Supramolecular Drug Delivery Systems Based on Water-Soluble Pillar[n]arenes.

Science.gov (United States)

Wu, Xuan; Gao, Lei; Hu, Xiao-Yu; Wang, Leyong

2016-06-01

Supramolecular drug delivery systems (SDDSs), including various kinds of nanostructures that are assembled by reversible noncovalent interactions, have attracted considerable attention as ideal drug carriers owing to their fascinating ability to undergo dynamic switching of structure, morphology, and function in response to various external stimuli, which provides a flexible and robust platform for designing and developing functional and smart supramolecular nano-drug carriers. Pillar[n]arenes represent a new generation of macrocyclic hosts, which have unique structures and excellent properties in host-guest chemistry. This account describes recent progress in our group to develop pillararene-based stimuli-responsive supramolecular nanostructures constructed by reversible host-guest interactions for controllable anticancer drug delivery. The potential applications of these supramolecular drug carriers in cancer treatment and the fundamental questions facing SDDSs are also discussed. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tailored protein encapsulation into a DNA host using geometrically organized supramolecular interactions

Science.gov (United States)

Sprengel, Andreas; Lill, Pascal; Stegemann, Pierre; Bravo-Rodriguez, Kenny; Schöneweiß, Elisa-C.; Merdanovic, Melisa; Gudnason, Daniel; Aznauryan, Mikayel; Gamrad, Lisa; Barcikowski, Stephan; Sanchez-Garcia, Elsa; Birkedal, Victoria; Gatsogiannis, Christos; Ehrmann, Michael; Saccà, Barbara

2017-02-01

The self-organizational properties of DNA have been used to realize synthetic hosts for protein encapsulation. However, current strategies of DNA-protein conjugation still limit true emulation of natural host-guest systems, whose formation relies on non-covalent bonds between geometrically matching interfaces. Here we report one of the largest DNA-protein complexes of semisynthetic origin held in place exclusively by spatially defined supramolecular interactions. Our approach is based on the decoration of the inner surface of a DNA origami hollow structure with multiple ligands converging to their corresponding binding sites on the protein surface with programmable symmetry and range-of-action. Our results demonstrate specific host-guest recognition in a 1:1 stoichiometry and selectivity for the guest whose size guarantees sufficient molecular diffusion preserving short intermolecular distances. DNA nanocontainers can be thus rationally designed to trap single guest molecules in their native form, mimicking natural strategies of molecular recognition and anticipating a new method of protein caging.

Computations between metallocalix(4)arene host and a series of four oil-based fuel pollutant guests

International Nuclear Information System (INIS)

Pathak, D.A.; Street, N.C.

2006-01-01

Calculations using PM3 and mechanics methods on metallocalix(4)arene hosts (1-10) and substituted dibenzothiophene guests (A-D), which are generally known as oil-based fuel pollutants, show that host-guest formation is energetically favored. Calculations have been carried out for both 1/1 and 1/4 ratios of host/guest. There is no direct bonding between the metal center of the host and the sulfur of the guest in the host-guest complex. Sterically hundered dibenzothiophene guests show similar energies to the unhindered analogs. For calix(4)arenas (5-10) in partial cone conformations and having hydrogen rather than p-tert-butyl groups on the wide rim, host-guest formation occurs within the narrow rim rather than the wide rim. Host-guest association appears to occur via Pie-Pie interactions between host and guest phenyl groups rather than via metal-sulfur bonding. The study has importance especially in oil refining to obtain environmentally safe fuel oils and help supramolecular chemists in designing and synthesizing more sophisticated host molecules for the removal of sulfur from crude oil / refinery oil. (author)

Hydrogen bonding assemblies in host guest complexes with 18-crown-6

Science.gov (United States)

Fonari, M. S.; Simonov, Yu. A.; Kravtsov, V. Ch.; Lipkowski, J.; Ganin, E. V.; Yavolovskii, A. A.

2003-02-01

Recent X-ray crystal structural data for two novel 1:2 host-guest complexes of 18-crown-6 with neutral organic molecules, thiaamide hydrazide of 2-aminobenzoic acid and thiaamide hydrazide of 4-amino-1,2,5-thiadiazole-3-carbonic acid are reported. The supramolecular structures of these two and five relative complexes are discussed from the point of view of participation of donor groups in coordination with the crown ether, and donor and acceptor groups in the self-assembly of the guest molecules. Guest molecules have incorporated amine and hydrazine moieties as proton donors and carbonyl oxygen and sulfur (in thiadiazole and in thiaamine moieties) as proton acceptors. The guest-guest interactions appeared to be crucial in the final architecture.

Rotaxane and catenane host structures for sensing charged guest species.

Science.gov (United States)

Langton, Matthew J; Beer, Paul D

2014-07-15

anion-induced conformational change can be used as a means of signal transduction. Electrochemical sensing has been realized by integration of the redox-active ferrocene functionality within a range of rotaxane and catenanes; binding of an anion perturbs the metallocene, leading to a cathodic shift in the ferrocene/ferrocenium redox couple. In order to obtain practical sensors for target charged guest species, confinement of receptors at a surface is necessary in order to develop robust, reuseable devices. Surface confinement also offers advantages over solution based receptors, including amplification of signal, enhanced guest binding thermodynamics and the negation of solubility problems. We have fabricated anion-templated rotaxanes and catenanes on gold electrode surfaces and demonstrated that the resulting mechanically bonded self-assembled monolayers are electrochemically responsive to the binding of anions, a crucial first step toward the advancement of sophisticated, highly selective, anion sensory devices. Rotaxane and catenane host molecules may be engineered to offer a superior level of molecular recognition, and the incorporation of optical or electrochemical reporter groups within these interlocked frameworks can allow for guest sensing. Advances in synthetic templation strategies has facilitated the synthesis of interlocked architectures and widened their interest as prototype molecular machines. However, their unique host-guest properties are only now beginning to be exploited as a sophisticated approach to chemical sensing. The development of functional host-guest sensory systems such as these is of great interest to the interdisciplinary field of supramolecular chemistry.

Chiral Binaphthylbis(4,4'-Bipyridin-1-Ium)/Cucurbit[8]Uril Supramolecular System and Its Induced Circularly Polarized Luminescence.

Science.gov (United States)

Chen, Xu-Man; Chen, Yong; Liang, Lu; Liu, Qiu-Jun; Liu, Yu

2018-05-01

Circularly polarized luminescence (CPL) induced by host-guest complexation remains a challenge in supramolecular chemistry. Herein, a couple of CPL-silent enantiomeric guest binaphthylbis(4,4'-bipyridinium) salts can emit obvious CPL in the presence of cucurbit[8]uril in aqueous media, due to the restriction of molecular rotation limitation effect. Such CPL can be reversibly adjusted by the addition of acid and base. Furthermore, the resultant supramolecular systems can interact with DNA, accompanied by the morphological conversion from branched supramolecular nanowires to exfoliated nanowires, which can enable to the exploration of such supramolecular systems as DNA markers by CPL signals. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Field-induced detrapping in disordered organic semiconducting host-guest systems

NARCIS (Netherlands)

Cottaar, J.; Coehoorn, R.; Bobbert, P.A.

2010-01-01

In a disordered organic semiconducting host-guest material, containing a relatively small concentration of guest molecules acting as traps, the charge transport may be viewed as resulting from carriers that are detrapped from the guest to the host. Commonly used theories include only detrapping due

Mechanism of host-guest complexation by cucurbituril.

Science.gov (United States)

Márquez, César; Hudgins, Robert R; Nau, Werner M

2004-05-12

The factors affecting host-guest complexation between the molecular container compound cucurbit[6]uril (CB6) and various guests in aqueous solution are studied, and a detailed complexation mechanism in the presence of cations is derived. The formation of the supramolecular complex is studied in detail for cyclohexylmethylammonium ion as guest. The kinetics and thermodynamics of complexation is monitored by NMR as a function of temperature, salt concentration, and cation size. The binding constants and the ingression rate constants decrease with increasing salt concentration and cation-binding constant, in agreement with a competitive binding of the ammonium site of the guest and the metal cation with the ureido carbonyl portals of CB6. Studies as a function of guest size indicate that the effective container volume of the CB6 cavity is approximately 105 A(3). It is suggested that larger guests are excluded for two reasons: a high activation barrier for ingression imposed by the tight CB6 portals and a destabilization of the complex due to steric repulsion inside. For example, in the case of the nearly spherical azoalkane homologues 2,3-diazabicyclo[2.2.1]hept-2-ene (DBH, volume ca. 96 A(3)) and 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO, volume ca. 110 A(3)), the former forms the CB6 complex promptly with a sizable binding constant (1300 M(-1)), while the latter does not form a complex even after several months at optimized complexation conditions. Molecular mechanics calculations are performed for several CB6/guest complexes. A qualitative agreement is found between experimental and calculated activation energies for ingression as a function of both guest size and state of protonation. The potential role of constrictive binding by CB6 is discussed.

Driving Forces Controlling Host-Guest Recognition in Supercritical Carbon Dioxide Solvent.

Science.gov (United States)

Ingrosso, Francesca; Altarsha, Muhannad; Dumarçay, Florence; Kevern, Gwendal; Barth, Danielle; Marsura, Alain; Ruiz-López, Manuel F

2016-02-24

The formation of supramolecular host-guest complexes is a very useful and widely employed tool in chemistry. However, supramolecular chemistry in non-conventional solvents such as supercritical carbon dioxide (scCO2 ), one of the most promising sustainable solvents, is still in its infancy. In this work, we explored a successful route to the development of green processes in supercritical CO2 by combining a theoretical approach with experiments. We were able to synthesize and characterize an inclusion complex between a polar aromatic molecule (benzoic acid) and peracetylated-β-cyclodextrin, which is soluble in the supercritical medium. This finding opens the way to wide, environmental friendly, applications of scCO2 in many areas of chemistry, including supramolecular synthesis, reactivity and catalysis, micro and nano-particle formation, molecular recognition, as well as enhanced extraction processes with increased selectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbohydrates in Supramolecular Chemistry.

Science.gov (United States)

Delbianco, Martina; Bharate, Priya; Varela-Aramburu, Silvia; Seeberger, Peter H

2016-02-24

Carbohydrates are involved in a variety of biological processes. The ability of sugars to form a large number of hydrogen bonds has made them important components for supramolecular chemistry. We discuss recent advances in the use of carbohydrates in supramolecular chemistry and reveal that carbohydrates are useful building blocks for the stabilization of complex architectures. Systems are presented according to the scaffold that supports the glyco-conjugate: organic macrocycles, dendrimers, nanomaterials, and polymers are considered. Glyco-conjugates can form host-guest complexes, and can self-assemble by using carbohydrate-carbohydrate interactions and other weak interactions such as π-π interactions. Finally, complex supramolecular architectures based on carbohydrate-protein interactions are discussed.

Synthesis, structure, and properties of a series of chiral tweezer-diamine complexes consisting of an achiral zinc(II) bisporphyrin host and chiral diamine guest: induction and rationalization of supramolecular chirality.

Science.gov (United States)

Brahma, Sanfaori; Ikbal, Sk Asif; Rath, Sankar Prasad

2014-01-06

We report here the synthesis, structure, and spectroscopic properties of a series of supramolecular chiral 1:1 tweezer-diamine complexes consisting of an achiral Zn(II) bisporphyrin (Zn2DPO) host and five different chiral diamine guests, namely, (R)-diaminopropane (DAP), (1S,2S)-diaminocyclohexane (CHDA), (S)-phenylpropane diamine (PPDA), (S)-phenyl ethylenediamine (PEDA), and (1R,2R)-diphenylethylene diamine (DPEA). The solid-state structures are preserved in solution, as reflected in their (1)H NMR spectra, which also revealed the remarkably large upfield shifts of the NH2 guest protons with the order Zn2DPO·DAP > Zn2DPO·CHDA > Zn2DPO·PPDA> Zn2DPO·PEDA ≫ Zn2DPO·DPEA, which happens to be the order of binding constants of the respective diamines with Zn2DPO. As the bulk of the substituent at the chiral center of the guest ligand increases, the Zn-Nax distance of the tweezer-diamine complex also increases, which eventually lowers the binding of the guest ligand toward the host. Also, the angle between the two porphyrin rings gradually increases with increasing bulk of the guest in order to accommodate the guest within the bisporphyrin cavity with minimal steric clash. The notably high amplitude bisignate CD signal response by Zn2DPO·DAP, Zn2DPO·CHDA, and Zn2DPO·PPDA can be ascribed to the complex's high stability and the formation of a unidirectional screw as observed in the X-ray structures of the complexes. A relatively lower value of CD amplitude shown by Zn2DPO·PEDA is due to the lower stability of the complex. The projection of the diamine binding sites of the chiral guest would make the two porphyrin macrocycles oriented in either a clockwise or anticlockwise direction in order to minimize host-guest steric clash. In sharp contrast, Zn2DPO·DPEA shows a very low amplitude bisignate CD signal due to the presence of both left- (dictated by the pre-existing chirality of (1R,2R)-DPEA) and right-handed screws (dictated by the steric differentiation at

Host-guest complexes between cucurbit[n]urils and acetanilides having aminopropyl units.

Science.gov (United States)

Buaki-Sogo, Mireia; Montes-Navajas, Pedro; Alvaro, Mercedes; Garcia, Hermenegildo

2013-06-01

2-(Propylamino)acetamide of aniline (1a), and bis-2-(propylamino)acetamide of ortho- (1b) and para-(1c) phenylenediamine form host-guest complexes with CB[6], CB[7] and CB[8] as evidenced by the variations in the (1)H NMR spectroscopy chemical shifts and observation in MALDI-TOF-MS and ESI-MS of ions at the corresponding mass. Binding constants for the 1:1 complexes were estimated from fluorescence titrations and were in the range 10(5)-10(6)M(-1). Models based on molecular mechanics for these supramolecular complexes are provided. In spite of the different geometries arising from the ortho- or para-substitution, phenylenediamides form complexes of similar strength in which the hydrophobic alkyl chains are accommodated inside the host cavity. Formation of these host-guest complexes in the solid state was also achieved by modifying an aminopropyl silica with chloroacetanilides and preparing three silica having analogues of compounds 1a-c anchored to the solid particles. Titrations showed, however, that these solids can adsorb a large percentage of CBs by unselective interactions that are not related to the formation of inclusion complexes. Copyright © 2013 Elsevier Inc. All rights reserved.

Double level selection in a constitutional dynamic library of coordination driven supramolecular polygons.

Science.gov (United States)

Rancan, Marzio; Tessarolo, Jacopo; Casarin, Maurizio; Zanonato, Pier Luigi; Quici, Silvio; Armelao, Lidia

2014-07-21

A constitutional dynamic library (CDL) of Cu(II) metallo-supramolecular polygons has been studied as a bench test to examine an interesting selection case based on molecular recognition. Sorting of the CDL polygons is achieved through a proper guest that is hosted into the triangular metallo-macrocycle constituent. Two selection mechanisms are observed, a guest induced path and a guest templated self-assembly (virtual library approach). Remarkably, the triangular host can accommodate several guests with a degree of selectivity ranging from ∼1 to ∼10(4) for all possible guest pairs. A double level selection operates: guests drive the CDL toward the triangular polygon, and, at the same time, this is able to pick a specific guest from a set of competitive molecules, according to a selectivity-affinity correlation. Association constants of the host-guest systems have been determined. Guest competition and exchange studies have been analyzed through variable temperature UV-Vis absorption spectroscopy and single crystal X-ray diffraction studies. Molecular structures and electronic properties of the triangular polygon and of the host-guest systems also have been studied by means of all electrons density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations including dispersive contributions. DFT outcomes ultimately indicate the dispersive nature of the host-guest interactions, while TDDFT results allow a thorough assignment of the host and host-guests spectral features.

Proton Mediated Chemistry and Catalysis in a Self-Assembled Supramolecular Host

Energy Technology Data Exchange (ETDEWEB)

Pluth, Michael; Bergman, Robert; Raymond, Kenneth

2009-04-10

Synthetic supramolecular host assemblies can impart unique reactivity to encapsulated guest molecules. Synthetic host molecules have been developed to carry out complex reactions within their cavities, despite the fact that they lack the type of specifically tailored functional groups normally located in the analogous active sites of enzymes. Over the past decade, the Raymond group has developed a series of self-assembled supramolecules and the Bergman group has developed and studied a number of catalytic transformations. In this Account, we detail recent collaborative work between these two groups, focusing on chemical catalysis stemming from the encapsulation of protonated guests and expanding to acid catalysis in basic solution. We initially investigated the ability of a water-soluble, self-assembled supramolecular host molecule to encapsulate protonated guests in its hydrophobic core. Our study of encapsulated protonated amines revealed rich host-guest chemistry. We established that self-exchange (that is, in-out guest movement) rates of protonated amines were dependent on the steric bulk of the amine rather than its basicity. The host molecule has purely rotational tetrahedral (T) symmetry, so guests with geminal N-methyl groups (and their attendant mirror plane) were effectively desymmetrized; this allowed for the observation and quantification of the barriers for nitrogen inversion followed by bond rotation. Furthermore, small nitrogen heterocycles, such as N-alkylaziridines, N-alkylazetidines, and N-alkylpyrrolidines, were found to be encapsulated as proton-bound homodimers or homotrimers. We further investigated the thermodynamic stabilization of protonated amines, showing that encapsulation makes the amines more basic in the cavity. Encapsulation raises the effective basicity of protonated amines by up to 4.5 pK{sub a} units, a difference almost as large as that between the moderate and strong bases carbonate and hydroxide. The thermodynamic stabilization

Proton-Mediated Chemistry and Catalysis in a Self-Assembled Supramolecular Host

International Nuclear Information System (INIS)

Pluth, Michael; Bergman, Robert; Raymond, Kenneth

2009-01-01

Synthetic supramolecular host assemblies can impart unique reactivity to encapsulated guest molecules. Synthetic host molecules have been developed to carry out complex reactions within their cavities, despite the fact that they lack the type of specifically tailored functional groups normally located in the analogous active sites of enzymes. Over the past decade, the Raymond group has developed a series of self-assembled supramolecules and the Bergman group has developed and studied a number of catalytic transformations. In this Account, we detail recent collaborative work between these two groups, focusing on chemical catalysis stemming from the encapsulation of protonated guests and expanding to acid catalysis in basic solution. We initially investigated the ability of a water-soluble, self-assembled supramolecular host molecule to encapsulate protonated guests in its hydrophobic core. Our study of encapsulated protonated amines revealed rich host-guest chemistry. We established that self-exchange (that is, in-out guest movement) rates of protonated amines were dependent on the steric bulk of the amine rather than its basicity. The host molecule has purely rotational tetrahedral (T) symmetry, so guests with geminal N-methyl groups (and their attendant mirror plane) were effectively desymmetrized; this allowed for the observation and quantification of the barriers for nitrogen inversion followed by bond rotation. Furthermore, small nitrogen heterocycles, such as N-alkylaziridines, N-alkylazetidines, and N-alkylpyrrolidines, were found to be encapsulated as proton-bound homodimers or homotrimers. We further investigated the thermodynamic stabilization of protonated amines, showing that encapsulation makes the amines more basic in the cavity. Encapsulation raises the effective basicity of protonated amines by up to 4.5 pK a units, a difference almost as large as that between the moderate and strong bases carbonate and hydroxide. The thermodynamic stabilization of

Analysis of supramolecular surface nanostructures using secondary ion mass spectrometry (poster)

International Nuclear Information System (INIS)

Halaszova, S.; Velic, D.

2013-01-01

Our system consists of host molecules β-cyclodextrin (C 42 H 70 O 35 ), of implemented Iron nanoparticles (guest). Whole supramolecular complex is placed on a gold substrate. In our project we work with monotiolated β-cyclodextrin (C 42 H 70 O 34 S), consisting of seven α-D-1-4 glucopyranose units. Cyclodextrins have been selected deliberately because of their ability to form inclusion complexes .They are also capable of forming structures similar to self-assembly monolayers. To study the formation of these supramolecular surface nanostructures mass secondary ion spectrometry is used. With this technique fragmentation of monotiolated β-cyclodextrin and the presence of the supramolecular complex on a gold surface can be examined. The observed fragments of monotiolated cyclodextrines films can be divided into three groups: Au X H Y S Z , fragments originating from cyclodextrin molecules associated with Au. Fragments as (C 42 H 70 O 34 S)Na + , (C 42 H 70 O 35 )Na + and (AuC 42 H 69 O 34 S)Na + were identified as well as fragments thereof in cationized form with K + . The main objective of the project is a detailed study and preparation of supramolecular nanostructures consisting of complex guest-host monotiolated β-cyclodextrin host-iron), and a gold substrate. (Authors)

Controlling the Host-Guest Interaction Mode through a Redox Stimulus.

