Face-selective [2]- and [3]rotaxanes: kinetic control of the threading direction of cyclodextrins

New [2]- and [3]pseudorotaxanes containing alpha-cyclodextrin (alpha-CDs) molecules as rotors and alkyl pyridinium derivatives as axles were prepared by a slipping process. The inclusion behavior of these rotaxanes was investigated by using one- and two-dimensional NMR spectroscopy. The methyl group at the 2-position of the pyridinium moiety at the end of each axle molecule was found to control the rates of threading of the alpha-CD onto the axle molecules. alpha-CD can approach axle molecules from a particular direction to form inclusion complexes. Axle molecules that contain a 2-methylpyridinium moiety at one end and a bulky stopper at the other end can regulate the direction of approach to give a [2]pseudorotaxane such as 2 b-alpha-CD. A [3]pseudorotaxane in which two alpha-CD molecules are arranged facing in the same direction at two stations of the tetracationic axle molecule was also obtained. These face-selective behaviors are dominated by kinetic processes rather than thermodynamic processes.     

Supramolecular design for multivalent interaction: maltose mobility along polyrotaxane enhanced binding with concanavalin A

High molecular mobility of maltose-conjugated alpha-cyclodextrins (alpha-CDs) along a poly(ethylene glycol) (PEG) chain due to the mechanically locked structure of polyrotaxanes enhanced multivalent interactions between maltose and concanavalin A (Con A). When maltose groups are conjugated with alpha-CDs that were threaded onto a PEG capped with benzyloxycarbonyl l-tyrosine (polyrotaxane), Con A-induced hemagglutination was greatly inhibited by polyrotaxanes with a certain threading % of alpha-CDs. Such an inhibitory effect was significantly superior to the other type of conjugates, in which poly(acrylic acid) was used as a backbone for maltose conjugation. The spin-spin relaxation time (T2) of the maltose C(1) proton in the polyrotaxane at a typical alpha-CD threading % was significantly larger than that of any other conjugate, which was well related to the inhibitory effect. Therefore, we concluded that the high mobility of maltose groups along the polyrotaxane structure contributes to enhanced Con A recognition.     

Triply fused Zn(II)-porphyrin oligomers: synthesis, properties, and supramolecular interactions with single-walled carbon nanotubes (SWNTs)

The photophysical, electrochemical, and self-assembly properties of a novel triply fused Zn(II)-porphyrin trimer were investigated and compared to the properties of a triply fused porphyrin dimer and the analogous monomer. The trimer exhibited significantly red-shifted absorption bands relative to the corresponding monomer and dimer. Electrochemical investigations indicated a clear trend in redox properties amongst the three porphyrin structures, with the lowest oxidation potential and the lowest HOMO-LUMO gap exhibited by the triply fused trimer. This electrochemical behavior is attributed to the extensive pi-electron delocalization in the trimeric structure relative to the monomer and dimer. Additionally, it was found that the trimer forms extremely strong and nearly irreversible supramolecular interactions with single-walled carbon nanotubes (SWNTs), resulting in stable solutions of porphyrin-nanotube complexes in THF. Formation of these complexes required the addition of trifluoroacetic acid (TFA) to the solvent. This allowed the oligomers to make close contact with the nanotubes, enabling the formation of stable supramolecular assemblies. Atomic force microscopy (AFM) was used to observe the supramolecular porphyrin-nanotube complexes and revealed that the porphyrin trimer formed a uniform coating on the SWNTs. Height profiles indicated that nanotube bundles could be exfoliated into either individual tubes or very small bundles by exposure to the porphyrin trimer during sonication.     

Spatial arrangement of alpha-cyclodextrins in a rotaxane. Insights from free-energy calculations

The rotaxane formed by alpha-cyclodextrins (alpha-CDs) threaded onto a poly(ethylene glycol) (PEG) chain was investigated in the gas phase and in an aqueous solution by means of molecular dynamics simulations. The free-energy difference between the three possible spatial arrangements of consecutive alpha-CD--viz.. head-to-head (HH), head-to-tail (HT), and tail-to-tail, was determined using free-energy perturbation calculations. These simulations reveal that the interaction of alpha-CD with the PEG chain is very similar in the two surroundings, whereas the mutual interaction of the macrocycles is stronger in the gas phase than in the aqueous solution. Moreover, difference in the overall interaction appears to stem primarily from changes in the electrostatic contribution. Analysis of intermolecular hydrogen bonds indicates that hydrogen bonds created between alpha-CD and water molecules weaken the hydrogen-bonding interaction of adjacent alpha-CDs. Comparison of the free-energy differences characteristic of the three possible spatial arrangements of contiguous alpha-CDs reveals that the HH motif of the rotaxane is the most stable in the gas phase due to the hydrogen-bond formation between the secondary hydroxyl groups of the two alpha-CDs, and the slight preference for the HT motif in aqueous solution, which can be related to the directionality of the dipole moment borne by the macrocycles in these two motifs.     

