Limitations and Extensions of the Lock-and-Key Principle: Differences between Gas State,Solution and Solid State Structures

The lock-and-key concept is discussed with respect to necessary extensions. Formation of supramolecular complexes depends not only, and often not even primarily on an optimal geometric fit between host and guest. Induced fit and allosteric interactions have long been known as important modifications. Different binding mechanisms, the medium used and pH effects can exert a major influence on the affinity. Stereoelectronic effects due to lone pair orientation can lead to variation of binding constants by orders of magnitude. Hydrophobic interactions due to high-energy water inside cavities modify the mechanical lock-and-key picture. That optimal affinities are observed if the cavity is only partially filled by the ligand can be in conflict with the lock-and-key principle. In crystals other forces than those between host and guest often dominate, leading to differences between solid state and solution structures. This is exemplified in particular with calixarene complexes, which by X-ray analysis more often than other hosts show guest molecules outside their cavity. In view of this the particular problems with the identification of weak interactions in crystals is discussed.     

β-环糊精超分子络合物的合成与表征

主要研究了β-环糊精分别与蒽酮、丙烯酸丁酯和三乙胺在水相中通过范德华力发生包合反应形成了主客体超分子络合物,并用核磁共振氢谱对络合物进行了表征。同时通过分子模拟计算,证实了发生包合反应的可行性。通过核磁共振分析给出了客体分子在环糊精空腔的可能构像。     

Kinetics Inside,Outside and Through Cucurbiturils

This review describes the kinetics at play in Cucurbituril (CB[n])/guest recognition within a very wide time frame, from picoseconds to days. We cover the kinetics of (1) radiative and non-radiative decays of fluorophores inside and outside CB[n]s, (2) guest motions in the CB[n] cavity, and (3) ingression, egression and threading mechanisms into, out of and through the macrocycles. We then show that the kinetics of guest release or capture can be controlled using CB[n]-capped mesoporous systems and micelles, or by coupling those processes to the kinetics of ancillary reactions. The last section is devoted to the latest examples of reactions catalyzed and inhibited by CB[n]s.     

Mechanism of Ir(ppy)3 Guest Exciton Formation with the Exciplex-Forming TCTA:TPBI Cohost within a Phosphorescent Organic Light-Emitting Diode Environment

Cohosts based on hole transporting and electron transporting materials often act as exciplexes in the form of intermolecular charge transfer complexes. Indeed, exciplex-forming cohosts have been widely developed as the host materials for efficient phosphorescent organic light-emitting diodes (OLEDs). In host–guest systems of OLEDs, the guest can be excited by two competing mechanisms, namely, excitation energy transfer (EET) and charge transfer (CT). Experimentally, it has been reported that the EET mechanism is dominant and the excitons are primarily formed in the host first and then transferred to the guest in phosphorescent OLEDs based on exciplex-forming cohosts. With this, exciplex-forming cohosts are widely employed for avoiding the formation of trapped charge carriers in the phosphorescent guest. However, theoretical studies are still lacking toward elucidating the relative importance between EET and CT processes in exciting the guest molecules in such systems. Here, we obtain the kinetics of guest excitation processes in a few trimer model systems consisting of an exciplex-forming cohost pair and a phosphorescent guest. We adopt the Förster resonance energy transfer (FRET) rate constants for the electronic transitions between excited states toward solving kinetic master equations. The input parameters for calculating the FRET rate constants are obtained from density functional theory (DFT) and time-dependent DFT. The results show that while the EET mechanism is important, the CT mechanism may still play a significant role in guest excitations. In fact, the relative importance of CT over EET depends strongly on the location of the guest molecule relative to the cohost pair. This is understandable as both the coupling for EET and the interaction energy for CT are strongly influenced by the geometric constraints. Understanding the energy transfer pathways from the exciplex state of cohost to the emissive state of guest may provide insights for improving exciplex-forming materials adopted in OLEDs.     

分子模拟技术在环糊精包结过程中的应用

环糊精具有疏水的空腔,可以选择性结合各种客体分子,形成稳定的包结物,在实验和理论研究中受到广泛的关注。本文总结了近年来分子模拟技术在环糊精包结过程中的应用,重点介绍半经验PM3方法、双层ONIOM方法及自然键轨道（NBO）分析方法。最后展望了分子模拟技术在环糊精领域的发展方向。     