Science.gov (United States)

Szalóki, György; Croué, Vincent; Carré, Vincent; Aubriet, Frédéric; Alévêque, Olivier; Levillain, Eric; Allain, Magali; Aragó, Juan; Ortí, Enrique; Goeb, Sébastien; Sallé, Marc

2017-12-18

A proof-of-concept related to the redox-control of the binding/releasing process in a host-guest system is achieved by designing a neutral and robust Pt-based redox-active metallacage involving two extended-tetrathiafulvalene (exTTF) ligands. When neutral, the cage is able to bind a planar polyaromatic guest (coronene). Remarkably, the chemical or electrochemical oxidation of the host-guest complex leads to the reversible expulsion of the guest outside the cavity, which is assigned to a drastic change of the host-guest interaction mode, illustrating the key role of counteranions along the exchange process. The reversible process is supported by various experimental data ( 1 H NMR spectroscopy, ESI-FTICR, and spectroelectrochemistry) as well as by in-depth theoretical calculations performed at the density functional theory (DFT) level. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Through-Space Paramagnetic NMR Effects in Host-Guest Complexes: Potential Ruthenium(III) Metallodrugs with Macrocyclic Carriers.

Science.gov (United States)

Chyba, Jan; Novák, Martin; Munzarová, Petra; Novotný, Jan; Marek, Radek

2018-04-05

The potential of paramagnetic ruthenium(III) compounds for use as anticancer metallodrugs has been investigated extensively during the past several decades. However, the means by which these ruthenium compounds are transported and distributed in living bodies remain relatively unexplored. In this work, we prepared several novel ruthenium(III) compounds with the general structure Na + [ trans-Ru III Cl 4 (DMSO)(L)] - (DMSO = dimethyl sulfoxide), where L stands for pyridine or imidazole linked with adamantane, a hydrophobic chemophore. The supramolecular interactions of these compounds with macrocyclic carriers of the cyclodextrin (CD) and cucurbit[ n]uril (CB) families were investigated by NMR spectroscopy, X-ray diffraction analysis, isothermal titration calorimetry, and relativistic DFT methods. The long-range hyperfine NMR effects of the paramagnetic guest on the host macrocycle are related to the distance between them and their relative orientation in the host-guest complex. The CD and CB macrocyclic carriers being studied in this account can be attached to a vector that attracts the drug-carrier system to a specific biological target and our investigation thus introduces a new possibility in the field of targeted delivery of anticancer metallodrugs based on ruthenium(III) compounds.

Supra-dendron Gelator Based on Azobenzene-Cyclodextrin Host-Guest Interactions: Photoswitched Optical and Chiroptical Reversibility.

Science.gov (United States)

Xie, Fan; Ouyang, Guanghui; Qin, Long; Liu, Minghua

2016-12-12

A novel amphiphilic dendron (AZOC 8 GAc) with three l-glutamic acid units and an azobenzene moiety covalently linked by an alkyl spacer has been designed. The compound formed hydrogels with water at very low concentration and self-assembled into chiral-twist structures. The gel showed a reversible macroscopic volume phase transition in response to pH variations and photo-irradiation. During the photo-triggered changes, although the gel showed complete reversibility in its optical absorptions, only an incomplete chiroptical property change was achieved. On the other hand, the dendron could form a 1:1 inclusion complex through a host-guest interaction with α-cyclodextrin (α-CD), designated as supra-dendron gelator AZOC 8 GAc/α-CD. The supra-dendron showed similar gelation behavior to that of AZOC 8 GAc, but with enhanced photoisomerization-transition efficiency and chiroptical switching capacity, which was completely reversible in terms of both optical and chiroptical performances. The self-assembly of the supra-dendron is a hierarchical or multi-supramolecular self-assembling process. This work has clearly illustrated that the hierarchical and multi-supramolecular self-assembling system endows the supramolecular nanostructures or materials with superior reversible optical and chiroptical switching. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular effects in dendritic systems containing photoactive groups

Directory of Open Access Journals (Sweden)

GIANLUCA CAMILLO AZZELLINI

2000-03-01

Full Text Available In this article are described dendritic structures containing photoactive groups at the surface or in the core. The observed supramolecular effects can be attributed to the nature of the photoactive group and their location in the dendritic architecture. The peripheric azobenzene groups in these dendrimeric compounds can be regarded as single residues that retain the spectroscopic and photochemical properties of free azobenzene moiety. The E and Z forms of higher generation dendrimer, functionalized with azobenzene groups, show different host ability towards eosin dye, suggesting the possibility of using such dendrimer in photocontrolled host-guest systems. The photophysical properties of many dendritic-bipyridine ruthenium complexes have been investigated. Particularly in aerated medium more intense emission and a longer excited-state lifetime are observed as compared to the parent unsubstituted bipyridine ruthenium complexes. These differences can be attributed to a shielding effect towards dioxygen quenching originated by the dendritic branches.

Cucurbit[8]uril templated supramolecular ring structure formation and protein assembly modulation

NARCIS (Netherlands)

Ramaekers, M.; Wijnands, S.P.W.; van Dongen, J.L.J.; Brunsveld, L.; Dankers, P.Y.W.

2015-01-01

The interplay of Phe-Gly-Gly (FGG)-tagged proteins and bivalent FGG-tagged penta(ethylene glycol) as guest molecules with cucurbit[8]uril (Q8) hosts is studied to modulate the supramolecular assembly process. Ring structure formation of the bivalent guest molecule with Q8 leads to enhanced binding

Vibrational spectroscopic and gravimetric study of some Hofmann-CBA-Type Host and host-guest compounds

International Nuclear Information System (INIS)

Aytekin, M.A.

2005-01-01

In this study, similar to Hofmann type M(C 4 H 7 NH 2 ) 2 Ni(CN) 4 (M=Ni or Co) host and M(C 4 H 7 NH 2 ) 2 Ni(CN) 4 .nG (M=Ni or Co; G=benzene, 1,2-, 1,3-dichlorobenzene; n=the number of guest) hostguest compounds were obtained chemically. The infrared spectra of these compounds were recorded with FT-IR spectrometer in the spectroscopic region of 4000cm-1-400cm-1. From these spectra the vibrational wave numbers of ligand molecule, Ni(CN) 4 2 - ion and guest molecules were determined. The absorption and the liberation processes of the guest molecules in the host compounds were examined at room temperature by gravimetric method. Otherwise, it was seen that the molecular structure was supported by making instrumental analysis of host and some host-guest compounds. By analysing the structures of host and host-guest compounds were found to be similar to those of Hofmann type compounds, ligand molecule cyclobutylamine were coordinated to M metal atom from cyclobutylamine's nitrogen atom, the guest molecules were imprisoned in the structural cavities between the sheets

Carborane-beta-cyclodextrin complexes as a supramolecular connector for bioactive surfaces

Czech Academy of Sciences Publication Activity Database

Neirynck, P.; Schimer, Jiří; Jonkheijm, P.; Milroy, L. G.; Cígler, Petr; Brunsveld, L.

2015-01-01

Roč. 3, č. 4 (2015), s. 539-545 ISSN 2050-750X R&D Projects: GA MŠk(CZ) LH11027 Institutional support: RVO:61388963 Keywords : beta-cyclodextrine/carborane host-guest system * supramolecular chemistry * bioactive surfaces Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.872, year: 2015 http://pubs.rsc.org/en/content/articlepdf/2015/tb/c4tb01489h

Novel photoluminescence enzyme immunoassay based on supramolecular host-guest recognition using L-arginine/6-aza-2-thiothymine-stabilized gold nanocluster.

Science.gov (United States)

Wang, Youmei; Lu, Minghua; Tang, Dianping

2018-06-30

A new photoluminescence (PL) enzyme immunoassay was designed for sensitive detection of aflatoxin B 1 (AFB 1 ) via an innovative enzyme substrate, 6-aza-2-thiothymine-stabilized gold nanocluster (AAT-AuNC) with L-arginine. The enzyme substrate with strong PL intensity was formed through supramolecular host-guest assembly between guanidine group of L-arginine and AAT capped on the surface of AuNC. Upon arginase introduction, the captured L-arginine was hydrolyzed into ornithine and urea, thus resulting in the decreasing PL intensity. Based on this principle, a novel competitive-type immunoreaction was first carried out on AFB 1 -bovine serum albumin (AFB 1 -BSA) conjugate-coated microplate, using arginase-labeled anti-AFB 1 antibody as the competitor. Under the optimum conditions, the PL intensity increased with the increment of target AFB 1 , and allowed the detection of the analyte at concentrations as low as 3.2 pg mL -1 (ppt). Moreover, L-arginine-AAT-AuNC-based PL enzyme immunoassay afforded good reproducibility and acceptable specificity. In addition, the accuracy of this methodology, referring to commercial AFB 1 ELISA kit, was evaluated to analyze naturally contaminated or spiked peanut samples, giving well-matched results between two methods, thus representing a useful scheme for practical application in quantitative monitoring of mycotoxins in foodstuff. Copyright © 2018 Elsevier B.V. All rights reserved.

Paramagnetic NMR investigation of dendrimer-based host-guest interactions.

Directory of Open Access Journals (Sweden)

Fei Wang

Full Text Available In this study, the host-guest behavior of poly(amidoamine (PAMAM dendrimers bearing amine, hydroxyl, or carboxylate surface functionalities were investigated by paramagnetic NMR studies. 2,2,6,6-Tetramethylpiperidinyloxy (TEMPO derivatives were used as paramagnetic guest molecules. The results showed that TEMPO-COOH significantly broaden the ¹H NMR peaks of amine- and hydroxyl-terminated PAMAM dendrimers. In comparison, no paramagnetic relaxation enhancement (PRE was observed between TEMPO-NH₂, TEMPO-OH and the three types of PAMAM dendrimers. The PRE phenomenon observed is correlated with the encapsulation of TEMPO-COOH within dendrimer pockets. Protonation of the tertiary amine groups within PAMAM dendrimers plays an important role during this process. Interestingly, the absence of TEMPO-COOH encapsulation within carboxylate-terminated PAMAM dendrimer is observed due to the repulsion of TEMPO-COO- anion and anionic dendrimer surface. The combination of paramagnetic probes and ¹H NMR linewidth analysis can be used as a powerful tool in the analysis of dendrimer-based host-guest systems.

Selectivity and stoichiometry boosting of beta-cyclodextrin in cationic/anionic surfactant systems: when host-guest equilibrium meets biased aggregation equilibrium.

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Jiang, Lingxiang; Yu, Caifang; Deng, Manli; Jin, Changwen; Wang, Yilin; Yan, Yun; Huang, Jianbin

2010-02-18

Cationic surfactant/anionic surfactant/beta-CD ternary aqueous systems provide a platform for the coexistence of the host-guest (beta-CD/surfactant) equilibrium and the biased aggregation (monomeric/aggregated surfactants) equilibrium. We report here that the interplay between the two equilibria dominates the systems as follows. (1) The biased aggregation equilibrium imposes an apparent selectivity on the host-guest equilibrium, namely, beta-CD has to always selectively bind the major surfactant (molar fraction > 0.5) even if binding constants of beta-CD to the pair of surfactants are quite similar. (2) In return, the host-guest equilibrium amplifies the bias of the aggregation equilibrium, that is, the selective binding partly removes the major surfactant from the aggregates and leaves the aggregate composition approaching the electroneutral mixing stoichiometry. (3) This composition variation enhances electrostatic attractions between oppositely charged surfactant head groups, thus resulting in less-curved aggregates. In particular, the present apparent host-guest selectivity is of remarkably high values, and the selectivity stems from the bias of the aggregation equilibrium rather than the difference in binding constants. Moreover, beta-CD is defined as a "stoichiometry booster" for the whole class of cationic/anionic surfactant systems, which provides an additional degree of freedom to directly adjust aggregate compositions of the systems. The stoichiometry boosting of the compositions can in turn affect or even determine microstructures and macroproperties of the systems.

Circularly Polarized Luminescence from Inorganic Materials: Encapsulating Guest Lanthanide Oxides in Chiral Silica Hosts.

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Sugimoto, Masumi; Liu, Xin-Ling; Tsunega, Seiji; Nakajima, Erika; Abe, Shunsuke; Nakashima, Takuya; Kawai, Tsuyoshi; Jin, Ren-Hua

2018-05-02

Recently, circularly polarized luminescence (CPL)-active systems have become a very hot and interesting subject in chirality- and optics-related areas. The CPL-active systems are usually available by two approaches: covalently combining a luminescent centre to chiral motif or associating the guest of luminescent probe to a chiral host. However, all the chiral components in CPL materials were organic, although the luminescent components were alternatively organics or inorganics. Herein, the first totally inorganic CPL-active system by "luminescent guest-chiral host" strategy is proposed. Luminescent sub-10 nm lanthanide oxides (Eu 2 O 3 or Tb 2 O 3 ) nanoparticles (guests) were encapsulated into chiral non-helical SiO 2 nanofibres (host) through calcination of chiral SiO 2 hybrid nanofibres, trapping Eu 3+ (or Tb 3+ ). These lanthanide oxides display circular dichroism (CD) optical activity in the ultraviolet wavelength and CPL signals around at 615 nm for Eu 3+ and 545 nm for Tb 3+ . This work has implications for inorganic-based CPL-active systems by incorporation of various luminescent guests within chiral inorganic hosts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enzyme-Like Catalysis of the Nazarov Cyclization by Supramolecular Encapsulation

Energy Technology Data Exchange (ETDEWEB)

Hastings, Courtney; Pluth, Michael; Bergman, Robert; Raymond, Kenneth

2010-03-29

A primary goal in the design and synthesis of molecular hosts has been the selective recognition and binding of a variety of guests using non-covalent interactions. Supramolecular catalysis, which is the application of such hosts towards catalysis, has much in common with many enzymatic reactions, chiefly the use of both spatially appropriate binding pockets and precisely oriented functional groups to recognize and activate specific substrate molecules. Although there are now many examples which demonstrate how selective encapsulation in a host cavity can enhance the reactivity of a bound guest, all have failed to reach the degree of increased reactivity typical of enzymes. We now report the catalysis of the Nazarov cyclization by a self-assembled coordination cage, a carbon-carbon bond-forming reaction which proceeds under mild, aqueous conditions. The acceleration in this system is over a million-fold, and represents the first example of supramolecular catalysis that achieves the level of rate enhancement comparable to that observed in several enzymes. We explain the unprecedented degree of rate increase as due to the combination of (a) preorganization of the encapsulated substrate molecule, (b) stabilization of the transition state of the cyclization by constrictive binding, and (c) increase in the basicity of the complexed alcohol functionality.

Energy-cascade organic photovoltaic devices incorporating a host-guest architecture.

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Menke, S Matthew; Holmes, Russell J

2015-02-04

In planar heterojunction organic photovoltaic devices (OPVs), broad spectral coverage can be realized by incorporating multiple molecular absorbers in an energy-cascade architecture. Here, this approach is combined with a host-guest donor layer architecture previously shown to optimize exciton transport for the fluorescent organic semiconductor boron subphthalocyanine chloride (SubPc) when diluted in an optically transparent host. In order to maximize the absorption efficiency, energy-cascade OPVs that utilize both photoactive host and guest donor materials are examined using the pairing of SubPc and boron subnaphthalocyanine chloride (SubNc), respectively. In a planar heterojunction architecture, excitons generated on the SubPc host rapidly energy transfer to the SubNc guest, where they may migrate toward the dissociating, donor-acceptor interface. Overall, the incorporation of a photoactive host leads to a 13% enhancement in the short-circuit current density and a 20% enhancement in the power conversion efficiency relative to an optimized host-guest OPV combining SubNc with a nonabsorbing host. This work underscores the potential for further design refinements in planar heterojunction OPVs and demonstrates progress toward the effective separation of functionality between constituent OPV materials.

Hierarchical self-assembly, coassembly, and self-organization of novel liquid crystalline lattices and superlattices from a twin-tapered dendritic benzamide and its four-cylinder-bundle supramolecular polymer.

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Percec, Virgil; Bera, Tushar K; Glodde, Martin; Fu, Qiongying; Balagurusamy, Venkatachalapathy S K; Heiney, Paul A

2003-02-17

The synthesis and structural analysis of the twin-dendritic benzamide 10, based on the first-generation, self-assembling, tapered dendrons 3,4,5-tris(4'-dodecyloxybenzyloxy)benzoic acid and 3,4,5-tris(4'-dodecyloxybenzyloxy)-1-aminobenzene, and the polymethacrylate, 20, which contains 10 as side groups, are presented. Benzamide 10 self-assembles into a supramolecular cylindrical dendrimer that self-organizes into a columnar hexagonal (Phi(h)) liquid crystalline (LC) phase. Polymer 20 self-assembles into an imperfect four-cylinder-bundle supramolecular dendrimer, and creates a giant vesicular supercylinder that self-organizes into a columnar nematic (N(c)) LC phase which displays short-range hexagonal order. In mixtures of 20 and 10, 10 acts as a guest and 20 as a host to create a perfect four-cylinder-bundle host-guest supramolecular dendrimer that coorganizes with 10. A diversity of Phi(h), simple rectangular columnar (Phi(r-s)) and centered rectangular columnar (Phi(r-c)), superlattices are produced at different ratios between 20 and 10. This diversity of LC lattices and superlattices is facilitated by the architecture of the twin-dendritic building block, polymethacrylate, the host-guest supramolecular assembly, and by hydrogen bonding along the center of the supramolecular cylinders generated from 10 and 20.

Molecular recognition: Comparative study of a tunable host-guest system by using a fluorescent model system and collision-induced dissociation mass spectrometry on dendrimers

DEFF Research Database (Denmark)

Pittelkow, M.; Nielsen, C.B.; Broeren, A.C.

2005-01-01

Host-guest interactions between the periphery of adamantylurea-functionalized dendrimers (host) and ureido acetic acid derivatives (guest) were shown to be specific, strong and spatially well-defined. The binding becomes stronger when using phosphonic or sulfonic acid derivatives. In the present...... work we have quantified the binding constants for the host-guest interactions between two different host motifs and six different guest molecules. The host molecules, which resemble the periphery of a poly(propylene imine) dendrimer, have been fitted with an anthracene-based fluorescent probe. The two...... host motifs differ in terms of the length of the spacer between a tertiary amine and two ureido functionalities. The guest molecules all contain an acidic moiety (either a carboxylic acid, a phosphonic acid, or a sulfonic acid) and three of them also contain an ureido moiety capable of forming multiple...

Guest Controlled Nonmonotonic Deep Cavity Cavitand Assembly State Switching.

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Tang, Du; Barnett, J Wesley; Gibb, Bruce C; Ashbaugh, Henry S

2017-11-30

Octa-acid (OA) and tetra-endo-methyl octa-acid (TEMOA) are water-soluble, deep-cavity cavitands with nanometer-sized nonpolar pockets that readily bind complementary guests, such as n-alkanes. Experimentally, OA exhibits a progression of 1:1 to 2:2 to 2:1 host/guest complexes (X:Y where X is the number of hosts and Y is the number of guests) with increasing alkane chain length from methane to tetradecane. Differing from OA only by the addition of four methyl groups ringing the portal of the pocket, TEMOA exhibits a nonmonotonic progression of assembly states from 1:1 to 2:2 to 1:1 to 2:1 with increasing guest length. Here we present a systematic molecular simulation study to parse the molecular and thermodynamic determinants that distinguish the succession of assembly stoichiometries observed for these similar hosts. Potentials of mean force between hosts and guests, determined via umbrella sampling, are used to characterize association free energies. These free energies are subsequently used in a reaction network model to predict the equilibrium distributions of assemblies. Our models accurately reproduce the experimentally observed trends, showing that TEMOA's endo-methyl units constrict the opening of the binding pocket, limiting the conformations available to bound guests and disrupting the balance between monomeric complexes and dimeric capsules. The success of our simulations demonstrate their utility at interpreting the impact of even simple chemical modifications on supramolecular assembly and highlight their potential to aid bottom-up design.

Host-guest chemistry of dendrimer-drug complexes. 2. Effects of molecular properties of guests and surface functionalities of dendrimers.

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Hu, Jingjing; Cheng, Yiyun; Wu, Qinglin; Zhao, Libo; Xu, Tongwen

2009-08-06

The host-guest chemistry of dendrimer-drug complexes is investigated by NMR techniques, including (1)H NMR and 2D-NOESY studies. The effects of molecular properties of drug molecules (protonation ability and spatial steric hindrance of charged groups) and surface functionalities of dendrimers (positively charged amine groups and negatively charged carboxylate groups) on the host-guest interactions are discussed. Different interaction mechanisms between dendrimers and drug molecules are proposed on the basis of NMR results. Primary amine- and secondary amine-containing drugs preferentially bind to negatively charged dendrimers by strong electrostatic interactions, whereas tertiary amine and quaternary ammonium-containing drugs have weak binding ability with dendrimers due to relatively low protonation ability of the tertiary amine group and serious steric hindrance of the quaternary ammonium group. Positively charged drugs locate only on the surface of negatively charged dendrimers, whereas negatively charged drugs locate both on the surface and in the interior cavities of positively charged dendrimers. The host-guest chemistry of dendrimer-drug complexes is promising for the development of new drug delivery systems.

Carbohydrate-Based Host-Guest Complexation of Hydrophobic Antibiotics for the Enhancement of Antibacterial Activity.

