests were examined by microcalorimetry with binding constants ranging between 10(7) and 10(3) M-1. A comparison of results obtained here with those from previous work with beta-cyclodextrin and cyclophane hosts, along with analysis of the entropy-enthalpy compensation data, indicate that there is a higher degree of guest desolvation with this host structure than with open-shell hosts. This accounts at least partially for the increase in affinity observed with these closed-shell hosts. Replacing a hydroxy group in the host portal with a hydrogen atom does not affect the binding constant, a finding consistent with the guest residing deeply buried within the host cavity. It was observed that aromatic guests are bound with higher affinity than aliphatic ones in agreement with results that point to the importance of London dispersion forces in the association of aromatic components in face-to-edge orientations. The correlation of changes in NMR chemical shift with microcalorimetry data supports a model in which increased CH-pi interactions strengthen association between host and guest due to the dominant role of van der Waals dispersion forces. Remarkably, the binding constant for the 1,4 isomer of dimethoxybenzene is 32 times higher than for the 1,2 isomer, and even greater discrimination is observed between the xylene guests since the binding constant for p-xylene is 80 times greater than that for o-xylene. This discrimination between isomeric guests by a rigid host indicates that changes in specific hydrophobic interactions have substantial effects upon binding affinity.     

Structure of a 4:1:4 supramolecular assembly of neutral TiiiiPO cavitands and tetrakis(N-methylpyridinium)porphyrin iodide

Four tetraphosphorylated TiiiiPO cavitands 1 encapsulate the pyridinium heads of a tetrakis(N-methylpyridinium)porphyrin iodide to form a 4:1:4 (host)4/guest4+/4I- complex. The single-crystal X-ray diffraction analysis shows the arrangement of the four cavities bound to the CH3N+ groups of the porphyrin moiety and the four iodide anions nested between the phenethyl substituents of the hosts. 1H NMR investigations show that the structure is preserved in chloroform solution and underscore the effect of the counteranions.     

Host/Guest Chemistry of Organic Onium Compounds—Clathrates,Crystalline Complexes,and Molecular Inclusion Compounds in Aqueous Solution

The importance of organic onium compounds for host/guest interactions in biological processes has been long recognized. In contrast, the versatility of synthetic onium compounds as host molecules in abiotic chemistry has only been investigated in detail for the last few years. Due to their inclusion ability and selectivities, organic ammonium, pyridinium, and phosphonium salts and other organic salts with specific structural features are interesting as clathrate-forming molecules. The crystal structures of the clathrates afford insight into the conformational adaptability of onium clathrands with limited flexibility to the geometric requirements of the guest molecules. Optically active onium hosts can be used for enantiomeric enrichment. In crystalline tetracyanoquinodimethane(TCNQ) complexes and radical anion salts, the structure of the organic heterocation has a marked effect on the electrical conductivity. Macrocyclic onium compounds of the phane type with “exohydrophilic” and “endolipophilic” cavities are suitable as models of enzymes and biological receptors. They can also be used to transfer aromatic and aliphatic guest molecules selectively into aqueous solution. Catalytic activity (including H/D exchange) has already been obtained with synthetic compounds having large cavities. The further development of such host/guest systems may contribute to the understanding of biological systems and the improvement of technical processes (catalysis in molecular cavities).     

Simulations of Guest Transport in Clathrates of Dianin’s Compound and Hydroquinone

Clathrates have been proposed for use in a variety of applications including gas storage, mixture separation and catalysis due to the potential for controlled guest diffusion through their porous lattices. Here molecular dynamics simulations are employed to study guest transport in clathrates of hydroquinone (HQ) and Dianin’s compound (DC). Systems investigated were HQ with methanol and acetonitrile, and DC with methanol and ethanol. Simulations were set up with one guest in the pore, two guests in the pore and one vacancy in the pore and a filled pore, and free‐energy barriers for movement between cavities of the pore were estimated for all cases. Comparison between these simulations indicates that guest transport most likely proceeds by molecules moving from full to empty cavities consecutively, one by one, rather than in a concerted manner. Thus, the presence of empty cavities is very important for guest transport, which becomes more energetically demanding in fully loaded systems. Flexibility of the host can assist guest transport. In the studied DC clathrates transport occurs via an intermediate conformation in which the hydroxyl group of the alcohol guest molecule participates in the hydrogen‐bonded ring of the host. We also address the issue of the number of methanol guest molecules that DC accommodates, for which conflicting information exists. We found that this is likely to be temperature dependent and suggest that under some conditions the system is most likely non‐stoichiometric.     