Chiral graphene nanoribbon inside a carbon nanotube: ab initio study

The dispersion-corrected density functional theory (DFT-D) is applied for investigation of structure and electronic properties of a sulfur-terminated graphene nanoribbon (S-GNR) encapsulated in a carbon nanotube. Two mechanisms of accommodation of the GNR in the carbon nanotube, distortion of the nanotube cross-section into an elliptic shape accompanied by bending of the GNR and transformation of the GNR to a helical conformation, are analyzed. Three types of elastic distortions of the nanotube and encapsulated GNR are revealed depending on the ratio of the diameter of the nanotube cavity to the GNR width. Helical states of the GNR are shown to be stabilized by the van der Waals attraction of sulfur atoms at neighbouring edges of adjacent turns of the GNR. The results of calculations are correlated with the experimental observations for the S-GNR synthesized recently inside the carbon nanotube. The hybrid DFT calculations of band structures of zigzag GNRs terminated with different atoms demonstrate that as opposed to O- and H-GNRs, the S-GNR is metallic even when deformed inside carbon nanotubes. Possible applications of GNRs encapsulated in carbon nanotubes are discussed.     

Photoresponsive Crown Ethers. Part 11. Azobenzene-Pillared Cylindrical Macrocycle As a Photoresponsive Receptor

A cylindrical ionophore (1) in which two diaza-crown ethers are linked by two azobenzene pillars serves as a photoresponsive host molecule. In alkaline solution containing K⁺, (1) forms a cascade complex with dianionic guest molecules, but photoirradiated (1) which has a shortened cylinder cannot bind the guest molecules so effectively as (1). (1) solubilised in acidic aqueous solution by protonation of four tertiary nitrogens provides a hydrophobic cavity to bind several anionic azo dyes. The association is also suppressed by photoirradiation. The results indicate that parallel array of the azobenzene segments in (1) provides a host cavity and the photoinduced structural change is readily reflected by the association tendency. This is the first example for the photoresponsive inclusion complex.     

Catching a molecule at the air-water interface: Dynamic pore array for molecular recognition

As a soft and flexible porous structure, a pore array of a steroid cyclophane SC(OH), which consists of the rigid 1,6,20,25-tetraaza[6.1.6.1]paracyclophane ring connected to four steroid moieties (cholic acid) through flexible L-lysine spacers, was prepared at the air-water interface. As confirmed by surface pressure (π)-molecular area (A) isotherms, transition between open conformation and cavity conformation of the SC(OH) molecule was reversibly induced upon repeated compression and expansion of its monolayer at pH 11 where amino groups of the lysine residues are not fully deprotonated. Capture and release of an aqueous fluorescent guest (TNS) by SC(OH) was observed upon dynamic cavity formation through surface fluorescence spectroscopy. At pH 12, dynamic cavity formation of SC(OH) was sufficiently suppressed, and the capture and release of an aqueous TNS by the monolayer was not virtually observed. Lessened electrostatic repulsion between the SC(OH) molecules due to conversion of ammonium to free amine may prevent the cavity from reopening. The importance of dynamic nature of cavity formation on the guest binding was also proved by control experiments using SC(H), which cannot form cavity conformation at any surface pressures at both pH 11 and 12.     

Catching a molecule at the air-water interface: Dynamic pore array for molecular recognition

As a soft and flexible porous structure, a pore array of a steroid cyclophane SC(OH), which consists of the rigid 1,6,20,25-tetraaza[6.1.6.1]paracyclophane ring connected to four steroid moieties (cholic acid) through flexible L-lysine spacers, was prepared at the air-water interface. As confirmed by surface pressure (π)-molecular area (A) isotherms, transition between open conformation and cavity conformation of the SC(OH) molecule was reversibly induced upon repeated compression and expansion of its monolayer at pH 11 where amino groups of the lysine residues are not fully deprotonated. Capture and release of an aqueous fluorescent guest (TNS) by SC(OH) was observed upon dynamic cavity formation through surface fluorescence spectroscopy. At pH 12, dynamic cavity formation of SC(OH) was sufficiently suppressed, and the capture and release of an aqueous TNS by the monolayer was not virtually observed. Lessened electrostatic repulsion between the SC(OH) molecules due to conversion of ammonium to free amine may prevent the cavity from reopening. The importance of dynamic nature of cavity formation on the guest binding was also proved by control experiments using SC(H), which cannot form cavity conformation at any surface pressures at both pH 11 and 12.     

Nature and Size of Included Guest Molecule Determines Architecture of Crystalline Cyclodextrin Host Matrix

Owing to its annular shape, the cyclic hexasaccharide α-cyclodextrin (α-CD) can form inclusion complexes in aqueous solution. If these are crystallized, the guest molecules are invariably accommodated in the cavities of the host. Depending on size and molecular or ionic character of the guest, different crystal modifications are formed belonging to the herringbone or brick-type cage structures or to the channel structures. Small molecular guests lead to herringbone cages, small aromatic guests crystallize in brick-type cages whereas ionic and long molecular guests are enclosed in infinite channels. Thus, there is a clear dependence of crystal packing on the physical properties of the guest molecule. Polyiodide cocrystallizes with α-CD in different channel forms with iodine atoms arranged linearly in the channels. The packing of the channels is in tetragonal, hexagonal or sheet-like arrays, depending on counterions which are located in voids between the channels. If a α-CD is replaced by the larger β-CD (channel diameters 5 and 6.2 Å resp.), polyiodide now adopts a zigzag structure — a clear case of an influence of host matrix geometry on guest configuration.     