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Jeong, Daham; Joo, Sang-Woo; Shinde, Vijay Vilas; Cho, Eunae; Jung, Seunho

2017-08-08

Host-guest complexation with various hydrophobic drugs has been used to enhance the solubility, permeability, and stability of guest drugs. Physical changes in hydrophobic drugs by complexation have been related to corresponding increases in the bioavailability of these drugs. Carbohydrates, including various derivatives of cyclodextrins, cyclosophoraoses, and some linear oligosaccharides, are generally used as host complexation agents in drug delivery systems. Many antibiotics with low bioavailability have some limitations to their clinical use due to their intrinsically poor aqueous solubility. Bioavailability enhancement is therefore an important step to achieve the desired concentration of antibiotics in the treatment of bacterial infections. Antibiotics encapsulated in a complexation-based drug delivery system will display improved antibacterial activity making it possible to reduce dosages and overcome the serious global problem of antibiotic resistance. Here, we review the present research trends in carbohydrate-based host-guest complexation of various hydrophobic antibiotics as an efficient delivery system to improve solubility, permeability, stability, and controlled release.

Incommensurate host-guest structures in compressed elements: Hume—Rothery effects as origin

International Nuclear Information System (INIS)

Degtyareva, V F

2015-01-01

Discovery of the incommensurate structure in the element Ba under pressure 15 years ago was followed by findings of a series of similar structures in other compressed elements. Incommensurately modulated structures of the host-guest type consist of a tetragonal host structure and a guest structure. The guest structure forms chains of atoms embedded in the channels of host atoms so that the axial ratio of these subcells along the c axis is not rational. Two types of the host-guest structures have been found so far: with the host cells containing 8 atoms and 16 atoms; in these both types the guest cells contain 2 atoms. These crystal structures contain a non-integer number of atoms in their unit cell: tI11* in Bi, Sb, As, Ba, Sr, Sc and tI19* in Na, K, Rb. We consider here a close structural relationship of these host-guest structures with the binary alloy phase Au 3 Cd 5 -tI32. This phase is related to the family of the Hume-Rothery phases that is stabilized by the Fermi sphere-Brillouin zone interaction. From similar considerations for alkali and alkaline-earth elements a necessary condition for structural stability emerges in which the valence electrons band overlaps with the upper core electrons and the valence electron count increases under compression. (paper)

Identification of Guest-Host Inclusion Complexes in the Gas Phase by Electrospray Ionization-Mass Spectrometry

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Mendes, De´bora C.; Ramamurthy, Vaidhyanathan; Da Silva, Jose´ P.

2015-01-01

In this laboratory experiment, students follow a step-by-step procedure to prepare and study guest-host complexes in the gas phase using electrospray ionization-mass spectrometry (ESI-MS). Model systems are the complexes of hosts cucurbit[7]uril (CB7) and cucurbit[8]uril (CB8) with the guest 4-styrylpyridine (SP). Aqueous solutions of CB7 or CB8…

Host-Guest Interaction between Corona[n]arene and Bisquaternary Ammonium Derivatives for Fabricating Supra-Amphiphile.

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Zeng, Lingda; Guo, Qing-Hui; Feng, Yuanning; Xu, Jiang-Fei; Wei, Yuhan; Li, Zhibo; Wang, Mei-Xiang; Zhang, Xi

2017-06-13

The interactions between a host, water-soluble corona[n]arene (S6-CAP), and a series of guests, bisquaternary ammonium derivatives (CnDAs), in water, were investigated. The host and guest can form 1:1 host-guest complex. Their binding constants decrease as the alkyl length of CnDAs increases, which can be tunable ranging from 10 3 to 10 6 M -1 . The binding processes are mainly entropy-driven, while the enthalpy changes also play an important role in enhancing the host-guest interactions. In addition, a supra-amphiphile was fabricated with S6-CAP and a normal surfactant bearing bisquaternary ammonium (C4R). The S6-CAP·C4R complex forms micellar aggregates in water, and the system possesses better assembling activity and dilution stability than its building block C4R. This study enriches the families of supra-amphiphiles with a new architecture, and employing such a supra-amphiphile in biofunctional materials is highly anticipated.

Spatial, Hysteretic, and Adaptive Host-Guest Chemistry in a Metal-Organic Framework with Open Watson-Crick Sites.

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Cai, Hong; Li, Mian; Lin, Xiao-Rong; Chen, Wei; Chen, Guang-Hui; Huang, Xiao-Chun; Li, Dan

2015-09-01

Biological and artificial molecules and assemblies capable of supramolecular recognition, especially those with nucleobase pairing, usually rely on autonomous or collective binding to function. Advanced site-specific recognition takes advantage of cooperative spatial effects, as in local folding in protein-DNA binding. Herein, we report a new nucleobase-tagged metal-organic framework (MOF), namely ZnBTCA (BTC=benzene-1,3,5-tricarboxyl, A=adenine), in which the exposed Watson-Crick faces of adenine residues are immobilized periodically on the interior crystalline surface. Systematic control experiments demonstrated the cooperation of the open Watson-Crick sites and spatial effects within the nanopores, and thermodynamic and kinetic studies revealed a hysteretic host-guest interaction attributed to mild chemisorption. We further exploited this behavior for adenine-thymine binding within the constrained pores, and a globally adaptive response of the MOF host was observed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermoresponsive Interplay of Water Insoluble Poly(2-alkyl-2-oxazolines Composition and Supramolecular Host–Guest Interactions

Directory of Open Access Journals (Sweden)

Victor R. de la Rosa

2015-04-01

Full Text Available A series of water insoluble poly[(2-ethyl-2-oxazoline-ran-(2-nonyl-2-oxazoline] amphiphilic copolymers was synthesized and their solubility properties in the presence of different supramolecular host molecules were investigated. The resulting polymer-cavitand assemblies exhibited a thermoresponsive behavior that could be modulated by variation of the copolymer composition and length. Interestingly, the large number of hydrophobic nonyl units across the polymer chain induced the formation of kinetically-trapped nanoparticles in solution. These nanoparticles further agglomerate into larger aggregates at a temperature that is dependent on the polymer composition and the cavitand type and concentration. The present research expands the understanding on the supramolecular interactions between water insoluble copolymers and supramolecular host molecules.

Elasticity-dependent fast underwater adhesion demonstrated by macroscopic supramolecular assembly.

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Ju, Guannan; Cheng, Mengjiao; Guo, Fengli; Zhang, Qian; Shi, Feng

2018-05-30

Macroscopic supramolecular assembly (MSA) is a recent progress in supramolecular chemistry to associate visible building blocks through non-covalent interactions in a multivalent manner. Although various substrates (e. g. hydrogels, rigid materials) have been used, a general design rule of building blocks in MSA systems and interpretation of the assembly mechanism are still lacking and urgently in demand. Here we design three model systems with varied modulus and correlated the MSA probability with the elasticity. Based on the effects of substrate deformability on multivalency, we have proposed an elastic-modulus-dependent rule that building blocks below a critical modulus of 2.5 MPa can achieve MSA for the used host/guest system. Moreover, this MSA rule applies well to the design of materials applicable for fast underwater adhesion: Soft substrates (0.5 MPa) can achieve underwater adhesion within 10 s with one magnitude higher strength than that of rigid substrates (2.5 MPa). © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Pyrene- and Phosphonate-Containing Fluorescent Probe as Guest Molecule in a Host Polymer Matrix

Directory of Open Access Journals (Sweden)

Jacqueline Marchand-Brynaert

2013-02-01

Full Text Available New host-guest materials have been prepared by incorporation of a home-made organic probe displaying a pyrene motif and a phosphonate function into a regular amphiphilic copolymer. Using powder X-Ray diffraction, photoluminescence and FT-IR spectroscopy, we have been able to study the non-covalent interactions between the host matrix and the guest molecule in the solid state. Interestingly, we have shown that the matrix directs the guest spatial localization and alters its properties. Thanks to the comparison of pyrene vs. N-pyrenylmaleimide derivatives, the influence of the chemical nature of the guest molecules on the non-covalent interactions with the host have been studied. In addition, using polyethylene glycol as a reference host, we have been able to evidence a true matrix effect within our new insertion materials. The phosphonated guest molecule appears to be a novel probe targeting the hydrophilic domain of the host copolymer.

Vibrational spectroscopic and quantum theoretical study of host-guest interactions in clathrates: I. Hofmann type clathrates

Directory of Open Access Journals (Sweden)

VLADIMIR M. PETRUSEVSKI

2000-06-01

Full Text Available Hofmann type clatharates are host-guest compounds with the general formula M(NH32M'(CN4·2G, in which M(NH32M'(CN4 is the host lattice and G is benzene, the guest molecule. In previous studies, host-guest interactions have been investigated by analyzing the RT and LNT vibrational (infrared, far infrared and Raman spectra of these clathrates. All the observed changes in the vibrational spectra of these clathrates are referred to a host-guest interaction originating from weak hydrogen bonding between the ammonia hydrogen atoms from the host lattice and the p electron cloud of the guest (benzene molecules. In order to obtain an insight into the relative importance of the local crystalline field vs. the anharmonicity effects on the spectroscopic properties of the guest species upon enclathration, as well as to explain the observed band shifts and splittings, several quantum theoretical approaches are proposed.

Uses of neutron scattering in supramolecular chemistry

International Nuclear Information System (INIS)

Lindoy, L.F.

1998-01-01

Full text: A major thrust in recent chemical research has been the development of supramolecular chemistry 1 - broadly the chemistry of large multicomponent molecular assemblies in which the component structural units are held together by either covalent linkages or by a variety of weaker (non-covalent) interactions that include hydrogen bonding, dipole stacking, π-stacking, van der Waals q forces and favourable hydrophobic interactions. Much of the activity in the area has been motivated by the known behaviour of biological molecules (such as enzymes). Thus molecular assemblies are ubiquitous in natural systems but, with a limited number of exceptions, have only recently been the subject of increasing investigation by chemists. A feature of much of this recent work has been its focus on molecular design for achieving complementarity between single molecule hosts and guests. The use of single crystal neutron diffraction coupled with molecular modelling and a range of other techniques to investigate the nature of individual supramolecular systems will be discussed. By way of example, in one such study the supramolecular array formed by co-crystallisation of 1,2- diaminoethane and benzoic acid has been investigated; the system self-assembles into an unusual layered structure composed of two-dimensional hydrogen bonded networks sandwiched between layers of edge-to-face stacked aromatic systems. The number of hydrogen-bond donors and acceptors is balanced in this structure

Supramolecular solubilization of fullerenes and radio-fullerenes in aqueous media

International Nuclear Information System (INIS)

Braun, T.

1999-01-01

In this paper we are dealing with the supramolecular complexation of fullerenes C 60 , C 70 , some functionalized fullerenes and of the dumbbell structured C 120 dimer, with two host molecules, namely γ-cyclo-dextrin (GCD), and sulfocalix[8]arene in order to make them soluble in water. Previous investigations by others have shown that the reactions of some mentioned fullerenes and cyclo-dextrins and calixarenes are very slow and tedious in liquid phase as a result of solvatation effects. That we have decided to pursue the supramolecular complexation as solid-solid reactions by using mechanochemical activation in a ball mill. A mechanochemical treatment was used to enhance chemical reactivity in solid-solid reactions in which GCD give a complex with the C 60 as 2:1 host-guest complex. The calix[8]arene complex with C 60 molecule has been prepared. The sulfonated form of the host is well soluble in water. Endohedral radio-fullerenes of the XandC60 type (where * X is a rare gas, e.g. Ar, Xe, Kr, radionuclide) were prepared by nuclear recoil after neutron irradiation, a method developed by the author The endohedrally labelled fullerenes were then mechanochemically complexed into a labelled supramolecular complex with cyclo-dextrin and calixarene hosts. (author)

Fabrication of supramolecular star-shaped amphiphilic copolymers for ROS-triggered drug release.

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Zuo, Cai; Peng, Jinlei; Cong, Yong; Dai, Xianyin; Zhang, Xiaolong; Zhao, Sijie; Zhang, Xianshuo; Ma, Liwei; Wang, Baoyan; Wei, Hua

2018-03-15

Star-shaped copolymers with branched structures can form unimolecular micelles with better stability than the micelles self-assembled from conventional linear copolymers. However, the synthesis of star-shaped copolymers with precisely controlled degree of branching (DB) suffers from complicated sequential polymerizations and multi-step purification procedures, as well as repeated optimizations of polymer compositions. The use of a supramolecular host-guest pair as the block junction would significantly simplify the preparation. Moreover, the star-shaped copolymer-based unimolecular micelle provides an elegant solution to the tradeoff between extracellular stability and intracellular high therapeutic efficacy if the association/dissociation of the supramolecular host-guest joint can be triggered by the biologically relevant stimuli. For this purpose, in this study, a panel of supramolecular star-shaped amphiphilic block copolymers with 9, 12, and 18 arms were designed and fabricated by host-guest complexations between the ring-opening polymerization (ROP)-synthesized star-shaped poly(ε-caprolactone) (PCL) with 3, 4, and 6 arms end-capped with ferrocene (Fc) (PCL-Fc) and the atom transfer radical polymerization (ATRP)-produced 3-arm poly(oligo ethylene glycol) methacrylates (POEGMA) with different degrees of polymerization (DPs) of 24, 30, 47 initiated by β-cyclodextrin (β-CD) (3Br-β-CD-POEGMA). The effect of DB and polymer composition on the self-assembled properties of the five star-shaped copolymers was investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM), and fluorescence spectrometery. Interestingly, the micelles self-assembled from 12-arm star-shaped copolymers exhibited greater stability than the 9- and 18-arm formulations. The potential of the resulting supramolecular star-shaped amphiphilic copolymers as drug carriers was evaluated by an in vitro drug release study, which confirmed the ROS-triggered accelerated drug

Multifunctional guest-host particles engineered by reversal nanoimprint lithography

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Ha, Uh-Myong; Kaban, Burhan; Tomita, Andreea; Krekić, Kristijan; Klintuch, Dieter; Pietschnig, Rudolf; Ehresmann, Arno; Holzinger, Dennis; Hillmer, Hartmut

2018-03-01

Particulate polymeric microfibers with incorporated europium(III)oxide (Eu2O3) nanoparticles were introduced as a magneto-photoluminescent multifunctional material fabricated via reversal nanoimprint lithography. To specifically address the volume properties of these guest-host particles, the guest, Eu2O3, was milled down to an average particle size of 350 nm in diameter and mixed with the host-polymer, AMONIL®, before in situ hardening in the imprint stamp. The variation of the fabrication process parameters, i.e. delay time, spin coating speed, as well as the concentration of Eu2O3 nanoparticles was proven to have a significant impact on both the structure quality and the stamp release of the microfibers with respect to the formation of a thinner residual layer. Structural characterization performed by SEM revealed optimum fabrication process parameters for a homogeneous spatial distribution of Eu2O3 nanoparticles within the microfibers while simultaneously avoiding the formation of undesired agglomerates. The magneto-photoluminescent properties of Eu2O3 nanoparticles, i.e. a red emission at 613 nm and a paramagnetic response, were found to be superimposed to the optic and the diamagnetic behaviors of AMONIL®. The results imply that guest-host interdependence of these properties can be excluded and that the suggested technique enables for specific tailoring of particulate multifunctional materials with focus on their volume properties.

Cucurbit[8]uril-Containing Multilayer Films for the Photocontrolled Binding and Release of a Guest Molecule.

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Nicolas, Henning; Yuan, Bin; Zhang, Xi; Schönhoff, Monika

2016-03-15

The powerful host-guest chemistry of cucurbit[8]uril (CB[8]) was employed to obtain photoresponsive polyelectrolyte multilayer films for the reversible and photocontrolled binding and release of an organic guest molecule. For this purpose, we designed and synthesized a polyelectrolyte with azobenzene side groups. Then, CB[8] was associated with the azo side group to obtain a supramolecular host-guest complex that was further used as building block in order to prepare photoresponsive and CB[8]-containing polyelectrolyte multilayer films. Ultraviolet spectroscopy and a dissipative quartz crystal microbalance are employed to monitor the formation of the host-guest complex and the layer-by-layer self-assembly of the multilayer films, respectively. We demonstrate that the photoresponsive properties of the azo side groups are maintained before and after host-guest complexation with CB[8] in solution and within the multilayer films, respectively. A guest molecule was then specifically included as second binding partner into the CB[8]-containing multilayer films. Subsequently, the release of the guest was performed by UV light irradiation due to the trans-cis isomerization of the adjacent azo side groups. Re-isomerization of the azo side groups was achieved by VIS light irradiation and enabled the rebinding of the guest into CB[8]. Finally, we demonstrate that the photocontrolled binding and release within CB[8]-containing multilayer films can reliably and reversibly be performed over a period of more than 2 weeks with constant binding efficiency. Therefore, we expect such novel type of photosensitive films to have promising future applications in the field of stimuli-responsive nanomaterials.

Supramolecular chemistry and crystal engineering

Indian Academy of Sciences (India)

supramolecular architectures, network structures, multi-component host–guest systems, cocrys- tals, and ... structures is illustrated by two important prototypes – the large unit cell of elusive saccharin hydrate ..... N––– H ··· π interaction is not seen in this view. (d) Infinite .... to atmospheric water vapor without color loss or.

Toward Improved Force-Field Accuracy through Sensitivity Analysis of Host-Guest Binding Thermodynamics

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Yin, Jian; Fenley, Andrew T.; Henriksen, Niel M.; Gilson, Michael K.

2015-01-01

Improving the capability of atomistic computer models to predict the thermodynamics of noncovalent binding is critical for successful structure-based drug design, and the accuracy of such calculations remains limited by non-optimal force field parameters. Ideally, one would incorporate protein-ligand affinity data into force field parametrization, but this would be inefficient and costly. We now demonstrate that sensitivity analysis can be used to efficiently tune Lennard-Jones parameters of aqueous host-guest systems for increasingly accurate calculations of binding enthalpy. These results highlight the promise of a comprehensive use of calorimetric host-guest binding data, along with existing validation data sets, to improve force field parameters for the simulation of noncovalent binding, with the ultimate goal of making protein-ligand modeling more accurate and hence speeding drug discovery. PMID:26181208

Temperature-regulated guest admission and release in microporous materials

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Li, Gang (Kevin); Shang, Jin; Gu, Qinfen; Awati, Rohan V.; Jensen, Nathan; Grant, Andrew; Zhang, Xueying; Sholl, David S.; Liu, Jefferson Z.; Webley, Paul A.; May, Eric F.

2017-06-01

While it has long been known that some highly adsorbing microporous materials suddenly become inaccessible to guest molecules below certain temperatures, previous attempts to explain this phenomenon have failed. Here we show that this anomalous sorption behaviour is a temperature-regulated guest admission process, where the pore-keeping group's thermal fluctuations are influenced by interactions with guest molecules. A physical model is presented to explain the atomic-level chemistry and structure of these thermally regulated micropores, which is crucial to systematic engineering of new functional materials such as tunable molecular sieves, gated membranes and controlled-release nanocontainers. The model was validated experimentally with H2, N2, Ar and CH4 on three classes of microporous materials: trapdoor zeolites, supramolecular host calixarenes and metal-organic frameworks. We demonstrate how temperature can be exploited to achieve appreciable hydrogen and methane storage in such materials without sustained pressure. These findings also open new avenues for gas sensing and isotope separation.

Can we beat the biotin-avidin pair?: cucurbit[7]uril-based ultrahigh affinity host-guest complexes and their applications.

Science.gov (United States)

Shetty, Dinesh; Khedkar, Jayshree K; Park, Kyeng Min; Kim, Kimoon

2015-12-07

The design of synthetic, monovalent host-guest molecular recognition pairs is still challenging and of particular interest to inquire into the limits of the affinity that can be achieved with designed systems. In this regard, cucurbit[7]uril (CB[7]), an important member of the host family cucurbit[n]uril (CB[n], n = 5-8, 10, 14), has attracted much attention because of its ability to form ultra-stable complexes with multiple guests. The strong hydrophobic effect between the host cavity and guests, ion-dipole and dipole-dipole interactions of guests with CB portals helps in cooperative and multiple noncovalent interactions that are essential for realizing such strong complexations. These highly selective, strong yet dynamic interactions can be exploited in many applications including affinity chromatography, biomolecule immobilization, protein isolation, biological catalysis, and sensor technologies. In this review, we summarize the progress in the development of high affinity guests for CB[7], factors affecting the stability of complexes, theoretical insights, and the utility of these high affinity pairs in different challenging applications.