Binding Affinity of Novel Cyclodextrin Dimers to Ethyl Orange

The interaction between ethyl orange (Eto, guest) and β-cyclodextrin dimers (1a～d, host) bridged with 2-t-butoxycarbonyl(Boc)-amino diacid was investigated. A remarkable synergic complexation of two cavities in host molecule was observed.     

Host–guest supramolecular polymers constructed of aniline derivatives and three-dimensional coordination polymers [(n-Bu3Sn)2(R3Sn)Fe(CN)6] n,R = n-Bu or Ph

The straightforward self-assembly reaction of R₃Sn⁺ and [Fe(CN)₆]^3? affords three-dimensional (3-D) coordination polymers [(n-Bu₃Sn)₂(R₃Sn)Fe(CN)₆] _n , R = n-Bu(I) or Ph(II). The architecture of these coordination polymers is closely related to zeolite and acts as a host with wide internal cavities or channels capable of encapsulating voluminous organic compounds. Aniline derivatives acting as guest are encapsulated within the cavities of the 3-D-polymeric hosts I and II by tribochemical reaction producing host–guest supramolecular polymers. The structures and physical properties of these hosts and their host–guest systems were investigated by elemental analysis, X-ray powder diffraction, IR, UV-vis, EPR, and magnetic measurements. The morphology of these systems was examined by scanning electron microscopy (SEM). The interesting feature of these host–guest supramolecular polymers is the enhanced electrical conductivities over those of the 3-D-coordination polymeric hosts upon encapsulation of conductive polymers within their cavities.     

Importance of packing coefficients of host cavities in the isomerization of open host frameworks: guest-size-dependent isomerization in cholic acid inclusion crystals with monosubstituted benzenes

The crystal structures of inclusion compounds of cholic acid (CA) with 28 monosubstituted benzenes have been systematically investigated. All of the crystals belong to the monoclinic space group P2(1) and have bilayer structures with one-dimensional molecular channels that can include guest compounds. They are classified into four types of host frameworks that depend on the conformations and stacking modes of the host compound. The host frameworks and the host-guest ratios depend primarily on the molecular volumes of the guest compounds. The packing coefficient of the host cavity (PCcavity), which is the volume ratio of the guest compound to the host cavity, is used to clarify the relationship between the guest volume and isomerization of the host frameworks. The value of PCcavity, for stable inclusion compounds lies in the range of 55-70%. Compounds out of this range induce isomerization of the host frameworks. The packing coefficients of other host-guest compounds, in which the guest components are included in the host cavities through steric dimensions and van der Waals forces, are also in this range. These results indicate that PCcavity is a useful parameter correlation for guest recognition and isomerization of the host frameworks.     

Fluorescence study of inclusion complexes between star-shaped cholic acid derivatives and polycyclic aromatic fluorescent probes and the size effects of host and guest molecules

Star-shaped host molecules containing two, three, and four cholic acid moieties have been used to form inclusion complexes with polycyclic aromatic hydrocarbon probes (guests) varying in size from four (pyrene) to five (benzo(e)pyrene) and seven aromatic rings (coronene) and investigated by steady-state fluorescence measurements and fluorescence lifetime techniques. The results indicated that these hydrophobic guest probes prefer to locate in the hydrophobic cavities formed by the host molecules in an aqueous solution. Further studies showed that the stoichiometric ratios of the complexes depended on the relative size of both the host and the guest. The complexes of 1:1 ratio (guest:host) were formed between pyrene and the host molecules of different sizes, while the complexes of 1:2 ratio (guest:host) were found for coronene in all cases. For benzo(e)pyrene with an intermediate size, the complexes with 1:1 and 1:2 ratios (guest:host) were formed depending on the relative sizes of the host molecules. The stability of the inclusion complexes was observed to change with the solvent polarity, indicative of an adaptation of the hydrophobicity of the host pockets to the polarity of the solvent. The formation of the complexes was driven by the solvophobic interactions.     

Thermoresponsive Supramolecular Dendronized Polymers

Combining the concepts of supramolecular polymers and dendronized polymers provides the opportunity to create bulky polymers with easy structural modification and tunable properties. In the present work, a novel class of side‐chain supramolecular dendronized polymethacrylates is prepared through the host–guest interaction. The host is a linear polymethacrylate (as the backbone) attached in each repeat unit with a β‐cyclodextrin (β‐CD) moiety, and the guest is constituted with three‐fold branched oligoethylene glycol (OEG)‐based first‐ (G1) and second‐generation (G2) dendrons with an adamantyl group core. The host and guest interaction in aqueous solution leads to the formation of the supramolecular polymers, which is supported with ¹H NMR spectroscopy and dynamic light scattering measurements. The supramolecular formation was also examined at different host/guest ratios. The water solubility of hosts and guests increases upon supramolecular formation. The supramolecular polymers show good solubility in water at room temperature, but exhibit thermoresponsive behavior at elevated temperatures. Their thermoresponsiveness is thus investigated with UV/Vis and ¹H NMR spectroscopy, and compared with their counterparts formed from individual β‐CD and the OEG dendritic guest. The effect of polymer concentration and molar ratio of host/guest was examined. It is found that the polar interior of the supramolecules contribute significantly to the thermally‐induced phase transitions for the G1 polymer, but this effect is negligible for the G2 polymer. Based on the temperature‐varied proton NMR spectra, it is found that the host–guest complex starts to decompose during the aggregation process upon heating to its dehydration temperature, and this decomposition is enhanced with an increase of solution temperature.     