Formation of spheres and siliceous plugs in synthesizing MCF materials

The unique pore structure combined with its high pore volume and large pore size make MCF material attractive as a catalyst support related to reactions with large molecules or as a capsule for storing and controlled release of organic guest substances. By varying the amount of TEOS, or the stirring temperature or the aging conditions in the synthesis, spheres are formed among the products. Siliceous plugs inside the MCF structures can also be produced in case of aging the synthesis mixtures at relatively low temperatures in flasks in oil baths instead of using the autoclave procedure. If the aging temperature is relatively high (such as 80°C), normal MCF material is also obtainable with this simplified procedure. These observations provide a further possibility to tune the morphology and the textural properties of the MCF materials.     

"Host-guest" chemistry in the synthesis of ordered nonsiliceous mesoporous materials

On the basis of the consideration of "host-guest" chemistry, the interactions between guest molecules are highlighted in the synthesis of nonsiliceous mesoporous materials by the "soft-template" and "hard-template" approaches. A generalized "acid-base pair" concept is utilized in selecting appropriate guest molecules to prepare highly ordered mesoporous metal oxides, phosphates, and borates with diversified structures. Mesoscopically ordered polymer and carbon frameworks with uniformly large pore sizes are derived from the self-assembly of an organic surfactant with an organic guest. Properly building the guest unit and decorating the host are important in replicating ordered nonsiliceous single-crystal nanoarrays. Outlooks on the potential possibilities for synthesizing ordered mesoporous nonsiliceous materials are presented as well.     

超低温球阀的结构设计特点及安装要求

详述了超低温球阀的结构特点及设计:采用加长阀盖设计及滴水板设计、防火及防静电设计、阀腔泄压阀门密封圈的设计等。同时针对阀门密封圈的设计,重点介绍了单活塞密封和双活塞密封型式的结构特点及密封原理。并介绍了阀门安装注意事项,如阀门安装角度的要求、阀门泄压的方向要求等。     

Diffusional and orientational dynamics of various single terylene diimide conjugates in mesoporous materials

Mesoporous silica materials are ideally suited as host–guest systems in nanoscience with applications ranging from molecular sieves, catalysts, nanosensors to drug-delivery-systems. For all these applications a thorough understanding of the interactions between the mesoporous host system and the guest molecules is vital. Here, we investigate these interactions using single molecule spectroscopy (SMS) to study the dynamics of three different terylene diimide (TDI) dyes acting as molecular probes in hexagonal and lamellar mesoporous silica films. The diffusion behaviour in the hexagonal phase is represented by the trajectories of the single molecules. These trajectories are highly structured and thus provide information about the underlying host structure, such as domain size or the presence of defects inside the host structure. The three structurally different TDI derivatives allowed studying the influence of the molecular structure of the guest on the translational diffusion behaviour in the hexagonal phase and the lamellar phase. In the lamellar phase, the differences between the three guests are quite dramatic. First, two populations of diffusing molecules – one with parallel orientation of the molecules to the lamellae and the other with perpendicular orientation – could be observed for two of the TDI derivatives. These populations differ drastically in their translational diffusion behaviour. Depending on the TDI derivative, the ratio between the two populations is different. Additionally, switching between the two populations was observed. These data provide new insights into host–guest interactions like the influence of the molecular structure of the guest molecules on their diffusional as well as on their orientational behaviour in structurally confined guest systems.     

Soap-free emulsion polymerization of n-butyl acrylate in aqueous solution in the presence of α- and methylated β-cyclodextrin

Butyl acrylate, a relative hydrophobic monomer, was found to become completely water soluble simply by mixing with either α-cyclodextrin or methyl-β-cyclodextrin. The both cyclodextrins were found to form 1:1 host–guest complexes with butyl acrylate. The complexes formed exhibited similar supramolecular structures, i.e., butyl group of butyl acrylate included in the cavity of cyclodextrins, but the double bond of the monomer locating outside of the cavity. Association constant values for α-cyclodextrin and methyl-β-cyclodextrin were determined to be 407.3 and 45.8?L/mol, respectively, indicating the better fitting of butyl acrylate with α-cyclodextrin than with methyl-β-cyclodextrin. It was found that the addition of either α-cyclodextrin or methyl-β-cyclodextrin, even at very low concentration, could markedly improve the reaction rate, reduce the amount of coagulum, and narrow the molecular weight distribution and particle-size distribution, in which α-cyclodextrin exhibited a better effect on polymerizations because of its stronger interaction with the monomer.     