Fluorescence-Based Comparative Binding Studies of the Supramolecular Host Properties of PAMAM Dendrimers Using Anilinonaphthalene Sulfonates: Unusual Host-Dependent Fluorescence Titration Behavior

Directory of Open Access Journals (Sweden)

Natasa Stojanovic

2010-04-01

Full Text Available This work describes the fluorescence enhancement of the anilinonaphthalene sulfonate probes 1,8-ANS, 2,6-ANS, and 2,6-TNS via complexation with PAMAM dendrimer hosts of Generation 4, 5 and 6. The use of this set of three very closely related probes allows for comparative binding studies, with specific pairs of probes differing only in shape (1,8-ANS and 2,6-ANS, or in the presence of a methyl substituent (2,6-TNS vs. 2,6-ANS. The fluorescence of all three probes was significantly enhanced upon binding with PAMAM dendrimers, however in all cases except one, a very unusual spike was consistently observed in the host fluorescence titration plots (fluorescence enhancement vs. host concentration at low dendrimer concentration. This unprecedented fluorescence titration curve shape makes fitting the data to a simple model such as 1:1 or 2:1 host: guest complexation very difficult; thus only qualitative comparisons of the relative binding of the three guests could be made based on host titrations. In the case of G4 and G5 dendrimers, the order of binding strength was qualitatively determined to be 1,8-ANS < 2,6-ANS indicating that the more streamlined 2,6-substituted probes are a better match for the dendrimer cavity shape than the bulkier 1,8-substituted probe. This order of binding strength was also indicated by double fluorometric titration experiments, involving both host and guest titrations. Further double fluorometric titration experiments on 2,6-ANS in G4 dendrimer revealed a host concentration-dependent change in the nature of the host: guest complexation, with multiple guests complexed per host molecule at very low host concentrations, but less than one guest per host at higher concentrations.

Supramolecular assembly affording a ratiometric two-photon fluorescent nanoprobe for quantitative detection and bioimaging.

Science.gov (United States)

Wang, Peng; Zhang, Cheng; Liu, Hong-Wen; Xiong, Mengyi; Yin, Sheng-Yan; Yang, Yue; Hu, Xiao-Xiao; Yin, Xia; Zhang, Xiao-Bing; Tan, Weihong

2017-12-01

Fluorescence quantitative analyses for vital biomolecules are in great demand in biomedical science owing to their unique detection advantages with rapid, sensitive, non-damaging and specific identification. However, available fluorescence strategies for quantitative detection are usually hard to design and achieve. Inspired by supramolecular chemistry, a two-photon-excited fluorescent supramolecular nanoplatform ( TPSNP ) was designed for quantitative analysis with three parts: host molecules (β-CD polymers), a guest fluorophore of sensing probes (Np-Ad) and a guest internal reference (NpRh-Ad). In this strategy, the TPSNP possesses the merits of (i) improved water-solubility and biocompatibility; (ii) increased tissue penetration depth for bioimaging by two-photon excitation; (iii) quantitative and tunable assembly of functional guest molecules to obtain optimized detection conditions; (iv) a common approach to avoid the limitation of complicated design by adjustment of sensing probes; and (v) accurate quantitative analysis by virtue of reference molecules. As a proof-of-concept, we utilized the two-photon fluorescent probe NHS-Ad-based TPSNP-1 to realize accurate quantitative analysis of hydrogen sulfide (H 2 S), with high sensitivity and good selectivity in live cells, deep tissues and ex vivo -dissected organs, suggesting that the TPSNP is an ideal quantitative indicator for clinical samples. What's more, TPSNP will pave the way for designing and preparing advanced supramolecular sensors for biosensing and biomedicine.

SANS contrast variation on a dendrimer host-guest complex

NARCIS (Netherlands)

Kleppinger, R.; Mortensen, K.; Meijer, E.W.

2002-01-01

Small-angle neutron scattering (SANS) technique was used to study the configurational changes in an oligoethyleneoxy-functionalized poly(propyleneimine) dendrimer (host) when forming complexes with rose bengal (guest). Guinier fits to the scattering data recorded at max. contrast indicated a

Observation of the energy transfer sequence in an organic host–guest system of a luminescent polymer and a phosphorescent molecule

International Nuclear Information System (INIS)

Basel, Tek; Sun, Dali; Gautam, Bhoj; Valy Vardeny, Z.

2014-01-01

We used steady state optical spectroscopies such as photoluminescence and photoinduced absorption (PA), and magnetic-field PA (MPA) for studying the energy transfer dynamics in films and organic light emitting diodes (OLED) based on host–guest blends with different guest concentrations of the fluorescent polymer poly-[2-methoxy, 5-(2′-ethyl-hexyloxy)phenylene vinylene] (MEHPPV-host), and phosphorescent molecule PtII-tetraphenyltetrabenzoporphyrin [Pt(tpbp); guest]. We show that the energy transfer process between the excited states of the host polymer and guest molecule takes a ‘ping-pong’ type sequence, because the lowest guest triplet exciton energy, E T (guest), lies higher than that of the host, E T (host). Upon photon excitation the photogenerated singlet excitons in the host polymer chains first undergo a Förster resonant energy transfer process to the guest singlet manifold, which subsequently reaches E T (guest) by intersystem crossing. Because E T (guest)>E T (host) there is a subsequent Dexter type energy transfer from E T (guest) to E T (host). This energy transfer sequence has profound influence on the photoluminescence and electroluminescence emission spectra in both films and OLED devices based on the MEHPPV-Pt(tpbp) system. - Highlights: • We studied electroluminescence of OLEDs based on host–guest blends. • The emission efficiency decreases with the guest concentration. • We found a dominant Dexter energy transfer from the triplet(guest) to triplet(host). • Energy transfer occurs from the host to guest and back to the host again

Synergy in supramolecular chemistry

CERN Document Server

Nabeshima, Tatsuya

2014-01-01

Synergy and Cooperativity in Multi-metal Supramolecular Systems, T. NabeshimaHierarchically Assembled Titanium Helicates, Markus AlbrechtSupramolecular Hosts and Catalysts Formed by Self-assembly of Multinuclear Zinc Complexes in Aqueous Solution, Shin AokiSupramolecular Assemblies Based on Interionic Interactions, H. MaedaSupramolecular Synergy in the Formation and Function of Guanosine Quadruplexes, Jeffery T. DavisOn-Surface Chirality in Porous Self-Assembled Monolayers at Liquid-Solid Interface, Kazukuni Tahar

Competitive Self-Assembly Manifests Supramolecular Darwinism in Soft-Oxometalates

Science.gov (United States)

Das, Santu; Kumar, Saurabh; Mallick, Apabrita; Roy, Soumyajit

2015-09-01

Topological transformation manifested in inorganic materials shows manifold possibilities. In our present work, we show a clear topological transformation in a soft-oxometalate (SOM) system which was formed from its polyoxometalate (POM) precursor [PMo12@Mo72Fe30]. This topological transformation was observed due to time dependent competitive self-assembly of two different length scale soft-oxometalate moieties formed from this two-component host-guest reaction. We characterized different morphologies by scanning electron microscopy, electron dispersive scattering spectroscopy, dynamic light scattering, horizontal attenuated total reflection-infrared spectroscopy and Raman spectroscopy. The predominant structure is selected by its size in a sort of supramolecular Darwinian competition in this process and is described here.

Host-guest interaction of styrene and ethylbenzene in MIL-53 studied by solid-state NMR.

Science.gov (United States)

Li, Shenhui; Li, Jing; Tang, Jing; Deng, Feng

Solid-state NMR was utilized to explore the host-guest interaction between adsorbate and adsorbent at atomic level to understand the separation mechanism of styrene (St) and ethylbenzene (EB) in MIL-53(Al). 13 C- 27 Al double-resonance NMR experiments revealed that the host-guest interaction between St and MIL-53 was much stronger than that of EB adsorption. In addition, 13 C DIPSHIFT experiments suggested that the adsorbed St was less mobile than EB confined inside the MIL-53 pore. Furthermore, the host-guest interaction model between St, EB and MIL-53 was established on the basis of the spatial proximities information extracted from 2D 1 H- 1 H homo-nuclear correlation NMR experiments. According to the experimental observation from solid-state NMR, it was found that the presence of π-π interaction between St and MIL-53 resulted in the stronger host-guest interaction and less mobility of St. This work provides direct experimental evidence for understanding the separation mechanism of St and EB using MIL-53 as an adsorbent. Copyright © 2017 Elsevier Inc. All rights reserved.

Multivalency at Interfaces: Supramolecular Carbohydrate-Functionalized Graphene Derivatives for Bacterial Capture, Release, and Disinfection.

Science.gov (United States)

Qi, Zhenhui; Bharate, Priya; Lai, Chian-Hui; Ziem, Benjamin; Böttcher, Christoph; Schulz, Andrea; Beckert, Fabian; Hatting, Benjamin; Mülhaupt, Rolf; Seeberger, Peter H; Haag, Rainer

2015-09-09

A supramolecular carbohydrate-functionalized two-dimensional (2D) surface was designed and synthesized by decorating thermally reduced graphene sheets with multivalent sugar ligands. The formation of host-guest inclusions on the carbon surface provides a versatile strategy, not only to increase the intrinsic water solubility of graphene-based materials, but more importantly to let the desired biofunctional binding groups bind to the surface. Combining the vital recognition role of carbohydrates and the unique 2D large flexible surface area of the graphene sheets, the addition of multivalent sugar ligands makes the resulting carbon material an excellent platform for selectively wrapping and agglutinating Escherichia coli (E. coli). By taking advantage of the responsive property of supramolecular interactions, the captured bacteria can then be partially released by adding a competitive guest. Compared to previously reported scaffolds, the unique thermal IR-absorption properties of graphene derivatives provide a facile method to kill the captured bacteria by IR-laser irradiation of the captured graphene-sugar-E. coli complex.

Observation of the energy transfer sequence in an organic host–guest system of a luminescent polymer and a phosphorescent molecule

Energy Technology Data Exchange (ETDEWEB)

Basel, Tek; Sun, Dali; Gautam, Bhoj; Valy Vardeny, Z., E-mail: val@physics.utah.edu

2014-11-15

We used steady state optical spectroscopies such as photoluminescence and photoinduced absorption (PA), and magnetic-field PA (MPA) for studying the energy transfer dynamics in films and organic light emitting diodes (OLED) based on host–guest blends with different guest concentrations of the fluorescent polymer poly-[2-methoxy, 5-(2′-ethyl-hexyloxy)phenylene vinylene] (MEHPPV-host), and phosphorescent molecule PtII-tetraphenyltetrabenzoporphyrin [Pt(tpbp); guest]. We show that the energy transfer process between the excited states of the host polymer and guest molecule takes a ‘ping-pong’ type sequence, because the lowest guest triplet exciton energy, E{sub T}(guest), lies higher than that of the host, E{sub T}(host). Upon photon excitation the photogenerated singlet excitons in the host polymer chains first undergo a Förster resonant energy transfer process to the guest singlet manifold, which subsequently reaches E{sub T}(guest) by intersystem crossing. Because E{sub T}(guest)>E{sub T}(host) there is a subsequent Dexter type energy transfer from E{sub T}(guest) to E{sub T}(host). This energy transfer sequence has profound influence on the photoluminescence and electroluminescence emission spectra in both films and OLED devices based on the MEHPPV-Pt(tpbp) system. - Highlights: • We studied electroluminescence of OLEDs based on host–guest blends. • The emission efficiency decreases with the guest concentration. • We found a dominant Dexter energy transfer from the triplet(guest) to triplet(host). • Energy transfer occurs from the host to guest and back to the host again.

3D Printing Polymers with Supramolecular Functionality for Biological Applications.

Science.gov (United States)

Pekkanen, Allison M; Mondschein, Ryan J; Williams, Christopher B; Long, Timothy E

2017-09-11

Supramolecular chemistry continues to experience widespread growth, as fine-tuned chemical structures lead to well-defined bulk materials. Previous literature described the roles of hydrogen bonding, ionic aggregation, guest/host interactions, and π-π stacking to tune mechanical, viscoelastic, and processing performance. The versatility of reversible interactions enables the more facile manufacturing of molded parts with tailored hierarchical structures such as tissue engineered scaffolds for biological applications. Recently, supramolecular polymers and additive manufacturing processes merged to provide parts with control of the molecular, macromolecular, and feature length scales. Additive manufacturing, or 3D printing, generates customizable constructs desirable for many applications, and the introduction of supramolecular interactions will potentially increase production speed, offer a tunable surface structure for controlling cell/scaffold interactions, and impart desired mechanical properties through reinforcing interlayer adhesion and introducing gradients or self-assembled structures. This review details the synthesis and characterization of supramolecular polymers suitable for additive manufacture and biomedical applications as well as the use of supramolecular polymers in additive manufacturing for drug delivery and complex tissue scaffold formation. The effect of supramolecular assembly and its dynamic behavior offers potential for controlling the anisotropy of the printed objects with exquisite geometrical control. The potential for supramolecular polymers to generate well-defined parts, hierarchical structures, and scaffolds with gradient properties/tuned surfaces provides an avenue for developing next-generation biomedical devices and tissue scaffolds.

Structural transitions and guest/host complexing of liquid crystal helical nanofilaments induced by nanoconfinement.

Science.gov (United States)

Kim, Hanim; Ryu, Seong Ho; Tuchband, Michael; Shin, Tae Joo; Korblova, Eva; Walba, David M; Clark, Noel A; Yoon, Dong Ki

2017-02-01

A lamellar liquid crystal (LC) phase of certain bent-core mesogenic molecules can be grown in a manner that generates a single chiral helical nanofilament in each of the cylindrical nanopores of an anodic aluminum oxide (AAO) membrane. By introducing guest molecules into the resulting composite chiral nanochannels, we explore the structures and functionality of the ordered guest/host LC complex, verifying the smectic-like positional order of the fluidic nematic LC phase, which is obtained by the combination of the LC organization and the nanoporous AAO superstructure. The guest nematic LC 4'- n -pentyl-4-cyanobiphenyl is found to form a distinctive fluid layered ordered LC complex at the nanofilament/guest interface with the host 1,3-phenylene bis[4-(4-nonyloxyphenyliminomethyl)benzoate], where this interface contacts the AAO cylinder wall. Filament growth form is strongly influenced by mixture parameters and pore dimensions.

Directed supramolecular surface assembly of SNAP-tag fusion proteins

NARCIS (Netherlands)

Uhlenheuer, D.A.; Wasserberg, D.; Haase, C.; Nguyen, H.; Schenkel, J.H.; Huskens, J.; Ravoo, B.J.; Jonkheijm, P.; Brunsveld, L.

2012-01-01

Supramolecular assembly of proteins on surfaces and vesicles was investigated by site-selective incorporation of a supramolecular guest element on proteins. Fluorescent proteins were site-selectively labeled with bisadamantane by SNAP-tag technology. The assembly of the bisadamantane functionalized

Directed Supramolecular Surface Assembly of SNAP-tag Fusion Proteins

NARCIS (Netherlands)

Uhlenheuer, D.A.; Wasserberg, D.; Haase, C.; Nguyen, Hoang D.; Schenkel, J.H.; Huskens, Jurriaan; Ravoo, B.J.; Jonkheijm, Pascal; Brunsveld, Luc

2012-01-01

Supramolecular assembly of proteins on surfaces and vesicles was investigated by site-selective incorporation of a supramolecular guest element on proteins. Fluorescent proteins were site-selectively labeled with bisadamantane by SNAP-tag technology. The assembly of the bisadamantane functionalized

Force and Stress along Simulated Dissociation Pathways of Cucurbituril-Guest Systems.

Science.gov (United States)

Velez-Vega, Camilo; Gilson, Michael K

2012-03-13

The field of host-guest chemistry provides computationally tractable yet informative model systems for biomolecular recognition. We applied molecular dynamics simulations to study the forces and mechanical stresses associated with forced dissociation of aqueous cucurbituril-guest complexes with high binding affinities. First, the unbinding transitions were modeled with constant velocity pulling (steered dynamics) and a soft spring constant, to model atomic force microscopy (AFM) experiments. The computed length-force profiles yield rupture forces in good agreement with available measurements. We also used steered dynamics with high spring constants to generate paths characterized by a tight control over the specified pulling distance; these paths were then equilibrated via umbrella sampling simulations and used to compute time-averaged mechanical stresses along the dissociation pathways. The stress calculations proved to be informative regarding the key interactions determining the length-force profiles and rupture forces. In particular, the unbinding transition of one complex is found to be a stepwise process, which is initially dominated by electrostatic interactions between the guest's ammoniums and the host's carbonyl groups, and subsequently limited by the extraction of the guest's bulky bicyclooctane moiety; the latter step requires some bond stretching at the cucurbituril's extraction portal. Conversely, the dissociation of a second complex with a more slender guest is mainly driven by successive electrostatic interactions between the different guest's ammoniums and the host's carbonyl groups. The calculations also provide information on the origins of thermodynamic irreversibilities in these forced dissociation processes.

Defined Host-Guest Chemistry on Nanocarbon for Sustained Inhibition of Cancer.

Science.gov (United States)

Ostadhossein, Fatemeh; Misra, Santosh K; Mukherjee, Prabuddha; Ostadhossein, Alireza; Daza, Enrique; Tiwari, Saumya; Mittal, Shachi; Gryka, Mark C; Bhargava, Rohit; Pan, Dipanjan

2016-08-22

Signal transducer and activator of transcription factor 3 (STAT-3) is known to be overexpressed in cancer stem cells. Poor solubility and variable drug absorption are linked to low bioavailability and decreased efficacy. Many of the drugs regulating STAT-3 expression lack aqueous solubility; hence hindering efficient bioavailability. A theranostics nanoplatform based on luminescent carbon particles decorated with cucurbit[6]uril is introduced for enhancing the solubility of niclosamide, a STAT-3 inhibitor. The host-guest chemistry between cucurbit[6]uril and niclosamide makes the delivery of the hydrophobic drug feasible while carbon nanoparticles enhance cellular internalization. Extensive physicochemical characterizations confirm successful synthesis. Subsequently, the host-guest chemistry of niclosamide and cucurbit[6]uril is studied experimentally and computationally. In vitro assessments in human breast cancer cells indicate approximately twofold enhancement in IC 50 of drug. Fourier transform infrared and fluorescence imaging demonstrate efficient cellular internalization. Furthermore, the catalytic biodegradation of the nanoplatforms occur upon exposure to human myeloperoxidase in short time. In vivo studies on athymic mice with MCF-7 xenograft indicate the size of tumor in the treatment group is half of the controls after 40 d. Immunohistochemistry corroborates the downregulation of STAT-3 phosphorylation. Overall, the host-guest chemistry on nanocarbon acts as a novel arsenal for STAT-3 inhibition. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dichroic dye-dependent studies in guest-host polymer-dispersed liquid crystal films

Energy Technology Data Exchange (ETDEWEB)

Malik, Praveen, E-mail: pmalik100@yahoo.co [Department of Physics, Dr. B.R. Ambedkar National Institute of Technology, Jalandhar 144011, Punjab (India); Raina, K.K. [Liquid Crystal Group, Materials Research Laboratory, School of Physics and Materials Science, Thapar University, Patiala 147004, Punjab (India)

2010-01-01

Guest-host polymer-dispersed liquid crystal (GHPDLC) films were prepared using a nematic liquid crystal, photo-curable polymer and dichroic dye (anthraquinone blue) by polymerization-induced phase separation (PIPS) technique. Non-ionic dichroic dye (1%, 2% and 4% wt./wt. ratio) was taken as guest in PDLC host. Polarizing microscopy shows that in the absence of electric field, liquid crystal (LC) droplets in polymer matrix mainly exhibit bipolar configuration, however, relatively at higher field, maltese-type crosses were observed. Our results show that approx1% dye-doped PDLC film shows better transmission and faster response times over pure polymer-dispersed nematic liquid crystal (PDNLC) and higher concentrated (2% and 4%) GHPDLC films.

Dichroic dye-dependent studies in guest-host polymer-dispersed liquid crystal films

International Nuclear Information System (INIS)

Malik, Praveen; Raina, K.K.

2010-01-01

Guest-host polymer-dispersed liquid crystal (GHPDLC) films were prepared using a nematic liquid crystal, photo-curable polymer and dichroic dye (anthraquinone blue) by polymerization-induced phase separation (PIPS) technique. Non-ionic dichroic dye (1%, 2% and 4% wt./wt. ratio) was taken as guest in PDLC host. Polarizing microscopy shows that in the absence of electric field, liquid crystal (LC) droplets in polymer matrix mainly exhibit bipolar configuration, however, relatively at higher field, maltese-type crosses were observed. Our results show that ∼1% dye-doped PDLC film shows better transmission and faster response times over pure polymer-dispersed nematic liquid crystal (PDNLC) and higher concentrated (2% and 4%) GHPDLC films.

Host-Guest Interaction of Cucurbit[8]uril with N-(3-Aminopropylcyclohexylamine: Cyclohexyl Encapsulation Triggered Ternary Complex

Directory of Open Access Journals (Sweden)

Yu Xia

2018-01-01

Full Text Available The host-guest interaction of a series of cyclohexyl-appended guests with cucurbit[8]uril (Q[8] was studied by 1H NMR spectroscopy, isothermal titration calorimetry (ITC, and X-ray crystallography. The X-ray structure revealed that two cycloalkane moieties can be simultaneously encapsulated in the hydrophobic cavity of the Q[8] host to form a ternary complex for the first time.

