Kinetics of molecular transport in a nanoporous crystal studied by confocal Raman microspectrometry: single-file diffusion in a densely filled tunnel

Confocal Raman microspectrometry has been used as an in situ probe of the transport of guest molecules along the one-dimensional tunnels in a crystalline urea inclusion compound, under conditions of guest exchange in which "new" guest molecules (pentadecane) are introduced at one end of the tunnel and displace the "original" guest molecules (1,8-dibromooctane). The Raman spectra, recorded as a function of position along the tunnel direction and as a function of time, have been used to establish details of the kinetics of the guest transport process. In particular, the transport of the new pentadecane guest molecules along the tunnel is found to exhibit a linear dependence on time, with the rate of the process in the region of 70-100 nm s-1. Mechanistic aspects relating to the guest transport process are discussed.     

Direct time-resolved and spatially resolved monitoring of molecular transport in a crystalline nanochannel system

Confocal Raman microspectrometry has been applied successfully as an in situ probe of the transport of guest molecules through the one-dimensional channel system in a crystalline inclusion compound, yielding insights into the spatial distribution of guest molecules and, in particular, the variation in the spatial distribution of the guest molecules as a function of time during the transport process.     

Infrared Spectroscopic Study of the Hofmann-daon-Type Clathrates : M(1,8-diaminooctane)Ni(CN)4⋅G (M=Co, Ni or Cd; G=Aromatic Guest Molecules)

Infrared spectra of M(1,8-diaminooctane)Ni(CN)4G (M= Co, Ni or Cd; G=benzene, chlorobenzene, toluene, p-xylene, naphthalene or biphenyl) compounds are reported. The 1,8-diaminooctane molecules in the host permit the inclusion of bulky guest molecules. The spectral features suggest that the compounds are similar in structure to the Hofmann-type clathrates.     

Amphiphilic Inclusion Spaces for Various Guests and Regulation of Fluorescence Intensity of 1,8‐Bis(4‐aminophenyl)anthracene Crystals

A host framework for inclusion of various guest molecules was investigated by preparation of inclusion crystals of 1,8‐bis(4‐aminophenyl)anthracene (1,8‐BAPA) with organic solvents. X‐ray crystallographic analysis revealed construction of the same inclusion space incorporating 1,8‐BAPA and eight guest molecules including both non‐polar (benzene) and polar guests (N,N‐dimethylformamide, DMF). Fluorescence efficiencies varied depending on guest molecule polarity; DMF inclusion crystals exhibited the highest fluorescence intensity (Φ_F=0.40), four times as high as that of a benzene inclusion crystal (Φ_F=0.10). According to systematic investigations of inclusion phenomena, strong host–guest interactions and filling of the inclusion space led to a high fluorescence intensity. Temperature‐dependent fluorescence spectral measurements revealed these factors effectively immobilised the host framework. Although hydrogen bonding commonly decreases fluorescence intensity, the present study demonstrated that such strong interactions provide excellent conditions for fluorescence enhancement. Thus, this remarkable behaviour has potential application toward sensing of highly polar molecules, such as biogenic compounds.     

PEO‐b‐PCL Block Copolymers: Synthesis,Detailed Characterization,and Selected Micellar Drug Encapsulation Behavior

Summary: A series of poly(ethylene glycol)‐block‐poly(ε‐caprolactone) diblock copolymers was synthesized and fully characterized. In particular, MALDI‐TOF MS results revealed interesting new insights into their molecular architecture. Small and defined micelles could be prepared from these block copolymers. Utilizing a high‐throughput screening approach, it was observed that these micelles are able to encapsulate/solubilize different guest molecules (e.g. drugs) depending on the solubility of the guest in water. Furthermore, it could be proven that a guest is located within a micelle and that these micelles can be utilized as transport vehicles for the encapsulated guest molecules.

PEO‐b‐PCL diblock copolymers can encapsulate small guest molecules in the core of the polymeric micelles.     

Ein neues makrobicyclisches Wirtmolekül-Synthese und ANS-Komplexierung

The synthesis of the new host molecule1b is described. Its complexation properties towards 1,8-ANS as a guest are reported. Compared to the monomacrocyclic host molecules2c and2e, the complex stabilities of1b with ANS as a guest are particularly higher, suggesting that the macrobicyclic host forms a better fitting niche to allow the nestling of guest molecules in solution.