Effect of laminar flow on the rate of mass transfer inside cubical cavities

An electrochemical technique which involved measuring the limiting current of the cathodic reduction of potassium ferricyanide was used to study the rate of mass transfer inside a cubical cavity machined in the wall of a vertical rectangular duct. Variables studied were side length, physical properties of the solution and flow rate of the solution. The mass transfer coefficient was found to decrease with increasing cavity size; in all cases, the mass transfer coefficient inside the cavity was less than that at the duct wall. Mass transfer data inside the cavity were correlated by the equation Sh_c = 0.525 (Sc Re d_e/L)^0.33. Comparison of the present results with the results obtained using other cavity geometries shows that cavity geometry plays an important role in determining the rate of mass transfer inside the cavity.     

Mass Spectrometric Evaluation of β-Cyclodextrins as Potential Hosts for Titanocene Dichloride

Bent metallocene dichlorides (Cp₂MCl₂, M = Ti, Mo, Nb, …) have found interest as anti-cancer drugs in order to overcome the drawbacks associated with platinum-based therapeutics. However, they suffer from poor hydrolytic stability at physiological pH. A promising approach to improve their hydrolytic stability is the formation of host-guest complexes with macrocyclic structures, such as cyclodextrins. In this work, we utilized nanoelectrospray ionization tandem mass spectrometry to probe the interaction of titanocene dichloride with β-cyclodextrin. Unlike the non-covalent binding of phenylalanine and oxaliplatin to β-cyclodextrin, the mixture of titanocene and β-cyclodextrin led to signals assigned as [βCD + Cp₂Ti–H]⁺, indicating a covalent character of the interaction. This finding is supported by titanated cyclodextrin fragment ions occurring from collisional activation. Employing di- and trimethylated β-cyclodextrins as hosts enabled the elucidation of the influence of the cyclodextrin hydroxy groups on the interaction with guest structures. Masking of the hydroxy groups was found to impair the covalent interaction and enabling the encapsulation of the guest structure within the hydrophobic cavity of the cyclodextrin. Findings are further supported by breakdown curves obtained by gas-phase dissociation of the various complexes.     

Molecular tweezers as synthetic receptors: molecular recognition of cationic substrates; an insight into the mechanism of complexation

The results of ¹H NMR binding studies of mole-cular tweezers 1a with various aliphatic and aromatic cations in organic solvents are described. By the use of the viologene substrates 11 and 12 bearing bulky endgroups and therefore having a dumb-bell topology it could be demonstrated that besides the obvious mechanism of complexation in which the guest molecule enters the tweezer's cavity through the open sides of the host, a second mechanism is available in which the substrate enters the cavity through a gap emerging after a substantial spreading of the tweezer's tips by at least of about 280 pm.     

Cucurbit[n]uril Host-Guest Complexes of Acids,Photoacids, and Super Photoacids

The supramolecular chemistry of host-guest complexes of cucurbit[n]urils (CB[n]) with acidic guests in the ground (HG⁺) and excited states (HG⁺*) are reviewed. The effects of CB[n] complexation on the guests’ pK_a and/or pK_a* values are related to relative binding constants and host-guest structures of the acid form of the guest and its conjugate base. Included are carbon acids, guests of biological and medicinal interest, dyes and related polyaromatic guests, and other organic and organometallic guests. The applications of the pK_a shifts to the solubility, stability, and bioavailabilty of drug molecules, the stability and enhanced spectral properties of dyes, and in pH-induced self-sorting, micelle formation, host-guest shuttling, and controlled guest release, are discussed.     

β-环糊精与罗丹明B及番红花红T包合作用的研究

合成了以β-环糊精为主体,罗丹明B及番红花红T为客体的包合物.用红外光谱、荧光光谱、共振瑞利散射光谱和差示扫描量热谱研究了β-环糊精与染料的包合机理.实验结果表明:β-环糊精与客体分子分别形成了1:1的包合物,客体分子进入β-环糊精分子的疏水性空腔内,当β-环糊精加入到一定浓度的客体溶液中时,罗丹明B体系的荧光强度和共振瑞利散射强度减弱,而番红花红T体系的荧光强度和共振瑞利散射强度增强.还通过荧光光谱法及共振瑞利散射光谱法分别测定了15、25和35 ℃ 3个不同温度时染料与β-环糊精包合体系的稳定常数.结果表明:包合物的形成主要取决于β-环糊精与客体分子的分子结构及两者作用力的大小,β-环糊精空腔大小与客体分子或其某些基团的大小越接近,越容易包合,包合物的稳定常数就越大.包合物的表观热力学常数显示,在上述包合体系反应的推动力是疏水作用力.