Quantitative analysis of the guest-concentration dependence of the mobility in a disordered fluorene-arylamine host-guest system in the guest-to-guest regime

NARCIS (Netherlands)

Nicolai, H. T.; Hof, A.J.; Lu, M.; Blom, P. W. M.; de Vries, R. J.; Coehoorn, R.

2011-01-01

The charge transport in a polyspirobifluorene derivative with copolymerized N,N,N',N'-tetraaryldiamino biphenyl (TAD) hole transport units is investigated as a function of the TAD content. For TAD concentrations larger than 5%, guest-to-guest transport is observed. It is demonstrated that in this

Quantitative analysis of the guest-concentration dependence of the mobility in a disordered fluorene-arylamine host-guest system in the guest-to-guest regime

NARCIS (Netherlands)

Nicolai, H.T.; Hof, A.J.; Lu, M.; Blom, P.W.M.; Vries, R.J. de; Coehoorn, R.

2011-01-01

The charge transport in a polyspirobifluorene derivative with copolymerized N,N,N',N'-tetraaryldiamino biphenyl (TAD) hole transport units is investigated as a function of the TAD content. For TAD concentrations larger than 5, guest-to-guest transport is observed. It is demonstrated that in this

Ab initio design of drug carriers for zoledronate guest molecule using phosphonated and sulfonated calix[4]arene and calix[4]resorcinarene host molecules

Science.gov (United States)

Jang, Yong-Man; Yu, Chol-Jun; Kim, Jin-Song; Kim, Song-Un

2018-04-01

Monomolecular drug carriers based on calix[n]-arenes and -resorcinarenes containing the interior cavity can enhance the affinity and specificity of the osteoporosis inhibitor drug zoledronate (ZOD). In this work we investigate the suitability of nine different calix[4]-arenes and -resorcinarenes based macrocycles as hosts for the ZOD guest molecule by conducting {\\it ab initio} density functional theory calculations for structures and energetics of eighteen different host-guest complexes. For the optimized molecular structures of the free, phosphonated, sulfonated calix[4]-arenes and -resorcinarenes, the geometric sizes of their interior cavities are measured and compared with those of the host-guest complexes in order to check the appropriateness for host-guest complex formation. Our calculations of binding energies indicate that in gaseous states some of the complexes might be unstable but in aqueous states almost all of the complexes can be formed spontaneously. Of the two different docking ways, the insertion of ZOD with the \\ce{P-C-P} branch into the cavity of host is easier than that with the nitrogen containing heterocycle of ZOD. The work will open a way for developing effective drug delivering systems for the ZOD drug and promote experimentalists to synthesize them.

Chapter 8: Selective Stoichiometric and Catalytic Reactivity in the Confines of a Chiral Supramolecular Assembly

Energy Technology Data Exchange (ETDEWEB)

University of California, Berkeley; Lawrence Berkeley National Laboratory; Raymond, Kenneth; Pluth, Michael D.; Bergman, Robert G.; Raymond, Kenneth N.

2007-09-27

Nature uses enzymes to activate otherwise unreactive compounds in remarkable ways. For example, DNases are capable of hydrolyzing phosphate diester bonds in DNA within seconds,[1-3]--a reaction with an estimated half-life of 200 million years without an enzyme.[4] The fundamental features of enzyme catalysis have been much discussed over the last sixty years in an effort to explain the dramatic rate increases and high selectivities of enzymes. As early as 1946, Linus Pauling suggested that enzymes must preferentially recognize and stabilize the transition state over the ground state of a substrate.[5] Despite the intense study of enzymatic selectivity and ability to catalyze chemical reactions, the entire nature of enzyme-based catalysis is still poorly understood. For example, Houk and co-workers recently reported a survey of binding affinities in a wide variety of enzyme-ligand, enzyme-transition-state, and synthetic host-guest complexes and found that the average binding affinities were insufficient to generate many of the rate accelerations observed in biological systems.[6] Therefore, transition-state stabilization cannot be the sole contributor to the high reactivity and selectivity of enzymes, but rather, other forces must contribute to the activation of substrate molecules. Inspired by the efficiency and selectivity of Nature, synthetic chemists have admired the ability of enzymes to activate otherwise unreactive molecules in the confines of an active site. Although much less complex than the evolved active sites of enzymes, synthetic host molecules have been developed that can carry out complex reactions with their cavities. While progress has been made toward highly efficient and selective reactivity inside of synthetic hosts, the lofty goal of duplicating enzymes specificity remains.[7-9] Pioneered by Lehn, Cram, Pedersen, and Breslow, supramolecular chemistry has evolved well beyond the crown ethers and cryptands originally studied.[10-12] Despite the

Host-Guest Interaction of Cucurbit[8]uril with N-(3-Aminopropyl)cyclohexylamine: Cyclohexyl Encapsulation Triggered Ternary Complex.

Science.gov (United States)

Xia, Yu; Wang, Chuan-Zeng; Tian, Mengkui; Tao, Zhu; Ni, Xin-Long; Prior, Timothy J; Redshaw, Carl

2018-01-15

The host-guest interaction of a series of cyclohexyl-appended guests with cucurbit[8]uril (Q[8]) was studied by ¹H NMR spectroscopy, isothermal titration calorimetry (ITC), and X-ray crystallography. The X-ray structure revealed that two cycloalkane moieties can be simultaneously encapsulated in the hydrophobic cavity of the Q[8] host to form a ternary complex for the first time.

Interactions and Supramolecular Organization of Sulfonated Indigo and Thioindigo Dyes in Layered Hydroxide Hosts.

Science.gov (United States)

Costa, Ana L; Gomes, Ana C; Pereira, Ricardo C; Pillinger, Martyn; Gonçalves, Isabel S; Pineiro, Marta; Seixas de Melo, J Sérgio

2018-01-09

Supramolecularly organized host-guest systems have been synthesized by intercalating water-soluble forms of indigo (indigo carmine, IC) and thioindigo (thioindigo-5,5'-disulfonate, TIS) in zinc-aluminum-layered double hydroxides (LDHs) and zinc-layered hydroxide salts (LHSs) by coprecipitation routes. The colors of the isolated powders were dark blue for hybrids containing only IC, purplish blue or dark lilac for cointercalated samples containing both dyes, and ruby/wine for hybrids containing only TIS. The as-synthesized and thermally treated materials were characterized by Fourier transform infrared, Fourier transform Raman, and nuclear magnetic resonance spectroscopies, powder X-ray diffraction, scanning electron microscopy, and elemental and thermogravimetric analyses. The basal spacings found for IC-LDH, TIS-LDH, IC-LHS, and TIS-LHS materials were 21.9, 21.05, 18.95, and 21.00 Å, respectively, with intermediate spacings being observed for the cointercalated samples that either decreased (LDHs) or increased (LHSs) with increasing TIS content. UV-visible and fluorescence spectroscopies (steady-state and time-resolved) were used to probe the molecular distribution of the immobilized dyes. The presence of aggregates together with the monomer units is suggested for IC-LDH, whereas for TIS-LDH, IC-LHS, and TIS-LHS, the dyes are closer to the isolated situation. Accordingly, while emission from the powder H 2 TIS is strongly quenched, an increment in the emission of about 1 order of magnitude was observed for the TIS-LDH/LHS hybrids. Double-exponential fluorescence decays were obtained and associated with two monomer species interacting differently with cointercalated water molecules. The incorporation of both TIS and IC in the LDH and LHS hosts leads to an almost complete quenching of the fluorescence, pointing to a very efficient energy transfer process from (fluorescent) TIS to (nonfluorescent) IC.

Toward a versatile toolbox for cucurbit[n]uril-based supramolecular hydrogel networks through in situ polymerization.

Science.gov (United States)

Liu, Ji; Soo Yun Tan, Cindy; Lan, Yang; Scherman, Oren A

2017-09-15

The success of exploiting cucurbit[ n ]uril (CB[ n ])-based molecular recognition in self-assembled systems has sparked a tremendous interest in polymer and materials chemistry. In this study, polymerization in the presence of host-guest complexes is applied as a modular synthetic approach toward a diverse set of CB[8]-based supramolecular hydrogels with desirable properties, such as mechanical strength, toughness, energy dissipation, self-healing, and shear-thinning. A range of vinyl monomers, including acrylamide-, acrylate-, and imidazolium-based hydrophilic monomers, could be easily incorporated as the polymer backbones, leading to a library of CB[8] hydrogel networks. This versatile strategy explores new horizons for the construction of supramolecular hydrogel networks and materials with emergent properties in wearable and self-healable electronic devices, sensors, and structural biomaterials. © 2017 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3105-3109.

Dual responsive supramolecular hydrogel with electrochemical activity.

Science.gov (United States)

Du, Ping; Liu, Jianghua; Chen, Guosong; Jiang, Ming

2011-08-02

Supramolecular materials with reversible responsiveness to environmental changes are of particular research interest in recent years. Inclusion complexation between cyclodextrin (CD) and ferrocene (Fc) is well-known and extensively studied because of its reversible association-dissociation controlled by the redox state of Fc. Although there are quite a few reported nanoscale materials incorporating this host-guest pair, polymeric hydrogels with electrochemical activity based on this interactive pair are still rare. Taking advantage of our previous reported hybrid inclusion complex (HIC) hydrogel structure, a new Fc-HIC was designed and obtained with β-CD-modified quantum dots as the core and Fc-ended diblock co-polymer p(DMA-b-NIPAM) as the shell, to achieve an electrochemically active hydrogel at elevated temperatures. Considering the two independent cross-linking strategies in the network structure, i.e., the interchain aggregation of pNIPAM and inclusion complexation between CD and Fc on the surface of the quantum dots, the hydrogel was fully thermo-reversible and its gel-sol transition was achieved after the addition of either an oxidizing agent or a competitive guest to Fc.

Host-guest chemistry of dendrimer-drug complexes: 7. Formation of stable inclusions between acetylated dendrimers and drugs bearing multiple charges.

Science.gov (United States)

Fang, Min; Zhang, Jiahai; Wu, Qinglin; Xu, Tongwen; Cheng, Yiyun

2012-03-15

Drug molecules bearing multiple charges usually form precipitates with cationic dendrimers, which presents a challenge during the preparation of dendrimer inclusions for these drugs. In the present study, fully acetylated polyamidoamine (PAMAM) dendrimers were proposed as stable vehicles for drug molecules bearing two negative charges such as Congo red and indocyanine green. NMR techniques including (1)H NMR and (1)H-(1)H NOESY were used to characterize the host-guest chemistry of acetylated dendrimer and these guest molecules. The cationic PAMAM dendrimer was found to form a precipitate with Congo red and indocyanine green, but the acetylated one avoided the formation of cross-linking structures in aqueous solutions. NOESY studies revealed the encapsulation of Congo red and indocyanine green within the interior cavities of PAMAM dendrimers at mild acidic conditions and acetylated dendrimers show much stronger ability to encapsulate the guest molecules than cationic ones. Also, UV-vis-NIR studies suggest that acetylated dendrimers significantly improve the photostability of indocyanine green and prevent the formation of indocyanine green J-aggregates in aqueous solutions. The present study provides a new insight into dendrimer-based host-guest systems, especially for those guest molecules bearing multiple charges. © 2012 American Chemical Society

Guest-Host Complex Formed between Ascorbic Acid and β-Cyclodextrin Immobilized on the Surface of an Electrode

Directory of Open Access Journals (Sweden)

María Teresa Ramírez-Silva

2014-05-01

Full Text Available This work deals with the formation of supramolecular complexes between ascorbic acid (AA, the guest, and β-cyclodextrin (β-CD, the host, that was first potentiodynamically immobilized on the surface of a carbon paste electrode (CPE throughout the formation of a β-CD-based conducting polymer (poly-β-CD. With the bare CPE and the β-CD-modified CPE, an electrochemical study was performed to understand the effect of such surface modification on the electrochemical response of the AA. From this study it was shown that on the modified-CPE, the AA was surface-immobilized through formation of an inclusion complex with β-CD, which provoked the adsorption of AA in such a way that this stage became the limiting step for the electrochemical oxidation of AA. Moreover, from the analysis of the experimental voltammetric plots recorded during AA oxidation on the CPE/poly-β-CD electrode surfaces, the Gibbs’ standard free energy of the inclusion complex formed by the oxidation product of AA and β-CD has been determined for the first time, ∆G0inclus = −36.4 kJ/mol.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Advances in supramolecular chemistry and crystal engineering reported from India within the last decade are highlighted in the categories of new intermolecular interactions, designed supramolecular architectures, network structures, multi-component host-guest systems, cocrystals, and polymorphs. Understanding ...

A targeted nanoglobular contrast agent from host-guest self-assembly for MR cancer molecular imaging.

Science.gov (United States)

Zhou, Zhuxian; Han, Zhen; Lu, Zheng-Rong

2016-04-01

The clinical application of nanoparticular Gd(III) based contrast agents for tumor molecular MRI has been hindered by safety concerns associated with prolonged tissue retention, although they can produce strong tumor enhancement. In this study, a targeted well-defined cyclodextrin-based nanoglobular contrast agent was developed through self-assembly driven by host-guest interactions for safe and effective cancer molecular MRI. Multiple β-cyclodextrins attached POSS (polyhedral oligomeric silsesquioxane) nanoglobule was used as host molecule. Adamantane-modified macrocyclic Gd(III) contrast agent, cRGD (cyclic RGDfK peptide) targeting ligand and fluorescent probe was used as guest molecules. The targeted host-guest nanoglobular contrast agent cRGD-POSS-βCD-(DOTA-Gd) specifically bond to αvβ3 integrin in malignant 4T1 breast tumor and provided greater contrast enhancement than the corresponding non-targeted agent. The agent also provided significant fluorescence signal in tumor tissue. The histological analysis of the tumor tissue confirmed its specific and effective targeting to αvβ3 integrin. The targeted imaging agent has a potential for specific cancer molecular MR and fluorescent imaging. Copyright © 2016 Elsevier Ltd. All rights reserved.

Supramolecular assembled three-dimensional graphene hybrids: Synthesis and applications in supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Ni, Lubin [College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu (China); Zhang, Wang [College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu (China); Graduate School of Convergence Science and Technology, Seoul National University, Seoul, 151-742 (Korea, Republic of); Wu, Zhen; Sun, Chunyu; Cai, Yin; Yang, Guang; Chen, Ming [College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu (China); Piao, Yuanzhe, E-mail: parkat9@snu.ac.kr [Graduate School of Convergence Science and Technology, Seoul National University, Seoul, 151-742 (Korea, Republic of); Diao, Guowang, E-mail: gwdiao@yzu.edu.cn [College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu (China)

2017-02-28

Graphical abstract: Supramolecular assembled three-dimensdional graphene-based architectures were built by host-guest interactions of β-cyclodextrin polymers(β-CDPs) with adamantine end-capped poly(ethylene oxide) polymer linker (PEG-AD), exhibit significantly improved electrochemical performances of supercapacitor in terms of high specific capacitance, remarkable rate capability, and excellent cycling stability compared to pristine reduced graphene oxide. - Highlights: • Supramolecular assembled three-Dimensional (3D) graphene was first fabricated by host-guest interactions of β-CDPs with PEG-AD linkers. • The incorporation of PEG-AD linker into rGO sheets can provide efficient 3D electron transfer pathways and ion diffusion channels. • The 3D self-assembled graphene exhibits high specific capacitance, remarkable rate capability, and excellent cycling stability. • This study shed new lights to design 3D self-assembled graphene materials and their urgent applications in energy storage. - Abstract: Graphene-based materials have received worldwide attention in the focus of forefront energy storage investigations. Currently, the design of novel three-dimensional (3D) graphene structures with high energy capability, superior electron and ion conductivity, and robust mechanical flexibility is still a great challenge. Herein, we have successfully demonstrated a novel approach to fabricate 3D assembled graphene through the supramolecular interactions of β-cyclodextrin polymers (β-CDP) with an adamantine end-capped poly(ethylene oxide) polymer linker (PEG-AD). The incorporation of PEG-AD linker into rGO sheets increased the interlayer spacing of rGO sheets to form 3D graphene materials, which can provide efficient 3D electron transfer pathways and ion diffusion channels, and facilitate the infiltration of gel electrolyte. The as-prepared 3D self-assembled graphene materials exhibit significantly improved electrochemical performances of supercapacitor in terms

Supramolecular assembled three-dimensional graphene hybrids: Synthesis and applications in supercapacitors

International Nuclear Information System (INIS)

Ni, Lubin; Zhang, Wang; Wu, Zhen; Sun, Chunyu; Cai, Yin; Yang, Guang; Chen, Ming; Piao, Yuanzhe; Diao, Guowang

2017-01-01

Graphical abstract: Supramolecular assembled three-dimensdional graphene-based architectures were built by host-guest interactions of β-cyclodextrin polymers(β-CDPs) with adamantine end-capped poly(ethylene oxide) polymer linker (PEG-AD), exhibit significantly improved electrochemical performances of supercapacitor in terms of high specific capacitance, remarkable rate capability, and excellent cycling stability compared to pristine reduced graphene oxide. - Highlights: • Supramolecular assembled three-Dimensional (3D) graphene was first fabricated by host-guest interactions of β-CDPs with PEG-AD linkers. • The incorporation of PEG-AD linker into rGO sheets can provide efficient 3D electron transfer pathways and ion diffusion channels. • The 3D self-assembled graphene exhibits high specific capacitance, remarkable rate capability, and excellent cycling stability. • This study shed new lights to design 3D self-assembled graphene materials and their urgent applications in energy storage. - Abstract: Graphene-based materials have received worldwide attention in the focus of forefront energy storage investigations. Currently, the design of novel three-dimensional (3D) graphene structures with high energy capability, superior electron and ion conductivity, and robust mechanical flexibility is still a great challenge. Herein, we have successfully demonstrated a novel approach to fabricate 3D assembled graphene through the supramolecular interactions of β-cyclodextrin polymers (β-CDP) with an adamantine end-capped poly(ethylene oxide) polymer linker (PEG-AD). The incorporation of PEG-AD linker into rGO sheets increased the interlayer spacing of rGO sheets to form 3D graphene materials, which can provide efficient 3D electron transfer pathways and ion diffusion channels, and facilitate the infiltration of gel electrolyte. The as-prepared 3D self-assembled graphene materials exhibit significantly improved electrochemical performances of supercapacitor in terms

Supramolecular Affinity Chromatography for Methylation-Targeted Proteomics.

Science.gov (United States)

Garnett, Graham A E; Starke, Melissa J; Shaurya, Alok; Li, Janessa; Hof, Fraser

2016-04-05

Proteome-wide studies of post-translationally methylated species using mass spectrometry are complicated by high sample diversity, competition for ionization among peptides, and mass redundancies. Antibody-based enrichment has powered methylation proteomics until now, but the reliability, pan-specificity, polyclonal nature, and stability of the available pan-specific antibodies are problematic and do not provide a standard, reliable platform for investigators. We have invented an anionic supramolecular host that can form host-guest complexes selectively with methyllysine-containing peptides and used it to create a methylysine-affinity column. The column resolves peptides on the basis of methylation-a feat impossible with a comparable commercial cation-exchange column. A proteolyzed nuclear extract was separated on the methyl-affinity column prior to standard proteomics analysis. This experiment demonstrates that such chemical methyl-affinity columns are capable of enriching and improving the analysis of methyllysine residues from complex protein mixtures. We discuss the importance of this advance in the context of biomolecule-driven enrichment methods.

A host-guest-recognition-based electrochemical aptasensor for thrombin detection.

Science.gov (United States)

Fan, Hao; Li, Hui; Wang, Qingjiang; He, Pingang; Fang, Yuzhi

2012-05-15

A sensitive electrochemical aptasensor for thrombin detection is presented based on the host-guest recognition technique. In this sensing protocol, a 15 based thrombin aptamer (ab. TBA) was dually labeled with a thiol at its 3' end and a 4-((4-(dimethylamino)phenyl)azo) benzoic acid (dabcyl) at its 5' end, respectively, which was previously immobilized on one Au electrode surface by AuS bond and used as the thrombin probe during the protein sensing procedure. One special electrochemical marker was prepared by modifying CdS nanoparticle with β-cyclodextrins (ab. CdS-CDs), which employed as electrochemical signal provider and would conjunct with the thrombin probe modified electrode through the host-guest recognition of CDs to dabcyl. In the absence of thrombin, the probe adopted linear structure to conjunct with CdS-CDs. In present of thrombin, the TBA bond with thrombin and transformed into its special G-quarter structure, which forced CdS-CDs into the solution. Therefore, the target-TBA binding event can be sensitively transduced via detecting the electrochemical oxidation current signal of Cd of CdS nanoparticles in the solution. Using this method, as low as 4.6 pM thrombin had been detected. Copyright © 2012 Elsevier B.V. All rights reserved.

Supramolecular Photodimerization of Coumarins

Directory of Open Access Journals (Sweden)

Koichi Tanaka

2012-02-01

Full Text Available Stereoselective photodimerization of coumarin and its derivatives in supra-molecular systems is reviewed. The enantioselective photodimerization of coumarin and thiocoumarin in inclusion crystals with optically active host compounds is also described.