     

Selective sensing and transport in bionic nanochannel based on macrocyclic host-guest chemistry

Imitating the signal transduction and transmembrane transport co ntrolled by biological channels in the cell membra ne,artificial nanochannels with a similar capability of sensing and transport are constructed as bionic nanochannels.To accomplish selective sensing and transport of biological analyte(as "guest"),the bionic nanochannels are modified with the artificial receptor(as "host"),Based on selective recognition between host and guest,bionic nanochannels translate the stimulus of the guest to electrochemical signal as sensors,and further regulate the transmission of guest as transporters.Howeve r,throughout all kinds of guests,the selective sensing and transpo rt of ions and chiral molecules is a challenging problem.And throughout all hosts of ions and chiral molecules,the macrocyclic hosts with multisite of recognition show better selectivity,such as crown ethers,cyclodextrins,calixarenes,and pillararenes.In this article,we highlight recent advances in the macrocyclic host-based nanochannels for the selective sensing and transport of ionic and chiral guests,summarize the similarities and differences of different kinds of macrocyclic host-based nanochannels,and expect the research direction and application prospect.     

Novel flexible frameworks of porous cobalt(II) coordination polymers that show selective guest adsorption based on the switching of hydrogen-bond pairs of amide groups

Four porous crystalline coordination polymers with two-dimensional frameworks of a double-edged axe-shaped motif, [[Co(NCS)(2)(3-pia)(2)] x 2 EtOH.11 H(2)O](n) (1 a), [[Co(NCS)(2)(3-pia)(2)] x 4 Me(2)CO](n) (3 a), [[Co(NCS)(2)(3-pia)(2)] x 4T HF](n) (3 b) and [[Co(NCS)(2)(3-pna)(2)](n)] (5), have been synthesized by the reaction of cobalt(II) thiocyanate with N-(3-pyridyl)isonicotinamide (3-pia) or N-(3-pyridyl)nicotinamide (3-pna). X-ray crystallographic characterization reveals that adjacent layers are stacked such that channels are created, except in 5. The channels form a hydrogen-bonded interior for guest molecules; in practice, 1 a contains ethanol and water molecules as guests in the channels with hydrogen bonds, whereas 3 b (3 a) contains tetrahydrofuran (acetone) molecules. In 1 a, the "double-edged axe-shaped" motifs in adjacent sheets are not located over the top of each other, while the motifs in 3 b stack so perfectly as to overlap each other in an edge-to-edge fashion. This subtle change in the three-dimensional framework is associated with the template effect of the guests. Compound 5 has no guest molecules and, therefore, the amide groups in one sheet are used for hydrogen-bonding links with adjacent sheets. Removal of the guest molecules from 1 a and 3 b (3 a) causes a structural conversion accompanied by a color change. Pink 1 a cannot retain its original framework and changes into a blue amorphous compound. On the other hand, the framework of pink 3 b (3 a) is transformed to a new crystalline framework of violet 4. Interestingly, 4 reverts to the original pink crystals of 3 b (3 a) when it is exposed to THF (or acetone) vapor. Spectroscopic measurements (visible, EPR, and IR) provide a clue to the crystal-to-crystal transformation; on removal of the guests, the amide groups are used to form the beta sheet-type hydrogen bonding between the sheets, and thus the framework withstands significant stress on removal of guest molecules. This mechanism is attributed to the arrangement of the adjacent sheets so suited in regularity that the beta sheet-type structure forms efficiently. The apohost 4 does not adsorb cyclopentane, showing a guest selectivity that, in addition to size, hydrogen-bonding capability is required for the guest molecules. The obtained compound is categorized as a member of a new generation of compounds tending towards functional porous coordination polymers.     