Relative rotational motion between alpha-Cyclodextrin Derivatives and a stiff axle molecule

Novel [2]rotaxanes bearing alpha-cyclodextrin (alpha-CD) derivatives and a diphenylacetylene axis molecule with trinitrobenzene as a bulky stopper have been prepared to investigate the relative rotary movement of a ring relative to an axis molecule and that of an axis molecule in a ring by NMR techniques. [2]Rotaxanes 2 and 3 were composed of alpha-CD derivatives (2: 6-phenyl-amide-alpha-CD; 3: 6-stilbene-amide-alpha-CD). The protons of alpha-CDs in rotaxanes were thoroughly assigned by the two-dimensional NMR techniques (TOCSY, COSY, ROESY, HMQC, and HMBC). The protons of alpha-CD in rotaxane 1 did not show splitting, whereas the resonance peak shifts and splitting for the corresponding protons of alpha-CD derivatives in rotaxanes 2 and 3 were observed by the shielding and deshielding effects from a diphenylacetylene axis molecule. The splitting of resonance peaks was closely related to the rotary movements of alpha-CDs and an axis molecule. We supposed that alpha-CD in rotaxane 1 rotates freely around a diphenylacetylene axis molecule, and vice versa, whereas the rotary movement of alpha-CD derivatives and the axis molecules of rotaxanes 2 and 3 were restricted by the steric repulsion between the substituent group of alpha-CD and the stopper group of an axis molecule. To estimate the relative rotary movement of CDs and an axis molecule in rotaxanes, the rotational correlation time (tauc) of rotaxanes was measured by 13C NMR. The results indicate that the corresponding rotary movement of the modified alpha-CD and the axis molecules in rotaxanes 2 and 3 depends on the size of the substituent group.     

Application of tetrahydrofuran dispersant in microemulsion for fabricating titania mesoporous thin film

A new strategy was used to fabricate titania mesoporous thin film by incorporating tetrahydrofuran (THF) into the CTAB/n-butyl alcohol/cyclohexane/water reverse microemulsion as a micelle disperser. Highly dispersed and congregated TiO(2) particles in the microemulsion with and without THF were observed by transmission electron microscopy (TEM), respectively. The photographs observed by field-emission scanning electron microscopy (FE-SEM) show that a uniform titania mesoporous thin film with monodisperse TiO(2) spherical nanoparticles of ca. 20 nm was obtained using the microemulsion with THF.     

Preparation of alpha-cyclodextrin-terminated polyrotaxane consisting of beta-cyclodextrins and pluronic as a building block of a biodegradable network

A beta-CD-based biodegradable polyrotaxane was prepared by capping both terminals of polypseudorotaxane consisting of hydrazide-terminated PEG-block-PPG-block-PEG (Pluronic P-105) and beta-CD-succinates with mono-aldehyde alpha-CDs. By decreasing pH, the fluorescent intensity of TNS was increased with time, indicating cleavage of the terminal hydrazone bonds followed by beta-CD-succinate release. The terminal alpha-CD moieties of the polyrotaxane are useful for self-assembled formation with some guest molecules. [Diagram: see text]     

Noncovalent functionalization and solubilization of carbon nanotubes by using a conjugated Zn-porphyrin polymer

A highly soluble, conjugated Zn-porphyrin polymer was synthesized and found to strongly interact with the surface of single-walled carbon nanotubes, producing a soluble polymer-nanotube complex. Successful complexation required the addition of trifluoroacetic acid to the solvent (THF). It was found that the complex remained soluble after excess free polymer was removed from solution, and could be centrifuged at high speed with no observable sedimentation. Furthermore, the polymer-nanotube assembly resulted in enhanced planarization and conjugation within the porphyrin polymer, which was manifested in a 127 nm bathochromic shift of the Q-band absorption. Control experiments with the Zn-porphyrin monomer indicated that homogeneous solutions could be prepared by means of sonication, but the monomer-nanotube interactions were significantly weaker, leading to nanotube precipitation within minutes. Atomic force microscopy (AFM) studies indicated that the polymer enables exfoliation of nanotube bundles and is able to "stitch" multiple nanotubes together into a series of long, interconnected strands.     