Pressure-induced chemistry in a nitrogen-hydrogen host-guest structure

Science.gov (United States)

Spaulding, Dylan K.; Weck, Gunnar; Loubeyre, Paul; Datchi, Fréderic; Dumas, Paul; Hanfland, Michael

2014-12-01

New topochemistry in simple molecular systems can be explored at high pressure. Here we examine the binary nitrogen/hydrogen system using Raman spectroscopy, synchrotron X-ray diffraction, synchrotron infrared microspectroscopy and visual observation. We find a eutectic-type binary phase diagram with two stable high-pressure van der Waals compounds, which we identify as (N2)6(H2)7 and N2(H2)2. The former represents a new type of van der Waals host-guest compound in which hydrogen molecules are contained within channels in a nitrogen lattice. This compound shows evidence for a gradual, pressure-induced change in bonding from van der Waals to ionic interactions near 50 GPa, forming an amorphous dinitrogen network containing ionized ammonia in a room-temperature analogue of the Haber-Bosch process. Hydrazine is recovered on decompression. The nitrogen-hydrogen system demonstrates the potential for new pressure-driven chemistry in high-pressure structures and the promise of tailoring molecular interactions for materials synthesis.

A Supramolecular Sensing Platform for Phosphate Anions and an Anthrax Biomarker in a Microfluidic Device

Directory of Open Access Journals (Sweden)

Jurriaan Huskens

2011-10-01

Full Text Available A supramolecular platform based on self-assembled monolayers (SAMs has been implemented in a microfluidic device. The system has been applied for the sensing of two different analyte types: biologically relevant phosphate anions and aromatic carboxylic acids, which are important for anthrax detection. A Eu(III-EDTA complex was bound to β-cyclodextrin monolayers via orthogonal supramolecular host-guest interactions. The self-assembly of the Eu(III-EDTA conjugate and naphthalene β-diketone as an antenna resulted in the formation of a highly luminescent lanthanide complex on the microchannel surface. Detection of different phosphate anions and aromatic carboxylic acids was demonstrated by monitoring the decrease in red emission following displacement of the antenna by the analyte. Among these analytes, adenosine triphosphate (ATP and pyrophosphate, as well as dipicolinic acid (DPA which is a biomarker for anthrax, showed a strong response. Parallel fabrication of five sensing SAMs in a single multichannel chip was performed, as a first demonstration of phosphate and carboxylic acid screening in a multiplexed format that allows a general detection platform for both analyte systems in a single test run with µM and nM detection sensitivity for ATP and DPA, respectively.

From Having Fun to Applause: The Study of Relationships among Festival Benefits, Festival Identity and Festival Support by Viewpoints of the Hosts and Guests

Directory of Open Access Journals (Sweden)

Kai-Chih Chang

2017-12-01

Full Text Available The sustainable development of the festival depends on the support and participation of residents and tourists. There are a number of practical and theoretical gaps regarding the hosts and guests in festival literature. This study attempts to fill the host–guest gap based on the theory of reasoned action to construct and exam a relationship model. Taking the 2016 Summer Festival during busy season as an example in Hualien, 1165 questionnaires were valid, and data were analyzed by SEM (structural equation modeling. Results showed that the hosts had higher perception than the guests in terms of the festival benefits, identity, and support. This study has two concept models: the guest model and the host model. In the host model, the local-development benefits have more positive relationships to affect the festival support and festival identity than the recreation-experience benefits. On the other hand, the recreation-experience benefits could affect the festival support, but the festival identity could not in the guest model. The results of this study indicate that the festival organizers or the public sectors must be pay attention to the viewpoints of the guests and hosts in order to achieve the sustainable development objectives.

Size-controlled and redox-responsive supramolecular nanoparticles

NARCIS (Netherlands)

Weinhart-Mejia, R.; Kronig, G.A.; Huskens, Jurriaan

2015-01-01

Control over the assembly and disassembly of nanoparticles is pivotal for their use as drug delivery vehicles. Here, we aim to form supramolecular nanoparticles (SNPs) by combining advantages of the reversible assembly properties of SNPs using host–guest interactions and of a stimulus-responsive

Induction and Rationalization of Supramolecular Chirality in the Tweezer-Diamine Complexes: Insights from Experimental and DFT Studies.

Science.gov (United States)

Dhamija, Avinash; Ikbal, Sk Asif; Rath, Sankar Prasad

2016-12-19

A series of supramolecular chiral 1:1 sandwich complexes (1 M ·L and 2 M ·L) consisting of diphenylether/ethane bridged metallobisporphyrin host (1 M and 2 M ; M: Zn/Mg) and chiral diamine guest (L) have been presented. The host-guest complexes are compared just upon changing the metal ion (Mg vs Zn) or the bridge (highly flexible ethane vs rigid diphenylether) keeping other factors similar. The factors that would influence the chirality induction process along with their contributions toward the sign and intensity of the CD couplet of the overall complex have been analyzed. Larger CD amplitude was observed in the host-guest complex with the more flexible ethane bridge as compared to the rigid diphenylether bridged one, irrespective of the metal ion used. Also, Zn complexes have displayed larger CD amplitude because of their stronger binding with the chiral diamines. A fairly linear dependence between the binding constant (K) and CD amplitude has been observed. Moreover, the amplitude of the CD couplet has been correlated with the relative steric bulk of the substituent at the stereogenic center: with increasing the bulk, CD intensity gradually increases. However, large increase of steric hindrance, after a threshold value, has diminished the intensity. The observation of a weak positive CD couplet between (1R,2R)-DPEA guest and Zn-bisporphyrin hosts indicates that the clockwise-twisted (steric-controlled) conformer is more populated as compared to the anticlockwise (chirality-controlled) one. In contrast, amplitude of the positive CD couplets is larger with Mg-bisporphyrin hosts, suggesting almost exclusive contribution of the clockwise-twisted conformer guided solely by sterics. DFT calculations support the experimental observations and have displayed the possible interconversion between clockwise and anticlockwise twisted conformers just upon changing the bulk of the substituent irrespective of the nature of chirality at the stereogenic center.

The death of the Job plot, transparency, open science and online tools, uncertainty estimation methods and other developments in supramolecular chemistry data analysis.

Science.gov (United States)

Brynn Hibbert, D; Thordarson, Pall

2016-10-25

Data analysis is central to understanding phenomena in host-guest chemistry. We describe here recent developments in this field starting with the revelation that the popular Job plot method is inappropriate for most problems in host-guest chemistry and that the focus should instead be on systematically fitting data and testing all reasonable binding models. We then discuss approaches for estimating uncertainties in binding studies using case studies and simulations to highlight key issues. Related to this is the need for ready access to data and transparency in the methodology or software used, and we demonstrate an example a webportal () that aims to address this issue. We conclude with a list of best-practice protocols for data analysis in supramolecular chemistry that could easily be translated to other related problems in chemistry including measuring rate constants or drug IC 50 values.

Host-Guest Complexes of Cyclodextrins and Nanodiamonds as a Strong Non-Covalent Binding Motif for Self-Assembled Nanomaterials.

Science.gov (United States)

Schibilla, Frauke; Voskuhl, Jens; Fokina, Natalie A; Dahl, Jeremy E P; Schreiner, Peter R; Ravoo, Bart Jan

2017-11-13

We report the inclusion of carboxy- and amine-substituted molecular nanodiamonds (NDs) adamantane, diamantane, and triamantane by β-cyclodextrin and γ-cyclodextrin (β-CD and γ-CD), which have particularly well-suited hydrophobicity and symmetry for an optimal fit of the host and guest molecules. We studied the host-guest interactions in detail and generally observed 1:1 association of the NDs with the larger γ-CD cavity, but observed 1:2 association for the largest ND in the series (triamantane) with β-CD. We found higher binding affinities for carboxy-substituted NDs than for amine-substituted NDs. Additionally, cyclodextrin vesicles (CDVs) were decorated with d-mannose by using adamantane, diamantane, and triamantane as non-covalent anchors, and the resulting vesicles were compared with the lectin concanavalin A in agglutination experiments. Agglutination was directly correlated to the host-guest association: adamantane showed lower agglutination than di- or triamantane with β-CDV and almost no agglutination with γ-CDV, whereas high agglutination was observed for di- and triamantane with γ-CDV. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical exploration of the nanoscale host-guest interactions between [n]cycloparaphenylenes (n = 10, 8 and 9) and fullerene C₆₀: from single- to three-potential well.

Science.gov (United States)

Yuan, Kun; Zhou, Cai-Hua; Zhu, Yuan-Cheng; Zhao, Xiang

2015-07-28

The nanoscale host-guest interactions between [n]cycloparaphenylene ([n]CPP; n = 10, 8 and 9) nano-ring and fullerene C60 were explored theoretically. It is found that relatively small variations in the sizes of the [n]CPP host lead to very significant changes in encapsulation property toward the fullerene C60 guest. Expectedly, one stable inclusion-configuration of [10]CPP⊃C60 and one floating-configuration of [8]CPP⊃C60 are located on the potential surfaces of the two complexes, respectively. Unexpectedly, besides a floating-configuration (F-[9]CPP⊃C60), another stable inclusion-configuration (I-[9]CPP⊃C60) is also located on the potential surface of [9]CPP⊃C60 host-guest complex. Interaction energies and natural steric analysis show that these complexes are stabilized by balancing concave-convex π-π attractive and steric repulsive host-guest interactions. In contrast, the steric repulsive energy (Es) between host and guest of I-[9]CPP⊃C60 is as high as 233.12 kJ mol(-1), which is much larger than those in other complexes. The movements of C60 guest through the cavities of [n]CPP host (n = 10, 8 and 9) are simulated by calculating the energy profile, and the results interestingly reveal that the encapsulation of C60 by [10]CPP is in the manner of a single-potential well, by [8]CPP in the manner of a double-potential well, and by [9]CPP in the special manner of a three-potential well. We predict that the movement of C60 guest through the cavity of [9]CPP host should be experimentally observable owing to the relatively low energy barrier (<50 kJ mol(-1), M06-2X/6-31G(d)). Charge population analysis shows that an obvious charge transfer between host and guest takes place during the formation of I-[9]CPP⊃C60, which is different from those during the formation of [8]CPP⊃C60, [10]CPP⊃C60 and F-[9]CPP⊃C60. Additionally, the host-guest interaction regions were detected and visualized in real space based on the electron density and reduced density

Photoactive assemblies of organic compounds and biomolecules: drug-protein supramolecular systems

OpenAIRE

Vayá Pérez, Ignacio; Lhiaubet-Vallet, Virginie Lyria; Jiménez Molero, María Consuelo; Miranda Alonso, Miguel Ángel

2014-01-01

[EN] The properties of singlet and triplet excited states are strongly medium-dependent. Hence, these species constitute valuable tools as reporters to probe compartmentalised microenvironments, including drug@protein supramolecular systems. In the present review, the attention is focused on the photophysical properties of the probe drugs (rather than those of the protein chromophores) using transport proteins (serum albumins and 1-acid glycoproteins) as hosts. Specifically, f...

Synthesis of C3-symmetric tri(alkylamino) guests and their interaction with cyclodextrins

Czech Academy of Sciences Publication Activity Database

Bednaříková, T.; Tošner, Z.; Horský, Jiří; Jindřich, J.

2015-01-01

Roč. 81, 1-2 (2015), s. 141-152 ISSN 0923-0750 Institutional support: RVO:61389013 Keywords : cyclodextrin * supramolecular interactions * C3-symmetric guests Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 1.253, year: 2015

Study on luminescence characteristics of blue OLED with phosphor-doped host-guest structure

Science.gov (United States)

Wang, Zhen; Liu, Fei; Zheng, Xin; Chen, Ai; Xie, Jia-feng; Zhang, Wen-xia

2018-05-01

In this study, we design and fabricate phosphor-doped host-guest structure organic light-emitting diodes (OLEDs), where the blue-ray iridium complex electrophosphorescent material FIrpic acts as object material. Properties of the device can be accommodated by changing the host materials, dopant concentration and thickness of the light-emitting layer. The study shows that the host material N,N'-dicarbazolyl-3,5-benzene (mCP) has a higher triplet excited state energy level, which can effectively prevent FIrpic triplet excited state energy backtracking to host material, thus the luminous efficiency is improved. When mCP is selected as the host material, the thickness of the light-emitting layer is 30 nm and the dopant concentration is 8 wt%, the excitons can be effectively confined in the light-emitting region. As a result, the maximum current efficiency and the maximum brightness of the blue device can reach 15.5 cd/A and 7 196.3 cd/m2, respectively.

A Three - Dimensional Channel Supramolecular Architecture Based on 3-Amino-2-(4-dimethylaminophenyldiazenyl)-1-phenylbut-2en-1-one and Aromatic Guests

Czech Academy of Sciences Publication Activity Database

Macháček, V.; Bertolasi, V.; Šimůnek, P.; Svobodová, M.; Svoboda, Jan; Černošková, E.

2010-01-01

Roč. 10, č. 1 (2010), s. 85-91 ISSN 1528-7483 Institutional research plan: CEZ:AV0Z40500505 Keywords : X-ray structure * host-guest inclusion * compounds Subject RIV: CC - Organic Chemistry Impact factor: 4.390, year: 2010

Growth mode transition of tetrahydrofuran clathrate hydrates in the guest/host concentration boundary layer.

Science.gov (United States)

Sabase, Yuichiro; Nagashima, Kazushige

2009-11-19

Clathrate hydrates are known to form a thin film along a guest/host boundary. We present here the first report of tetrahydrofuran (THF) clathrate hydrate formation in a THF/water concentration boundary layer. We found that the THF-water system also forms a hydrate film separating the guest/host phases. The lateral growth rate of the film increases as supercooling increases. The thickness of the film at the growth tip decreases as supercooling and the lateral growth rate increase. These tendencies are consistent with reports of experiments for other hydrates and predictions of heat-transfer models. After film formation and slight melting, two types of growth modes are observed, depending on temperature T. At T = 3.0 degrees C, the film slowly thickens. The thickening rate is much lower than the lateral growth rate, as reported for other hydrates. At T agglomerate of small polycrystalline hydrates forms in each phase. Grain boundaries in the film and pore spaces in the agglomerate act as paths for permeation of each liquid. Timing when continuous nucleation starts is dominantly controlled by the time of initiation of liquid permeation through the film. Digital particle image velocimetry analysis of the agglomerate shows that it expands not by growth at the advancing front but rather by continuous nucleation in the interior. Expansion rates of the agglomerate tend to be higher for the cases of multipermeation paths in the film and the thinner film. We suppose that the growth mode transition to continuous nucleation is caused by the memory effect due to slight melting of the hydrate film.

Charge transport in disordered organic host-guest systems: effects of carrier density and electric field

NARCIS (Netherlands)

Yimer, Y.Y.; Bobbert, P.A.; Coehoorn, R.

2008-01-01

We investigate charge transport in disordered organic host–guest systems with a bimodal Gaussian density of states (DOS). The energy difference between the two Gaussians defines the trap depth. By solving the Pauli master equation for the hopping of charge carriers on a regular lattice with site

[Analysis on property of meridian supramolecules by biological evolution path].

Science.gov (United States)

Deng, Kaiwen; Tao, Yeqin; Tang, Wenhan; He, Fuyuan; Liu, Wenlong; Shi, Jilian; Yang, Yantao; Zhou, Yiqun; Chang, Xiaorong

2017-03-12

With human placed in the whole nature, by following the biologic evolution path, the property of channel structure for "imprinting template" in meridian and zang-fu was explored with supramolecular chemistry. In the history of biologic evolution, each molecule in "molecule society" gradually developed into various highly-ordered supramolecular bodies based on self-identification, self-assembly, self-organization, self-replicating of"imprinting template", and thereby the original biochemical system was established, and finally evolved into human. In the forming process of supramolecular bodies, the channel structure of"imprinting template" in guest supramolecular bodies would be kept by host supramolecular bodies, and communicate with the outside to exchange materials, energy, information, otherwise life phenomenon could not continue, for which it was the chemical nature of biolo-gical supramolecular bodies for body to develop meridian. Therefore, the human was a gigantic and complicated supramolecules body in biological nature, and possessed the supramolecules "imprinting template" at each stage of evolution, for which the meridians were formed. When meridians converged, acupoints appeared; when acupointsconverged, zang-fu appeared. With the promotion of the blood from heart, according to"imprinting template", the guest supramolecular bodies and host meridian produced qi -analysis, which was the qi -phenomenon of guest in meridian. It presented as zang-fu image of physiology and pathology as well as action regularities of medication and acupuncture tolerance, by which current various meridian viewpoints could be explained and propose the hypothesis of meridian supramolecular bodies. The meridian and its phenomenon was decide by its "imprinting template" of supramolecular bodies and self-reaction regularities, which abided through the living nature. This was the substance for meridian biology.

Host-guest complexes of 2-hydroxypropyl-β-cyclodextrin/β-cyclodextrin and nifedipine: 1H NMR, molecular modeling, and dissolution studies

Science.gov (United States)

de Araújo, Márcia Valéria Gaspar; Vieira, João Victor Francisco; da Silva, Caroline W. P.; Barison, Andersson; Andrade, George Ricardo Santana; da Costa, Nivan Bezerra; Barboza, Fernanda Malaquias; Nadal, Jessica Mendes; Novatski, Andressa; Farago, Paulo Vitor; Zawadzki, Sônia Faria

2017-12-01

Nifedipine (NIF) is a hydrophobic drug widely used for treating cardiovascular diseases. This calcium channel blocker can present a higher apparent solubility by its inclusion into different cyclodextrins (CDs) as host-guest complexes. This paper focused on the structural investigation and dissolution behavior of inclusion complexes prepared with 2-hydroxypropyl-β-cyclodextrin (HPβCD) or β-cyclodextrin (βCD) and NIF. Drug amorphization was observed for HPβCD/NIF and βCD/NIF inclusion complexes by X-ray diffractometry (XRD). The sharp endothermic peak of NIF was not observed for these both host-guest complexes by differential scanning calorimetry (DSC). These results of XRD and DSC provide evidences of complexation between drug and the investigated CDs. 1H and saturation transfer difference nuclear magnetic resonance studies revealed the enhancement in the signal at 2.27 ppm for HPβCD/NIF and βCD/NIF inclusion complexes that corresponded to the methyl groups of NIF from the non-aromatic ring. This result suggested that non-aromatic ring of NIF was inserted into HPβCD and βCD cavities. Considering the mathematical simulations, it was observed that the inclusion process can occur in the both NH-in or NH-out forms. However, since it was used aqueous medium, it is possible to indicate that the obtained host-guest complexes HPβCD/NIF and βCD/NIF are in NH-in form which corresponded to the previous results obtained by 1H NMR experiments. Dissolution assays demonstrated that NIF inclusion complexes improved the drug release nevertheless without changing its biexponential release behavior. These host-guest complexes can be further used as feasible NIF carriers in solid dosage forms.

Charge transport in disordered organic host-guest systems: effects of carrier density and electric field

NARCIS (Netherlands)

Yimer, Y.Y.; Bobbert, P.A.; Coehoorn, R.

2009-01-01

We investigate charge transport in disordered organic host–guest systems with a bimodal Gaussian density of states. The energy difference between the peaks of the two Gaussians defines the trap depth. By solving the Pauli master equation for the hopping of charge carriers on a regular lattice we

Smart protein biogate as a mediator to regulate competitive host-guest interaction for sensitive ratiometric electrochemical assay of prion

Science.gov (United States)

Yu, Peng; Zhang, Xiaohua; Zhou, Jiawan; Xiong, Erhu; Li, Xiaoyu; Chen, Jinhua

2015-11-01

A novel competitive host-guest strategy regulated by protein biogate was developed for sensitive and selective analysis of prion protein. The methylene blue (MB)-tagged prion aptamer (MB-Apt) was introduced to the multiwalled carbon nanotubes-β-cyclodextrins (MWCNTs-β-CD) composites-modified glassy carbon (GC) electrode through the host-guest interaction between β-CD and MB. In the absence of prion, MB-Apt could be displaced by ferrocenecarboxylic acid (FCA) due to its stronger binding affinity to β-CD, resulting in a large oxidation peak of FCA. However, in the presence of prion, the specific prion-aptamer interaction drove the formation of protein biogate to seal the cavity of β-CD, which hindered the guest displacement of MB by FCA and resulted in the oxidation peak current of MB (IMB) increased and that of FCA (IFCA) decreased. The developed aptasensor showed good response towards the target (prion protein) with a low detection limit of 160 fM. By changing the specific aptamers, this strategy could be easily extended to detect other proteins, showing promising potential for extensive applications in bioanalysis.