Raman spectra of gas hydrates--differences and analogies to ice 1h and (gas saturated) water

It is generally accepted that Raman spectroscopic investigations of gas hydrates provide vital information regarding the structure of the hydrate, hydrate composition and cage occupancies, but most research is focused on the vibrational spectra of the guest molecules. We show that the shape and position of the Raman signals of the host molecules (H(2)O) also contain useful additional information. In this study, Raman spectra (200-4000 cm(-1)) of (mixed) gas hydrates with variable compositions and different structures are presented. The bands in the OH stretching region (3000-3800 cm(-1)), the O-H bending region (1600-1700 cm(-1)) and the O-O hydrogen bonded stretching region (100-400 cm(-1)) are compared with the corresponding bands in Raman spectra of ice Ih and liquid water. The interpretation of the differences and similarities with respect to the crystal structure and possible interactions between guest and host molecules are presented.     

Liquid crystalline polyethers based on conformational isomerism. XIX. Synthesis and characterization of flexible polyethers based on 1-(4-hydroxyphenyl)-2-(2-r-4-hydroxyphenyl) ethane with H,F, CH3, Br,Cl, and CF3 as R groups

The synthesis of 1-(4-hydroxyphenyl)-2-(2-fluoro-4-hydroxyphenyl)ethane ( FBPE ), 1-(4-hydroxyphenyl)-2-(2-chloro-4-hydroxyphenyl)ethane ( CIBPE ), 1-(4-hydroxyphenyl)-2-(2-bromo-4-hydroxyphenyl)ethane ( BrBPE ), and 1-(4-hydroxyphenyl)-2-(2-trifluoromethyl-4-hydroxyphenyl)ethane ( CF₃BPE ), of the corresponding polymers based on 1,5-dibromopentane ( RBPE-5) , 1,8-dibromooctane ( RBPE-8 ), and of the copolymers based on various ratios of 1,5-dibromopentane and 1,8-dibromooctane [ RBPE-5/8(A/B )] is described. The phase transition temperatures and thermodynamic parameters of RBPE-5 and RBPE-8 polymers were compared to those of the corresponding polyethers based on 1,2-bis(4-hydroxyphenyl)ethane ( BPE ) and 1-(4-hydroxyphenyl)-2-(2-methyl-4-hydroxyphenyl)ethane ( MBPE ) which were reported previously. Both isotropic-nematic transition temperatures and corresponding thermodynamic parameters (i.e., enthalpy and entropy changes) decrease in the following order of the substituent R: H > F > CH₃ > Cl > Br > CF₃. This order corresponds to the increase of the breadth of the RBPE molecules, and agrees with the similar trends observed in low molar mass liquid crystals.     

Probing the limit of weak host-guest interactions: insertion compounds of mercury(II) halides with microporous SiO(2) hosts

Mercury(II) halides HgX(2) (X=Cl, Br, I) were inserted into the voids of the crystalline microporous SiO(2) modifications deca-dodecasil 3R (short term: DDR), silica-theta-1 (TON), silica-ferrierite (FER) and silicalite-1 (MFI) by vapour phase loading. The properties of the occluded guest species were studied by X-ray absorption spectroscopy (X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis), UV/Vis spectroscopy, and IR and Raman spectroscopy. The methods reveal the presence of HgX(2) molecules in the insertion compounds. The interactions between these electroneutral guest molecules and the electroneutral surrounding SiO(2) framework are weak. In addition, no indication of any significant guest-guest interaction between the embedded molecules was found, in contrast to the analogous iodine insertion compounds, where these become more important with increasing pore dimensionality (G. Wirnsberger et al., Angew. Chem. 1996, 108, 2951-2953; Angew. Chem. Int. Ed. Engl. 1996, 35, 2777). Analysis of the HgL(3) EXAFS confirms a coordination number of two for Hg and gives HgX bond lengths of 2.26 +/- 0.02, 2.38 +/- 0.02 and 2.57 +/- 0.02 A for the trapped HgCl(2), HgBr(2) and HgI(2) molecules, respectively. These values are very close to those of the corresponding molecules in the vapour phase and are the shortest determined for HgX(2) molecules in solid-state compounds to date (a comparably short distance only appears in the recently reported [Cu(2-pyrazinecarboxylato)(2)HgI(2)] x HgI(2) with d(Hg[bond]I)=2.577(2) A; Dong et al., Angew. Chem. 2000, 112, 4441-4443; Angew. Chem. Int. Ed. 2000, 39, 4271). Thus, there emerges a picture of almost unperturbed HgX(2) molecules, similar to those in the vapour phase or in non-coordinating solvents, in a solid crystalline matrix of high temperature stability, a very unusual state of matter. Despite the weakness of the host-guest interactions, investigations on small crystallites of the HgX(2)-TON composites using a Raman microscope show a strong polarization dependence, providing evidence for an orientational alignment of the HgX(2) molecules inside the one-dimensional pore system of this host. For these reasons, the host matrices used in this study can be viewed as orienting solid solvents, coordinating only very weakly to the inserted HgX(2) guest molecules, but exhibiting a strong geometrical template function for their alignment. The concept of using electroneutral SiO(2) modifications as host components for a modular construction of new host-guest compounds thus allows the designed construction of ordered guest assemblies, with the pore systems of the rigid host matrices acting as space-confining and ordering templates for the guest components.     