Clathrate inclusiom compounds of bis(isothiocyanato) tetrakis (4-methylpyridine) nickel II: II. Arrangement of guest molecules in the β-Ni(NCS)2(4-methylpyrldine)4 porous crystals

In this paper crystal structures of three tetragonal 14₁/a β-Ni(NCS)₂(4-Methylpyridine)₄ clathrates containing p-xylene (1:1), m-xylene (1:1) and methanol (2:1 mole of guest/mole of host), respectively, as the guest components are reported and discussed.The guest molecules were found to occupy centrosymmetric cavities in the hoat structure. Non-centrosymmetric m-xylene molecules are disordered to at least two orientations interrelated by inversion; methanol molecules enter the cavities as centrosymmetric pairs.     

1H NMR chemical shift calculations as a probe of supramolecular host-guest geometry

The self-assembled supramolecular host [Ga(4)L(6)](12-) (1; L = 1,5-bis[2,3-dihydroxybenzamido]naphthalene) can encapsulate cationic guest molecules within its hydrophobic cavity and catalyze the chemical transformations of bound guests. The cavity of host 1 is lined with aromatic naphthalene groups, which create a magnetically shielded interior environment, resulting in upfield shifted (1-3 ppm) NMR resonances for encapsulated guest molecules. Using gauge independent atomic orbital (GIAO) DFT computations, we show that (1)H NMR chemical shifts for guests encapsulated in 1 can be efficiently and accurately calculated and that valuable structural information is obtained by comparing calculated and experimental chemical shifts. The (1)H NMR chemical shift calculations are used to map the magnetic environment of the interior of 1, discriminate between different host-guest geometries, and explain the unexpected downfield chemical shift observed for a particular guest molecule interacting with host 1.     

Guest–host chemistry with dendrimers: Stable polymer assemblies by rational design

A new type of guest has been designed and synthesized for the exo‐type supramolecular functionalization of adamantyl‐urea‐terminated poly(propylene imine) dendrimers. This new type of guest motif features a uriedo methane sulfonic acid moiety that binds very selectively to the surfaces of dendrimers via a combination of noncovalent interactions forming well‐defined complexes. The guest–host properties have been examined for a fifth‐generation adamantyl‐urea‐functionalized poly(propylene imine) dendrimer capable of binding 32 guest molecules and for a model host molecule that can bind only one guest molecule. The guest–host chemistry has been studied with ¹H NMR spectroscopy, nuclear Overhauser enhancement spectroscopy NMR spectroscopy, T₁‐relaxation NMR experiments, and IR spectroscopy. The 1:32 ratio with the dendrimer has been confirmed unambiguously from ¹H NMR spectra of the complex after size exclusion chromatography. Competition experiments with guests bearing a carboxylic acid instead of a sulfonic acid in the binding motif have demonstrated that the sulfonic acid has superior binding strength. Also, the importance of a combination of noncovalent interactions has been shown via competition experiments with a guest lacking the uriedo moiety. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3792–3799, 2004     

Mechanism of Host–Guest Complex Formation and Identification of Intermediates through NMR Titration and Diffusion NMR Spectroscopy

The formation of host–guest (H‐G) complexes between 1,8‐bis[(diethylgallanyl)ethynyl]anthracene (H) and the N‐heterocycles pyridine and pyrimidine (G) was studied in solution using a combination of NMR titration and diffusion NMR experiments. For the latter, diffusion coefficients of potential host–guest structures in solution were compared with those of tailor‐made reference compounds of similar shape (synthesized and characterized by NMR, HRMS, and in part XRD). Highly dynamic behavior was observed in both cases, but with different host–guest species and equilibria. With increasing concentrations of the pyridine guest, the equilibrium H₂?H₂κ¹‐G₁?HG₂ is observed (in the second step a host dimer coordinates one guest molecule); for pyrimidine the equilibrium H₂→H₁κ²‐G₁?HG₂ is observed (the formation of a 1:1 aggregate is the second step).