Organic light-emitting diodes for lighting: High color quality by controlling energy transfer processes in host-guest-systems

Science.gov (United States)

Weichsel, Caroline; Reineke, Sebastian; Furno, Mauro; Lüssem, Björn; Leo, Karl

2012-02-01

Exciton generation and transfer processes in a multilayer organic light-emitting diode (OLED) are studied in order to realize OLEDs with warm white color coordinates and high color-rendering index (CRI). We investigate a host-guest-system containing four phosphorescent emitters and two matrix materials with different transport properties. We show, by time-resolved spectroscopy, that an energy back-transfer from the blue emitter to the matrix materials occurs, which can be used to transport excitons to the other emitter molecules. Furthermore, we investigate the excitonic and electronic transfer processes by designing suitable emission layer stacks. As a result, we obtain an OLED with Commission Internationale de lÉclairage (CIE) coordinates of (0.444;0.409), a CRI of 82, and a spectrum independent of the applied current. The OLED shows an external quantum efficiency of 10% and a luminous efficacy of 17.4 lm/W at 1000 cd/m2.

Photophysics Applied to Cavitands and Capsules.

Science.gov (United States)

Berryman, Orion B; Dube, Henry; Rebek, Julius

2011-07-01

The use of light as a stimulus to control functional materials or nano-devices is appealing as it provides convenient control of triggering events where and when they are desired without introducing extra components to the system. Many photophysical and photochemical processes are extremely fast, giving rise to nearly instantaneous onset of events. However, these fast processes can be challenging to engineer into chemical systems. Supramolecular chemistry offers a convenient way to study and control photoprocesses. Given the reversible and self-programmed nature of modern host-guest systems, a modular approach can be considered in which different photoprocesses are coupled to obtain complex functions that emerge and are controlled solely by light inputs. In this review, we highlight recent examples of photoswitching and photophysics applied in the context of supramolecular host-guest systems, with a particular emphasis on resorcinarene based cavitands and hydrogen bonded capsules.

Investigation of the host-guest complexation between 4-sulfocalix[4]arene and nedaplatin for potential use in drug delivery

Science.gov (United States)

Fahmy, Sherif Ashraf; Ponte, Fortuna; Abd El-Rahman, Mohamed K.; Russo, Nino; Sicilia, Emilia; Shoeib, Tamer

2018-03-01

Macromolecules including macrocyclic species have been reported to have the potential to encapsulate biologically active compounds such as drugs through host-guest complexation to increase their solubility, stability and bioavailability. In this paper the first experimental and theoretical investigation of the complexation between nedaplatin, a second generation antineoplastic drug, and p-4-sulfocalix[4]arene, a macromolecule possessing a bipolar amphiphilic structure with good biocompatibility and relatively low haemolytic toxicity for potential use as a drug delivery system is presented. Data from 1H NMR, UV, Job's plot analysis, HPLC and DFT calculations are detailed and suggest the formation of a 1:1 complex. The stability constant of the complex was experimentally estimated to be 3.6 × 104 M- 1 and 2.1 × 104 M- 1 which correspond to values of - 6.2 and - 5.9 kcal mol- 1, respectively for the free energy of complexation while the interaction free energy is calculated to be - 4.9 kcal mol- 1. The formed species is shown to be stabilised in solution through hydrogen bonding between the host and the guest which may allow for this strategy to be effective for potential use in drug delivery.

Supramolecular Nanostructures Based on Cyclodextrin and Poly(ethylene oxide: Syntheses, Structural Characterizations and Applications for Drug Delivery

Directory of Open Access Journals (Sweden)

Yue Zheng

2016-05-01

Full Text Available Cyclodextrins (CDs have been extensively studied as drug delivery carriers through host–guest interactions. CD-based poly(pseudorotaxanes, which are composed of one or more CD rings threading on the polymer chain with or without bulky groups (or stoppers, have attracted great interest in the development of supramolecular biomaterials. Poly(ethylene oxide (PEO is a water-soluble, biocompatible polymer. Depending on the molecular weight, PEO can be used as a plasticizer or as a toughening agent. Moreover, the hydrogels of PEO are also extensively studied because of their outstanding characteristics in biological drug delivery systems. These biomaterials based on CD and PEO for controlled drug delivery have received increasing attention in recent years. In this review, we summarize the recent progress in supramolecular architectures, focusing on poly(pseudorotaxanes, vesicles and supramolecular hydrogels based on CDs and PEO for drug delivery. Particular focus will be devoted to the structures and properties of supramolecular copolymers based on these materials as well as their use for the design and synthesis of supramolecular hydrogels. Moreover, the various applications of drug delivery techniques such as drug absorption, controlled release and drug targeting based CD/PEO supramolecular complexes, are also discussed.

Thermosensitive Triterpenoid-Appended Polymers with Broad Temperature Tunability Regulated by Host-Guest Chemistry.

Science.gov (United States)

Hao, Jie; Gao, Yuxia; Li, Ying; Yan, Qiang; Hu, Jun; Ju, Yong

2017-09-05

Thermoresponsive water-soluble polymers are of great importance since they typically show a lower critical solution temperature (LCST) in aqueous media. In this research, the LCST change in broad temperature ranges of copolymers composed of natural glycyrrhetinic acid (GA)-based methacrylate and N,N'-dimethylacrylamides (DMAs) was investigated as a function of the concentration and the content of GA pendants. By complexation of GA pendants with β-cyclodextrin (β-CD), a side-chain polypseudorotaxane was obtained, which exhibited a significant increase in the LCST of copolymers. Moreover, the precisely reversible control of the LCST behavior was realized through adding a competing guest molecule, sodium 1-admantylcarboxylate. This work illustrates a simple and effective approach to endow water-soluble polymers with broad temperature tunability and helps us further understand the effect of a biocompatible host-guest complementary β-CD/GA pair on the thermoresponsive process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anticancer efficacy of a supramolecular complex of a 2-diethylaminoethyl–dextran–MMA graft copolymer and paclitaxel used as an artificial enzyme

Directory of Open Access Journals (Sweden)

Yasuhiko Onishi

2014-12-01

Full Text Available The anticancer efficacy of a supramolecular complex that was used as an artificial enzyme against multi-drug-resistant cancer cells was confirmed. A complex of diethylaminoethyl–dextran–methacrylic acid methylester copolymer (DDMC/paclitaxel (PTX, obtained with PTX as the guest and DDMC as the host, formed a nanoparticle 50–300 nm in size. This complex is considered to be useful as a drug delivery system (DDS for anticancer compounds since it formed a stable polymeric micelle in water. The resistance of B16F10 melanoma cells to PTX was shown clearly through a maximum survival curve. Conversely, the DDMC/PTX complex showed a superior anticancer efficacy and cell killing rate, as determined through a Michaelis–Menten-type equation, which may promote an allosteric supramolecular reaction to tubulin, in the same manner as an enzymatic reaction. The DDMC/PTX complex showed significantly higher anticancer activity compared to PTX alone in mouse skin in vivo. The median survival times of the saline, PTX, DDMC/PTX4 (particle size 50 nm, and DDMC/PTX5 (particle size 290 nm groups were 120 h (treatment (T/control (C, 1.0, 176 h (T/C, 1.46, 328 h (T/C, 2.73, and 280 h (T/C, 2.33, respectively. The supramolecular DDMC/PTX complex showed twice the effectiveness of PTX alone (p < 0.036. Above all, the DDMC/PTX complex is not degraded in cells and acts as an intact supramolecular assembly, which adds a new species to the range of DDS.

Optimization of the host–guest system within an OLED using different models of mobility

Energy Technology Data Exchange (ETDEWEB)

Adames Prada, Rosana, E-mail: rdadamesp@unal.edu.co; Ardila Vargas, Angel Miguel, E-mail: amardilav@unal.edu.co

2014-12-15

To optimize the host–guest system of organic light emitting devices (OLEDs), it were performed simulations by doping a small molecule organic semiconductor (acting as host) with the transition organometallic complex known as Ir(ppy){sub 2}(acac) (acting as a guest). The simulation was carried out using simOLED with different mobility models: the Pool–Frenkel Model (PFM), the Extended Gaussian Disorder Model (EGDM) and Extended Correlated Disorder Model (ECDM), with the aim to determine the magnitude of some parameters like temperature, applied electric field, film thickness and charge carrier density that improve the electrical and optical properties of OLEDs with a more simplified structure like ITO/CBP/CBP:Ir(ppy){sub 2}(acac)/TPBi/LiF/Al.

Final Technical Report: Targeting DOE-Relevant Ions with Supramolecular Strategies, DE-SC0010555

Energy Technology Data Exchange (ETDEWEB)

Bowman-James, Kristin [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemistry

2017-04-13

the pyrazine π system. Additionally appendages capable of influencing solvation effects can be introduced, and a number of other potential applications can be realized in areas such as soft materials chemistry, catalysis, sensing, and proton switches, the latter for binding and release of targeted guests. These findings provide a better foundation for understanding the selective binding of anions by targeted placement of hydrogen binding sites, and the strengths and weaknesses of various functional groups, that will allow for more the design of more effective anion sequestering agents. Our design strategy also used simple, cost-effective building blocks for host synthesis to allow for scale-up should real-world applications be forthcoming.

A Tunable Cyclic Container: Guest-Induced Conformational Switching, Efficient Guest Exchange, and Selective Isolation of C70 from a Fullerene Mixture.

Science.gov (United States)

Mondal, Pritam; Rath, Sankar Prasad

2017-07-18

An adaptable cyclic porphyrin dimer with highly flexible linkers has been used as an artificial molecular container that can efficiently encapsulate various aromatic guests (TCNQ/C 60 /C 70 ) through strong π-π interactions by adjusting its cavity size and conformation. The planar aromatic guest (TCNQ) can be easily and selectively exchanged with larger aromatic guests (C 60 /C 70 ). During the guest-exchange process, the two porphyrin rings switch their relative orientation according to the size and shape of the guests. This behavior of the cyclic container has been thoroughly investigated by using UV/Vis spectroscopy, NMR spectroscopy, and X-ray crystal structure determination of the host-guest assemblies. The electrochemical and photophysical studies demonstrated the occurrence of photoinduced electron transfer from bisporphyrin to TCNQ/C 60 /C 70 in the respective host-guest assemblies. The cyclic host can form complexes with C 60 and C 70 with association constants of (2.8±0.2)×10 5 and (1.9±0.3)×10 8  m -1 , respectively; the latter value represents the highest binding affinity for C 70 reported so far for zinc(II) bisporphyrinic receptors. This high selectivity for the binding of C 70 versus C 60 allows the easy extraction and efficient isolation of C 70 from a C 60 /C 70 fullerene mixture. Experimental evidence was substantiated by DFT calculations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

PPII propensity of multiple-guest amino acids in a proline-rich environment.

Science.gov (United States)

Moradi, Mahmoud; Babin, Volodymyr; Sagui, Celeste; Roland, Christopher

2011-07-07

There has been considerable debate about the intrinsic PPII propensity of amino acid residues in denatured polypeptides. Experimentally, this scale is based on the behavior of guest amino acid residues placed in the middle of proline-based hosts. We have used classical molecular dynamics simulations combined with replica-exchange methods to carry out a comprehensive analysis of the conformational equilibria of proline-based host oligopeptides with multiple guest amino acids including alanine, glutamine, valine, and asparagine. The tracked structural characteristics include the secondary structural motifs based on the Ramachandran angles and the cis/trans isomerization of the prolyl bonds. In agreement with our recent study of single amino acid guests, we did not observe an intrinsic PPII propensity in any of the guest amino acids in a multiple-guest setting. Instead, the experimental results can be explained in terms of (i) the steric restrictions imposed on the C-terminal guest amino acid that is immediately followed by a proline residue and (ii) an increase in the trans content of the prolyl bonds due to the presence of guest residues. In terms of the latter, we found that the more guests added to the system, the larger the increase in the trans content of the prolyl bonds, which results in an effective increase in the PPII content of the peptide.

Passivation of ZnO Nanowire Guests and 3D Inverse Opal Host Photoanodes for Dye-Sensitized Solar Cells

KAUST Repository

Labouchere, Philippe; Chandiran, Aravind Kumar; Moehl, Thomas; Harms, Hauke; Chavhan, Sudam; Tena-Zaera, Ramon; Nazeeruddin, Mohammad Khaja; Graetzel, Michael; Tetreault, Nicolas

2014-01-01

A hierarchical host-guest nanostructured photoanode is reported for dye-sensitized solar cells. It is composed of ZnO nanowires grown in situ into the macropores of a 3D ZnO inverse opal structure, which acts both as a seed layer and as a conductive

Adamantane-bearing benzylamines and benzylamides: novel building blocks for supramolecular systems with finely tuned binding properties towards β-cyclodextrin

Czech Academy of Sciences Publication Activity Database

Rouchal, M.; Matelová, A.; de Carvalho, F. P.; Bernat, R.; Grbić, D.; Kuřitka, I.; Babinský, M.; Marek, R.; Čmelík, Richard; Vícha, R.

2013-01-01

Roč. 25, č. 6 (2013), s. 349-361 ISSN 1061-0278 Institutional support: RVO:68081715 Keywords : host-guest system * cyclodextrins * adamantane Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.132, year: 2013

Formation and thermodynamic stability of (polymer + porphyrin) supramolecular structures in aqueous solutions

International Nuclear Information System (INIS)

Costa, Viviana C.P. da; Hwang, Barrington J.; Eggen, Spencer E.; Wallace, Megan J.; Annunziata, Onofrio

2014-01-01

Highlights: • Thermodynamic stability of a (polymer + porphyrin) supramolecular structure was characterized. • Isothermal titration calorimetry provided two ways to determine reaction enthalpies. • Exothermic (polymer + porphyrin) binding competes with porphyrin self-association. • (Polymer + porphyrin) binding is entropically favored with respect to porphyrin self-association. • Spectral shifts show importance of porphyrin central hydrogens in polymer binding. - Abstract: Optical properties of porphyrins can be tuned through (polymer + porphyrin) (host + guest) binding in solution. This gives rise to the formation of supramolecular structures. In this paper, the formation, thermodynamic stability and spectroscopic properties of (polymer + porphyrin) supramolecular structures and their competition with porphyrin self-association were investigated by both isothermal titration calorimetry (ITC) and absorption spectroscopy. Specifically, reaction enthalpies and equilibrium constants were measured for meso-tetrakis(4-sulfonatophenyl) porphyrin (TPPS) self-association and TPPS binding to the polymer poly(vinylpyrrolidone) (PVP, 40 kg/mol) in aqueous solutions at pH 7 and three different temperatures (12, 25 and 37 °C). ITC, compared to spectroscopic techniques, provides two independent means to determine reaction enthalpies: direct measurements and Van’t Hoff plot. This was used as a criterion to assess that (1) self-association of TPPS is limited to the formation of dimers and (2) TPPS binds to PVP in its monomeric state only. The formation of TPPS dimers and (PVP + TPPS) supramolecular structures are both enthalpically driven. However, (polymer + porphyrin) binding was found to be entropically favored compared to dimerization. Furthermore, the reaction enthalpies of these two processes significantly depend on temperature. This behavior was attributed to hydrophobic interactions. Finally, the limiting absorption spectra of monomeric, dimeric and polymer

Enhancement of Wound Healing in Normal and Diabetic Mice by Topical Application of Amorphous Polyphosphate. Superior Effect of a Host–Guest Composite Material Composed of Collagen (Host and Polyphosphate (Guest

Directory of Open Access Journals (Sweden)

Werner E.G. Müller

2017-07-01

Full Text Available The effect of polyphosphate (polyP microparticles on wound healing was tested both in vitro and in a mice model in vivo. Two approaches were used: pure salts of polyphosphate, fabricated as amorphous microparticles (MPs, consisting of calcium and magnesium salts of polyP, “Ca–polyp-MPs” and “Mg–polyp-MPs”, and host–guest composite particles, prepared from amorphous collagen (host and polyphosphate (guest, termed “col/polyp-MPs”. Animal experiments with polyP on healing of excisional wounds were performed using both normal mice and diabetic mice. After a healing period of 7 days “Ca–polyp-MP” significantly improved re-epithelialization in normal mice from 31% (control to 72% (polyP microparticle-treated. Importantly, in diabetic mice, particularly the host–guest particles “col/polyp-MP”, increased the rate of re-epithelialization to ≈40% (control, 23%. In addition, those particles increased the expression of COL-I and COL-III as well as the expression the α-smooth muscle actin and the plasminogen activator inhibitor-1. We propose that “Ca–polyp-MPs”, and particularly the host–guest “col/polyp-MPs” are useful for topical treatment of wounds.

Fabrication of CO2 Facilitated Transport Channels in Block Copolymer through Supramolecular Assembly

Directory of Open Access Journals (Sweden)

Yao Wang

2014-05-01

Full Text Available In this paper, the molecule 12-amidine dodecanoic acid (M with ending groups of carboxyl and amidine groups respectively was designed and synthesized as CO2-responsive guest molecules. The block copolymer polystyrene-b-polyethylene oxide (PS-b-PEO was chosen as the host polymer to fabricate a composite membrane through H-bonding assembly with guest molecule M. We attempted to tune the phase separation structure of the annealed film by varying the amount of M added, and investigated the nanostructures via transmission electron microscope (TEM, fourier transform infrared (FT-IR etc. As a result, a reverse worm-like morphology in TEM image of bright PS phase in dark PEO/M matrix was observed for PS-b-PEO/M1 membrane in which the molar ratio of EO unit to M was 1:1. The following gas permeation measurement indicated that the gas flux of the annealed membranes dramatically increased due to the forming of ordered phase separation structure. As we expected, the obtained composite membrane PS-b-PEO/M1 with EO:M mole ratio of 1:1 presented an evident selectivity for moist CO2 permeance, which is identical with our initial proposal that the guest molecule M in the membranes will play the key role for CO2 facilitated transportation since the amidine groups of M could react reversibly with CO2 molecules in membranes. This work provides a supramolecular approach to fabricating CO2 facilitated transport membranes.

Radical polymerization by a supramolecular catalyst: cyclodextrin with a RAFT reagent

Directory of Open Access Journals (Sweden)

Kohei Koyanagi

2016-11-01

Full Text Available Supramolecular catalysts have received a great deal of attention because they improve the selectivity and efficiency of reactions. Catalysts with host molecules exhibit specific reaction properties and recognize substrates via host–guest interactions. Here, we examined radical polymerization reactions with a chain transfer agent (CTA that has α-cyclodextrin (α-CD as a host molecule (α-CD-CTA. Prior to the polymerization of N,N-dimethylacrylamide (DMA, we investigated the complex formation of α-CD with DMA. Single X-ray analysis demonstrated that α-CD includes DMA inside its cavity. When DMA was polymerized in the presence of α-CD-CTA using 2,2'-azobis[2-(2-imidazolin-2-ylpropane dihydrochloride (VA-044 as an initiator in an aqueous solution, poly(DMA was obtained in good yield and with narrow molecular weight distribution. In contrast, the polymerization of DMA without α-CD-CTA produced more widely distributed polymers. In the presence of 1,6-hexanediol (C6 diol which works as a competitive molecule by being included in the α-CD cavity, the reaction yield was lower than that without C6 diol.

Host-guest chemistry of dendrimer-drug complexes. 4. An in-depth look into the binding/encapsulation of guanosine monophosphate by dendrimers.

Science.gov (United States)

Hu, Jingjing; Fang, Min; Cheng, Yiyun; Zhang, Jiahai; Wu, Qinglin; Xu, Tongwen

2010-06-03

In the present study, we investigated the host-guest chemistry of dendrimer/guanosine monophosphate (GMP) and present an in-depth look into the binding/encapsulation of GMP by dendrimers using NMR studies. (1)H NMR spectra showed a significant downfield shift of methylene protons in the outmost layer of the G5 dendrimer, indicating the formation of ion pairs between cationic amine groups of dendrimer and anionic phosphate groups of GMP. Chemical shift titration results showed that the binding constant between G5 dendrimer and GMP is 17,400 M(-1) and each G5 dendrimer has 107 binding sites. The binding of GMP to dendrimers prevents its aggregation in aqueous solutions and thereby enhances its stability. Nuclear Overhauser effect measurements indicated that a GMP binding and encapsulation balance occurs on the surface and in the interior of dendrimer. The binding/encapsulation transitions can be easily tailored by altering the surface and interior charge densities of the dendrimer. All these findings provide a new insight into the host-guest chemistry of dendrimer/guest complexes and may play important roles in the study of dendrimer/DNA aggregates by a "bottom-up" strategy.

Colloidal chirality in wormlike micellar systems exclusively originated from achiral species: Role of secondary assembly and stimulus responsivity.