An infrared and raman spectroscopic study of metal(II) Di(2-methylpyridine) tetracyanonickelate complexes: Ni(C6H7N)2Ni(CN)4 and Cd(C6H7N)2Ni(CN)4

The results of an infrared and Raman spectroscopic study are reported for two new metal 2-methylpyridine tetracyanonickelate complexes, M(C₆H₇N)₂Ni(CN)₄, M=Ni or Cd. Their structure consists of corrugated polymeric layers of {M-Ni(CN)₄} with 2-methylpyridine molecules bound directly to the metal (M). These complexes can act as host lattices in the formation of inclusion compounds with dioxane guest molecules.     

Release from silica SBA-3-like mesoporous fibers: cross-wall transport and external diffusion barrier.

The transport of guest molecules between adjacent pore channels (cross-wall transport) is the limiting factor in the release of guest molecules from SBA-3-like fibers. This specific mode of diffusion is identified by microscopic observation and studied quantitatively in a UV/Vis-monitored release experiment. Analysis of release curves reveals that the external particle surface offers resistance to the guest molecules passing through it (external diffusion barrier). This barrier is native to as-synthesized fibers and can be effectively modified to slow down the release. Extremely effective slowdown is achieved by deposition of a nanometer-thick layer of sodium silicate, that is, the guest molecules are then safely stored in the particles.     

A nonlinear group contribution method for predicting the free energies of inclusion complexation of organic molecules with alpha- and beta-cyclodextrins

A group-contribution method was developed for calculating the binding constants or the free energies of complexation between native alpha- or beta-cyclodextrin (CD) and organic guest molecules. The nonlinear models for binary (1:1 stoichiometry) complexes of alpha- and beta-CDs were derived with squared correlation coefficients (r(2)) of 0.868 and 0.917 based on a database consisting of 102 and 218 diverse guest molecules, respectively. The parameters used in the models are first-order molecular connectivity index as a measure of molecular bulk and atom/group counts in the guest molecules. The models allow accurate estimations for the wide range of guests containing C, H, N, O, S, and/or all halogens by summing the contribution values of each defined group present in the chemical structure of the guest along with guest's molecular size factors (linear and square terms) and then the summation to a constant coefficient value. The predictive performance of the models was tested by extra set of 27 compounds which were not included in the original data set. The predicted values by the models are in good agreement with the experimentally determined data.     

Transport of Guest Molecules by Unimolecular Micelles Evidenced in Analytical Ultracentrifugation Experiments

The ability of star‐shaped, block copolymer‐based unimolecular micelles to encapsulate and transport guest molecules was studied. Analytical ultracentrifugation studies clearly showed that methyl‐orange guest molecules could be encapsulated and transported, together with unimolecular micelles consisting of 5‐arm, star‐shaped block copolymers with a poly(ethylene glycol) core and a poly(ε‐caprolactone) corona. Sedimentation‐velocity and equilibrium measurements were performed to determine the sedimentation coefficients, molar masses, and diffusion coefficients of the loaded, unimolecular micelles. It was observed that the transport of guest molecules by unimolecular micelles was a function of the molecular weight of the star‐shaped block copolymers and therefore also of their size.