Gold nanoparticles coated with semi-fluorinated oligo(ethylene glycol) produce sub-100 nm nanoparticle vesicles without templates

Gold nanoparticles (NPs) with diameters of 5, 10, and 20 nm coated with semifluorinated oligo(ethylene glycol) ligands were formed into sub-100 nm hollow NP assemblies (NP vesicles) in THF without the use of a template. The NP vesicles maintained their structure even after the solvent was changed from THF to other solvents such as butanol or CH(2)Cl(2). NMR analyses indicated that the fluorinated ligands are bundled on the NPs and that the solvophobic feature of the fluorinated bundles is the driving force for NP assembly. The formed NP vesicles were surface-enhanced Raman scattering-active capsules.     

Supramolecular self-assembly of inclusion complexes of a multiarm hyperbranched polyether with cyclodextrins

A new class of crystalline inclusion complexes of a multiarm hyperbranched polyether combined with various cyclodextrins (CDs) was successfully prepared. Using self-condensing ring-opening polymerization, a kind of multiarm polyether with a hyperbranched poly(3-ethyl-3-oxetanemethanol) core and multiple linear poly(ethylene glycol) (PEG) arms was obtained. It has been found that this kind of hyperbranched polyether can be dissolved in water. Adding alpha-CDs to the multiarm hyperbranched polyether solution, molecular recognition results in the formation of crystalline inclusion complexes based on the noncovalent interactions between the linear PEG arms of the polyether particles and the alpha-CDs. These multiarm polyether inclusion complexes have been well characterized. Interestingly, quite different from inclusion complexes of CDs and linear polymeric guests, the complexes of the multiarm hyperbranched polyether with alpha-CDs show a novel lamellar morphology. The experimental results validate that the resultant lamellar crystals have a juxtaposed structure. In addition, the formation mechanism of these inclusion complexes of a multiarm polyether with alpha-CDs has also been well described. Besides the role of displacement of associated water molecules and the presence of hydrogen bonding between CDs in channel structure CD inclusion complexes, the noncovalent intermolecular forces between CDs and polymers also play an important role in the formation of complex architectures.     

超声法制备硫化铅/二氧化硅核壳结构亚微米粒子

0 引言 纳米微粒具有的小尺寸效应,表面效应、量子尺寸效应及宏观量子隧道效应等导致纳米粒子的热、磁、光、敏感特性和表面稳定性等不同于常规粒子,这就使得它具有广阔的应用前景.     

Synthesis of reversible fluorescent organogel containing 2-(2′-hydroxyphenyl)benzoxazole: fluorescence enhancement upon gelation and detecting property for nerve gas simulant

A new low molecular mass organogelator 1 containing 2-(2′-hydroxyphenyl)benzoxazole (HPB) group with long alkyl chain was synthesized by the reaction with 5-amino-2-(2′-hydroxy-4′-methylphenyl)benzoxazole and dodecyl isocyanate in THF at room temperature. The reversible gelation ability of 1 was investigated using a heating-cooling method in various organic solvents. The stable organogel was formed from carbon tetrachloride or from cyclohexane at the concentration as low as 0.9%. The self-assembled supramolecular gel structure formed by non-covalent bonding was confirmed with field emission-scanning electron microscope (FE-SEM) exhibiting fibril- or ribbon-shaped structure depending on the solvent used. Regarding the aggregation-induced emission enhancement (AIEE) phenomenon, the optical properties were investigated in its solution and gelled state. The detecting properties of resulting organogel toward nerve gas simulant were monitored by UV-vis and fluorescence spectroscopy. Both color change from colorless to greenish yellow and disruption of gel structure resulting from alteration in intermolecular forces were observed upon the exposure to nerve gas simulant.     

Formation of ordered mesoporous films from in situ structure inversion of azo polymer colloidal arrays

This work shows that mesoporous polymeric films with spherical and elliptical pores can be obtained by in situ structure inversion of the azo polymer colloid arrays through selective interaction with solvent. The epoxy-based azo polymer contained both the pseudo-stilbene-type azo chromophores and the hydrophilic carboxyl groups. The colloidal spheres of the azo polymer were prepared by gradual hydrophobic aggregation of the polymeric chains in THF-H2O media, induced by a steady increase in the water content. Ordered 2D arrays of the hexagonally close-packed colloidal spheres were obtained by the vertical deposition method. After the solvent (THF) annealing, the ordered 2D arrays were directly transformed to mesoporous films through the sphere-pore inversion. Under the same condition, the 2D arrays composed of the ellipsoidal colloids, which were obtained by the irradiation of a polarized Ar+ laser beam on the colloidal sphere arrays, could be transformed to films with ordered elliptical pores. To our knowledge, this is the first example to demonstrate that mesoporous structures can be directly formed from the colloidal arrays of a homopolymer through structure inversion. This observation can shed new light on the nature of self-assembly processes and provide a feasible approach to fabricate mesoporous structures without the infiltration-removal step. By exploring the photoresponsive properties of the materials, mesoporous film with special pore structure and properties can be expected.     

钌掺杂MCM-48介孔分子筛的表征及催化氧化环己烷性能的研究

以在室温条件下快速制备的一系列Ru掺杂的MCM-48介孔分子筛为催化剂,进行了无溶剂条件下空气催化氧化环己烷制环己醇和环己酮的反应研究,并通过XRD、N2吸附脱附、FT-IR等多种表征手段对该催化剂进行系统研究.表征结果表明该催化剂具有典型的MCM-48介孔材料结构,合成过程中加入的Ru以不同形态同时存在于催化剂中.催化反应的结果显示该催化剂在较温和反应条件下具有良好催化活性,并且不同的Ru物种在反应中呈现不同的活性.     

Hartree-Fock and density functional theory study of alpha-cyclodextrin conformers

Herein, we report the geometry optimization of four conformers of alpha-cyclodextrin (alpha-CD) by means of PM3, HF/STO-3G, HF/3-21G, HF/6-31G(d), B3LYP/6-31G(d), and X3LYP/6-31G(d) calculations. The analysis of several geometrical parameters indicates that all conformers possess bond lengths, angles, and dihedrals that agree fairly well with the crystalline structure of alpha-CD. However, only three of them (1-3) resemble the polar character of CDs and show intramolecular hydrogen-bonding patterns that agree with experimental NMR data. Among them, conformer 3 appears to be the most stable species both in the gas phase and in solution; therefore, it is expected to be the most suitable representative structure for alpha-CD conformation. The purpose of selecting such a species is to identify an appropriate structure to be employed as a starting point for reliable computational studies on complexation phenomena. Our results indicate that the choice of a particular alpha-CD conformer should affect the results of ab initio computational studies on the inclusion complexation with this cyclodextrin since both the direction and the magnitude of the dipole moment depend strongly on the conformation of alpha-CD.     

Inclusion complex formation between alpha-cyclodextrin and biodegradable aliphatic polyesters

Inclusion complexes (ICs) between alpha-cyclodextrin (alpha-CD) and three kinds of biodegradable aliphatic polyesters with different sequence lengths of the monomeric repeating units poly(3-hydroxypropionate) [P(3HP)], poly(4-hydroxybutyrate) [P(4HB)] and poly(epsilon-caprolactone)(PCL) were prepared by mixing a solution of alpha-CD with that of the polymer, followed by stirring. The ICs were obtained as insoluble precipitates and characterized by FT-IR, WAXD and DSC. All measurements showed that the polymer chains of all three kinds of polyester were included into the alpha-CD cavity and formed ICs with different stoichiometries. WAXD patterns and thermal analysis indicated that these ICs possessed a channel structure and the crystallization of the polyester chains was suppressed upon inclusion into the alpha-CD cavity.     