     

Design of pi-conjugated organic materials for one-dimensional energy transport in nanochannels

Various end-substituted distyrylbenzenes have been synthesized to serve as guest molecules in inclusion compounds to promote efficient energy transport along one-dimensional channels. Their optical and photophysical properties have been characterized at both experimental and theoretical levels. All molecules display a large transition dipole moment between the ground state and lowest excited state and hence a short radiative lifetime (on the order of 1-2 ns). They also exhibit a large spectral overlap between the emission and absorption spectra, which enables efficient energy transport between molecules arranged in a head-to-tail configuration in nanochannels. Hopping rates on the order of 10(12) s(-1) are calculated at a full quantum-chemical level; this is much larger than the radiative lifetimes and opens the way for energy migration over large distances. Changes in the nature of the terminal substituents are found to modulate the optical properties weakly but to impact significantly the energy transfer rates.     

A study of DFT and surface enhanced Raman scattering in silver colloids for thymine

The vibrational spectrum of crystal thymine is calculated by density functional theory (DFT) at the B3LYP complex function. Considering the effect of intermolecular H-bonds, we add two water molecules that can form H-bonds with the CO and NH groups of thymine. The experimental spectra of normal Raman of thymine in solid state and surface enhanced Raman (SERS) of thymine adsorbed in silver colloids are presented in this study. The calculated Raman spectrum of thymine by DFT is in agreement with the experimental result of normal Raman spectrum. The appearance of new bands of thymine in SERS shows that molecules of thymine are adsorbed in the surface of silver nanoparticles with a perpendicular orientation through an oxygen atom (O7).     

Diffusion in coiled pores - learning from microrelease and microsurgery

The anisotropic diffusion in coiled pore systems of SBA-3-type microparticles has been studied by the release of guest molecules. The diffusion turns out as an example of the influence of hierarchical structuring on physical properties. Two modes of diffusion, associated with transport along and across the mesopores, can be identified and measured using optical microscopy. Redistribution between the two modes has been achieved by mesopore opening using two methods of "microsurgery"-either focused ion beams (FIB) or mechanical tools. The particles trimmed by FIB have revealed risks of misinterpretation of sample preparation with this tool. Instead of pure pore opening, the cutting by FIB resulted in simultaneous sealing of the mesopores.     

Load–Collapse–Release Cascades of Amphiphilic Guest Molecules in Charged Dendronized Polymers through Spatial Separation of Noncovalent Forces

The ability to pack guest molecules into charged dendronized polymers (denpols) and the possibility to release these guest molecules from subsequently densely aggregated denpols in a load–collapse–release cascade is described. Charged denpols, which constitute molecular objects with a persistent, well‐defined envelope and interior, are capable of incorporating large amounts of amphiphilic guest molecules. Simultaneously, multivalent ions can coordinate to the surfaces of charged denpols, leading to counterion‐induced aggregation of the already guest‐loaded host structures. Thus, although the local guest concentration in denpol‐based molecular transport might already be initially high due to the dense guest packing inside the dendritic denpol scaffolding, the “local” guest concentration can nonetheless be further increased by packing (through aggregation) of the host–guest complexes themselves. Subsequent release of guest compounds from densely aggregated dendronized polymers is then possible (e.g., through increasing the solution concentration of imidazolium‐based ions). Augmented with this release possibility, the concept of twofold packing of guests, firstly through hosting itself and secondly through aggregation of the hosts, gives rise to a load–collapse–release cascade that strikingly displays the high potential of dendronized macromolecules for future molecular transport applications.     

Molecular recognition of naphthalenediamine by polyamine modified β-cyclodextrin:yttrium metal complexes

The 6-OH group of β-cyclodextrin was modified by diethylene triamine and triethylene tetramine, respectively, mono[6-diethylenetriamino]-6-deoxy-β-cyclodextrin (DTCD) and mono[6-triethylenetetraamino]-6-deoxy-β-cyclodextrin (TTCD) were synthesized, which included 1,5-naphthalenediamine and 1,8-naphthalenediamine, respectively, in the presence of rare earth metal yttrium chloride. As a result, four ternary inclusion complexes (host–guest-metal) formed, which were characterized via ¹HNMR spectroscopy. The chemical shift variations of host and guest molecules were studied. The stoichiometric proportion of host and guest molecules is 2:1 for all the complexes. Signal degeneration still exists for the guest molecules after the inclusion process, which verifies the symmetrical conformation of guest molecules inside the cavities of two host molecules. All the four complexes exhibit “sandwich”-typed structure.