四氢呋喃聚合介孔催化剂Zr-PHTS合成、表征及反应性能

在水-有机溶剂复合体系中,以P123为结构导向剂水热直接合成了锆掺杂介孔固体酸催化剂(Zr-PHTS),运用XRD、TEM、N2吸附-脱附以及NH3-TPD、Py-FTIR等手段对催化剂进行了表征.结果表明,在硅锆摩尔比20-100考察范围内,所得Zr-PHTS样品均显示有序二维六方晶相结构,具有以L酸为主的中等强度的酸性中心;随着锆引入量的变化Zr-PHTS的比表面积仅显示少量的变化,孔径维持在9.8 nm;在四氢呋喃聚合反应中Zr-PHTS显示出较好的催化活性,硅锆摩尔比30的样品表现出最佳的催化性能,聚合物收率达到40.4%,数均分子量2 135,推测催化剂表面酸性和孔结构决定了催化剂对四氢呋喃的聚合性能.     

Novel bifunctional periodic mesoporous organosilicas, BPMOs: synthesis, characterization, properties and in-situ selective hydroboration-alcoholysis reactions of functional groups

A new class of bifunctional periodic mesoporous organosilicas (BPMOs) containing two differently bonded organic moieties in a mesoporous host has been synthesized and characterized. By incorporating bridge-bonded ethylene groups into the walls and terminally bonded vinyl groups protruding into the channel space, both the chemistry and physical properties of the resulting BPMO could be modified. The materials have periodic mesoporous structures in which the bridging ethylene plays a structural and mechanical role and the vinyl groups are readily accessible for chemical transformations. The vinyl groups in the material underwent hydroboration with BH(3).THF and the resulting organoborane in the BPMO was quantitatively transformed into an alcohol using either H(2)O(2)/NaOH or NaBO(3).4H(2)O. The materials retained ordered structures after subsequent in situ reactions with largely unchanged pore volumes, specific surface areas and pore size distributions. Other organic functionalized BPMO materials may be synthesized in a similar manner or by further functionalizing the resulting borylated or alcohol functionalized BPMO materials. The thermal properties of the BPMO materials have also been investigated and are compared to those of the periodic mesoporous organosilica (PMO) materials. Noteworthy thermal events concern intrachannel reactions between residual silanols or atmospheric oxygen and organics in BPMOs. They begin around 300 degrees C and smoothly interconvert bridging ethylene to terminal vinyl groups and terminal vinyl to gaseous ethene and ethane, ultimately producing periodic mesoporous silica at 900 degrees C that exhibits good structural order and a unit-cell size decreased relative to that of the parent BPMO.     

Precursor-induced hydrothermal synthesis of flowerlike cupped-end microrod bundles of ZnO

Flowerlike cupped-end ZnO microrod bundles have been hydrothermally synthesized from precursor ZnCl2(N2H4)2 in sheet shape at 140 degrees C for 12 h; under the same conditions using the same precursor in rod shape, uniform ZnO nanorods were obtained. XRD pattern indicated the sample is ZnO with hexagonal cell contants a = 3.251 A and c = 5.206 A. FE-SEM and TEM show the formation process of the ZnO sample. HRTEM revealed that the flowerlike cupped-end ZnO microrod bundles grow along the [101] axis. The UV emission peak at approximately 396 nm and the blue band emission peak at approximately 469 nm were observed by PL spectra. A possible formation mechanism was proposed.     

Chiral recognition ability of alpha-cyclodextrin with regard to some monoterpenoids under gas-liquid chromatographic conditions

Gas-liquid chromatography was applied to investigate the mechanism of alpha-cyclodextrin (alpha-CD) complexation processes with some chiral monoterpenoids differing from each other in chemical properties and structure. They were chosen from hydrocarbons, alcohols, aldehydes and ketones of acyclic, monocyclic and bicyclic structure. The relationships between the retention factor, k, of a guest solute (G) and alpha-CD concentration were studied. The obtained data enabled the stoichiometry, the stability of individual complexes and the separation factor of enantiomers to be determined. It was found that almost all the investigated monoterpenoids, apart from the acyclic ones, form inclusion complexes with alpha-CD. Straight-line relations (r vs. [alpha-CD]) were observed for monocyclic alcohols and pulegone, without any trace of enantioselectivity. This behaviour indicates that the 1:1 stoichiometry of the G-CD complexes does not lead to chiral recognition. Parabolic relations arising from 1:2 stoichiometry were found for limonene, alpha-phellandrene, some monocycylic ketones and all the investigated bicyclic terpenoids. It appeared that only the second step of complexation displayed marked enantioselectivity. However, a loss of efficiency resulting from slower equilibration is then noticeable. Attempts are made to rationalize the chromatographic results with respect to the structure of the investigated compounds.