Science.gov (United States)

Zhao, Wenrong; Hao, Jingcheng

2016-09-15

Colloidal chirality in wormlike micellar systems exclusively originated from achiral species and discussion of the role of secondary assembly of fiber-like aggregates in chirality generation were presented in this paper. Herein, formation of colloidal wormlike micelles for the first time incorporated chirality and redox-responsiveness into one design via noncovalent interaction. A dual-stimuli-responsive gel of wormlike micelles which were designed by employing a dual-responsive cationic surfactant (FTMA) and a strong gelator (AzoNa4) and regulated by redox reaction and host-guest inclusion is presented. Both the redox and host-guest interaction play an important role in regulating the viscosity and supramolecular chirality of gels of the wormlike micelles. The supramolecular chirality and viscosity of the wormlike micelle gels were switched reversibly by exerting chemical redox onto the ferrocenyl groups. For the amphiphile FTMA containing redox-active ferrocenyl group, reversible control of the oxidation state of ferrocenyl groups leads to the charge and hydrophobicity changes of FTMA, therefore change its self-assembly behavior. Of equal interest, β-CD successfully detached the wormlike micelles via the recognition-inclusion behavior with FTMA and invalidate the H-bond and hydrophobic interaction between FTMA and AzoH4. This designed system provides a new strategy to tune the supramolecular chirality of colloidal aggregates and explore the specific packing mode detail within the micelles or the secondary assembly of the inter-micelles. We anticipate this dual-responsive H-bond-directed chiral gel switch could propose a new strategy when researchers designing new, multi-responsive functional gel materials. Copyright © 2016 Elsevier Inc. All rights reserved.

Host-Guest Inclusion Complexes between Amlodipine Enantiomers in the Biphasic Recognition Chiral Extraction System using Tartaric Acid and β-Cyclodextrin Derivatives as Positive Confirmation by using their Enantioselective Extraction.

Science.gov (United States)

Al Azzam, Khaldun M; Abdallah, Hassan H; Halim, Hairul N Abdul; Ahmad, Maizatul Akmam; Shaibah, Hassan

2015-01-01

The current work reports an extended theoretical study from our previous experimental work for the enantioselective extraction of amlodipine enantiomers in a biphasic recognition chiral extraction system (BRCES) consisting of hydrophobic D-diisopropyl tartrate dissolved in organic phase (n-decanol) and hydrophilic hydroxypropyl-β-cyclodextrin (HP-β-CD) in aqueous phase (acetate buffer) which preferentially recognize the R-enantiomer and S-enantiomer, respectively. The calculations were simulated using a semi-empirical PM3 method as a part of the Gaussian09 software package and were used to optimize the structures of the hosts, guests, and host-guest complexes in the gas phase without any restrictions. It was found that HP-β-CD has the strongest recognition ability among the three β-CD derivatives studied, namely HP-β-CD, hydroxyethyl-β-cyclodextrin (HE-β-CD), and methylated-β-cyclodextrin (Me-β-CD), due to the large interaction energies (Ecomp = -14.3025 kcal/ mol), while D-diisopropyl tartrate has the strongest ability among the four tartaric acid derivatives studied namely; L-diisopropyl tartrate, D-diisopropyl tartrate, L-diethyl tartrate, and D-diethyl tartrate (Ecomp = -5.9964 kcal/ mol). The computational calculations for the enantioselective partitioning of amlodipine enantiomers rationalized the reasons for the different behaviors for this extraction. The present theoretical results may be informative to scientists who are devoting themselves to developing models for their experimental parts or for enhancing the hydrophobic drug solubility in drug delivery systems.

Host-Guest Inclusion Complexes between Amlodipine Enantiomers in the Biphasic Recognition Chiral Extraction System using Tartaric Acid and β-Cyclodextrin Derivatives as Positive Confirmation by using their Enantioselective Extraction

Science.gov (United States)

Al Azzam, Khaldun M.; Abdallah, Hassan H.; Halim, Hairul N. Abdul; Ahmad, Maizatul Akmam; Shaibah, Hassan

2015-01-01

The current work reports an extended theoretical study from our previous experimental work for the enantioselective extraction of amlodipine enantiomers in a biphasic recognition chiral extraction system (BRCES) consisting of hydrophobic D-diisopropyl tartrate dissolved in organic phase (n-decanol) and hydrophilic hydroxypropyl-β-cyclodextrin (HP-β-CD) in aqueous phase (acetate buffer) which preferentially recognize the R-enantiomer and S-enantiomer, respectively. The calculations were simulated using a semi-empirical PM3 method as a part of the Gaussian09 software package and were used to optimize the structures of the hosts, guests, and host-guest complexes in the gas phase without any restrictions. It was found that HP-β-CD has the strongest recognition ability among the three β-CD derivatives studied, namely HP-β-CD, hydroxyethyl-β-cyclodextrin (HE-β-CD), and methylated-β-cyclodextrin (Me-β-CD), due to the large interaction energies (Ecomp = −14.3025 kcal/ mol), while D-diisopropyl tartrate has the strongest ability among the four tartaric acid derivatives studied namely; L-diisopropyl tartrate, D-diisopropyl tartrate, L-diethyl tartrate, and D-diethyl tartrate (Ecomp = −5.9964 kcal/ mol). The computational calculations for the enantioselective partitioning of amlodipine enantiomers rationalized the reasons for the different behaviors for this extraction. The present theoretical results may be informative to scientists who are devoting themselves to developing models for their experimental parts or for enhancing the hydrophobic drug solubility in drug delivery systems. PMID:26839848

Foreign Guests in Ancient Greece

Directory of Open Access Journals (Sweden)

Zora Žbontar

2013-12-01

Full Text Available Xenía was a special relationship between a foreign guest and his host in Ancient Greece. The ritual of hosting a foreigner included an exchange of objects, feasting, and the establishment of friendship between people from different social backgrounds. This relationship implied trust, loyalty, friendship, and mutual aid between the people involved. Goods and services were also exchanged without any form of payment. There were no formal laws governing xenía – it was based entirely on a moral appeal. Mutual appreciation between the host and the guest was established during the ritual, but the host did retain a certain level of superiority over the guest. Xenía was one of the most important institutions in Ancient Greece. It had a lot of features and obligations similar to kinship and marriage. In literary sources the word xénos varies in meaning from “enemy stranger”, “friendly stranger”, “foreigner”, “guest”, “host” to “ritual friend”, and it is often hard to tell which usage is appropriate in a given passage. The paper describes the emphasis on hospitality towards foreigners. It presents an example of a depiction indicating xenía is presented, as well as several objects which were traded during the ritual. The paper also addresses the importance of hospitality in Greek drama in general, especially with examples of violations of the hospitality code.

Passivation of ZnO Nanowire Guests and 3D Inverse Opal Host Photoanodes for Dye-Sensitized Solar Cells

KAUST Repository

Labouchere, Philippe

2014-04-23

A hierarchical host-guest nanostructured photoanode is reported for dye-sensitized solar cells. It is composed of ZnO nanowires grown in situ into the macropores of a 3D ZnO inverse opal structure, which acts both as a seed layer and as a conductive backbone host. Using a combination of self-assembly, hydrothermal or electrodeposition of single crystalline ZnO nanowires and TiO2 passivation, a novel photoanode with scattering capability for optimal light harvesting is fabricated. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective molecular recognition, C-H bond activation, and catalysis in nanoscale reaction vessels

Energy Technology Data Exchange (ETDEWEB)

Fiedler, Dorothea; Leung, Dennis H.; Raymond, Kenneth N.; Bergman, Robert G.

2004-11-27

Supramolecular chemistry represents a way to mimic enzyme reactivity by using specially designed container molecules. We have shown that a chiral self-assembled M{sub 4}L{sub 6} supramolecular tetrahedron can encapsulate a variety of cationic guests, with varying degrees of stereoselectivity. Reactive iridium guests can be encapsulated and the C-H bond activation of aldehydes occurs, with the host cavity controlling the ability of substrates to interact with the metal center based upon size and shape. In addition, the host container can act as a catalyst by itself. By restricting reaction space and preorganizing the substrates into reactive conformations, it accelerates the sigmatropic rearrangement of enammonium cations.

Guest-host chemistry with dendrimers—binding of carboxylates in aqueous solution

DEFF Research Database (Denmark)

Ficker, Mario; Petersen, Johannes Fabritius; Hansen, Jon Stefan

2015-01-01

Recognition and binding of anions in water is difficult due to the ability of water molecules to form strong hydrogen bonds and to solvate the anions. The complexation of two different carboxylates with 1-(4-carbomethoxypyrrolidone)-terminated PAMAM dendrimers was studied in aqueous solution using...... the carboxylate-dendrimer interaction selectively. The binding stoichiometry for 3-hydroxy-2-naphthoate was found to be two strongly bound guest molecules per dendrimer and an additional 40 molecules with weak binding affinity. The NOESY NMR showed a clear binding correlation of sodium 3-hydroxy-2-naphthoate...... with the lyophilic dendrimer core, possibly with the two high affinity guest molecules. In comparison, sodium 2-naphthoate showed a weaker binding strength and had a stoichiometry of two guests per dendrimer with no additional weakly bound guests. This stronger dendrimer interaction with sodium 3-hydroxy-2...

Dynamic Softening or Stiffening a Supramolecular Hydrogel by Ultraviolet or Near-Infrared Light.

Science.gov (United States)

Zheng, Zhao; Hu, Jingjing; Wang, Hui; Huang, Junlin; Yu, Yihua; Zhang, Qiang; Cheng, Yiyun

2017-07-26

The development of light-responsive hydrogels that exhibit switchable size and mechanical properties with temporal and spatial resolution is of great importance in many fields. However, it remains challenging to prepare smart hydrogels that dramatically change their properties in response to both ultraviolet (UV) and near-infrared (NIR) lights. Here, we designed a dual-light responsive supramolecular gel by integrating UV light-switchable host-guest recognition, temperature responsiveness, and NIR photothermal ability in the gel. The gel could rapidly self-heal and is capable of both softening and stiffening controlled by UV and NIR lights, respectively. Besides stiffness modulation, the bending direction of the gel can be controlled by UV or NIR light irradiation. The smart gel makes it possible to generate dynamic materials that respond to both UV and NIR lights and represents a useful tool that might be used to modulate cellular microenvironments with spatiotemporal resolution.

Microcalorimetric and spectrographic studies on host-guest interactions of {alpha}-, {beta}-, {gamma}- and M{beta}-cyclodextrin with resveratrol

Energy Technology Data Exchange (ETDEWEB)

Li, Hui; Xu, Xiangyu; Liu, Min [College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, Shandong Province (China); Sun, Dezhi, E-mail: sundezhisdz@163.com [College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, Shandong Province (China); Li, Linwei, E-mail: lilinwei@lcu.edu.cn [College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, Shandong Province (China)

2010-10-20

Thermal effects of inclusion processes of {alpha}-, {beta}-, {gamma}- and M{beta}-cyclodextrin with resveratrol (RES) in aqueous solutions were determined by isothermal titration calorimetry (ITC) with nanowatt sensitivity at the temperature of 298.15 K. Standard enthalpy changes, stoichiometry and equilibrium constants of the inclusion complexes were derived from the direct calorimetric data utilizing nonlinear simulation. The thermodynamic parameters were discussed in the light of weak interactions between the host and the guest molecules combining with UV spectral message. The results indicate that all of the complexes formed in the aqueous solutions are in 1:1 stoichiometry. The binding processes of {alpha}-, {beta}- and M{beta}-cyclodextrin with the guest are mainly driven by enthalpy, while that of {gamma}-cyclodextrin with the drug is driven by both enthalpy and entropy.

Binding abilities of a chiral calix[4]resorcinarene: a polarimetric investigation on a complex case of study

Directory of Open Access Journals (Sweden)

Marco Russo

2017-12-01

Full Text Available Polarimetry was used to investigate the binding abilities of a chiral calix[4]resorcinarene derivative, bearing L-proline subunits, towards a set of suitably selected organic guests. The simultaneous formation of 1:1 and 2:1 host–guest inclusion complexes was observed in several cases, depending on both the charge status of the host and the structure of the guest. Thus, the use of the polarimetric method was thoroughly revisited, in order to keep into account the occurrence of multiple equilibria. Our data indicate that the stability of the host–guest complexes is affected by an interplay between Coulomb interactions, π–π interactions, desolvation effects and entropy-unfavorable conformational dynamic restraints. Polarimetry is confirmed as a very useful and versatile tool for the investigation of supramolecular interactions with chiral hosts, even in complex systems involving multiple equilibria.

Interactions between 4-thiothymidine and water-soluble cyclodextrins: Evidence for supramolecular structures in aqueous solutions

OpenAIRE

Rizzi, Vito; Matera, Sergio; Semeraro, Paola; Fini, Paola; Cosma, Pinalysa

2016-01-01

Since several years the inclusion of organic compounds (guests) within the hydrophobic cavity (host) of cyclodextrins (CDs) has been the subject of many investigations. Interestingly, the formation of inclusion complexes could affect the properties of the guest molecules and, for example, the influence of the delivery system can be a method to improve/change the photochemical behavior of the guest. In particular, very recent studies have shown the protective role of CDs preventing the degrada...

Intelligent Chiral Sensing Based on Supramolecular and Interfacial Concepts

Directory of Open Access Journals (Sweden)

Hironori Izawa

2010-07-01

Full Text Available Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized.

Analyses of polycyclic aromatic hydrocarbon (PAH) and chiral-PAH analogues-methyl-β-cyclodextrin guest-host inclusion complexes by fluorescence spectrophotometry and multivariate regression analysis.

Science.gov (United States)

Greene, LaVana; Elzey, Brianda; Franklin, Mariah; Fakayode, Sayo O

2017-03-05

The negative health impact of polycyclic aromatic hydrocarbons (PAHs) and differences in pharmacological activity of enantiomers of chiral molecules in humans highlights the need for analysis of PAHs and their chiral analogue molecules in humans. Herein, the first use of cyclodextrin guest-host inclusion complexation, fluorescence spectrophotometry, and chemometric approach to PAH (anthracene) and chiral-PAH analogue derivatives (1-(9-anthryl)-2,2,2-triflouroethanol (TFE)) analyses are reported. The binding constants (K b ), stoichiometry (n), and thermodynamic properties (Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS)) of anthracene and enantiomers of TFE-methyl-β-cyclodextrin (Me-β-CD) guest-host complexes were also determined. Chemometric partial-least-square (PLS) regression analysis of emission spectra data of Me-β-CD-guest-host inclusion complexes was used for the determination of anthracene and TFE enantiomer concentrations in Me-β-CD-guest-host inclusion complex samples. The values of calculated K b and negative ΔG suggest the thermodynamic favorability of anthracene-Me-β-CD and enantiomeric of TFE-Me-β-CD inclusion complexation reactions. However, anthracene-Me-β-CD and enantiomer TFE-Me-β-CD inclusion complexations showed notable differences in the binding affinity behaviors and thermodynamic properties. The PLS regression analysis resulted in square-correlation-coefficients of 0.997530 or better and a low LOD of 3.81×10 -7 M for anthracene and 3.48×10 -8 M for TFE enantiomers at physiological conditions. Most importantly, PLS regression accurately determined the anthracene and TFE enantiomer concentrations with an average low error of 2.31% for anthracene, 4.44% for R-TFE and 3.60% for S-TFE. The results of the study are highly significant because of its high sensitivity and accuracy for analysis of PAH and chiral PAH analogue derivatives without the need of an expensive chiral column, enantiomeric resolution, or use of a polarized

Colligative thermoelectric transport properties in n-type filled CoSb3 determined by guest electrons in a host lattice

International Nuclear Information System (INIS)

Lim, Young Soo; Park, Kwan-Ho; Tak, Jang Yeul; Lee, Soonil; Seo, Won-Seon; Park, Cheol-Hee; Kim, Tae Hoon; Park, PumSuk; Kim, Il-Ho; Yang, Jihui

2016-01-01

Among many kinds of thermoelectric materials, CoSb 3 has received exceptional attention for automotive waste heat recovery. Its cage structure provides an ideal framework for the realization of phonon-glass electron-crystal strategy, and there have been numerous reports on the enhanced thermoelectric performance through the independent control of the thermal and electrical conductivity by introducing fillers into its cage sites. Herein, we report colligative thermoelectric transport properties in n-type CoSb 3 from the viewpoint of “guest electrons in a host lattice.” Both the Seebeck coefficient and the charge transport properties are fundamentally determined by the concentration of the guest electrons, which are mostly donated by the fillers, in the conduction band of the host CoSb 3 . Comparing this observation to our previous results, colligative relations for both the Seebeck coefficient and the mobility were deduced as functions of the carrier concentration, and thermoelectric transport constants were defined to predict the power factor in filled CoSb 3 . This discovery not only increases the degree of freedom for choosing a filler but also provides the predictability of power factor in designing and engineering the n-type filled CoSb 3 materials.

On the characterization of dynamic supramolecular systems: a general mathematical association model for linear supramolecular copolymers and application on a complex two-component hydrogen-bonding system.

Science.gov (United States)

Odille, Fabrice G J; Jónsson, Stefán; Stjernqvist, Susann; Rydén, Tobias; Wärnmark, Kenneth

2007-01-01

A general mathematical model for the characterization of the dynamic (kinetically labile) association of supramolecular assemblies in solution is presented. It is an extension of the equal K (EK) model by the stringent use of linear algebra to allow for the simultaneous presence of an unlimited number of different units in the resulting assemblies. It allows for the analysis of highly complex dynamic equilibrium systems in solution, including both supramolecular homo- and copolymers without the recourse to extensive approximations, in a field in which other analytical methods are difficult. The derived mathematical methodology makes it possible to analyze dynamic systems such as supramolecular copolymers regarding for instance the degree of polymerization, the distribution of a given monomer in different copolymers as well as its position in an aggregate. It is to date the only general means to characterize weak supramolecular systems. The model was fitted to NMR dilution titration data by using the program Matlab, and a detailed algorithm for the optimization of the different parameters has been developed. The methodology is applied to a case study, a hydrogen-bonded supramolecular system, salen 4+porphyrin 5. The system is formally a two-component system but in reality a three-component system. This results in a complex dynamic system in which all monomers are associated to each other by hydrogen bonding with different association constants, resulting in homo- and copolymers 4n5m as well as cyclic structures 6 and 7, in addition to free 4 and 5. The system was analyzed by extensive NMR dilution titrations at variable temperatures. All chemical shifts observed at different temperatures were used in the fitting to obtain the DeltaH degrees and DeltaS degrees values producing the best global fit. From the derived general mathematical expressions, system 4+5 could be characterized with respect to above-mentioned parameters.

Construction of Supramolecular Architectures via Self-assembly

Institute of Scientific and Technical Information of China (English)

Takeharu; Haino

2007-01-01

1 Results In this paper we report supramolecular polymeric nano networks formed by the molecular-recognition-directed self-assembly between a calix[5]arene and C60[1]. Covalently-linked double-calix[5]arenes take up C60 into their cavities[2]. This complementary interaction creates a strong non-covalent bonding; thus,the iterative self-assembly between dumbbell fullerene 1 and ditopic host 2 can produce the supramolecular polymer networks (See Fig.1).

Supramolecular chemistry and chemical warfare agents: from fundamentals of recognition to catalysis and sensing.

Science.gov (United States)

Sambrook, M R; Notman, S

2013-12-21

Supramolecular chemistry presents many possible avenues for the mitigation of the effects of chemical warfare agents (CWAs), including sensing, catalysis and sequestration. To-date, efforts in this field both to study fundamental interactions between CWAs and to design and exploit host systems remain sporadic. In this tutorial review the non-covalent recognition of CWAs is considered from first principles, including taking inspiration from enzymatic systems, and gaps in fundamental knowledge are indicated. Examples of synthetic systems developed for the recognition of CWAs are discussed with a focus on the supramolecular complexation behaviour and non-covalent approaches rather than on the proposed applications.

Solid-state {sup 2}H NMR investigations in guest-host systems and plastic crystals

Energy Technology Data Exchange (ETDEWEB)

Garibay, J.A.V.

2004-07-01

Variable temperature {sup 2}H NMR investigations have been carried out to study the molecular behavior of perdeuterated benzene and pyridine in the inclusion compound with tris-(1,2-dioxyphenyl)-cyclotriphosphazene. Here, a comprehensive variable temperature {sup 2}H NMR study is presented comprising line shape studies and relaxation experiments. The experimental data clearly indicate the presence of highly mobile guest species. Sample cooling gives rise to characteristic line shape effects that can be attributed to a slow-down of the rotational motion. Additional {sup 2}H NMR measurements were performed on the plastic crystal 1,4-diazabicyclo[2,2,2]octane where highly mobile species were observed. A quantitative analysis of the experimental data is achieved by appropriate computer simulations taking into account various molecular motions for each studied system. The analysis of these theoretical data give rise to the kinetic parameters that are in the order of related systems. (orig.)

Biasing hydrogen bond donating host systems towards chemical warfare agent recognition.

Science.gov (United States)

Hiscock, Jennifer R; Wells, Neil J; Ede, Jayne A; Gale, Philip A; Sambrook, Mark R

2016-10-12

A series of neutral ditopic and negatively charged, monotopic host molecules have been evaluated for their ability to bind chloride and dihydrogen phosphate anions, and neutral organophosphorus species dimethyl methylphosphonate (DMMP), pinacolyl methylphosphonate (PMP) and the chemical warfare agent (CWA) pinacolyl methylphosphonofluoridate (GD, soman) in organic solvent via hydrogen bonding. Urea, thiourea and boronic acid groups are shown to bind anions and neutral guests through the formation of hydrogen bonds, with the urea and thiourea groups typically exhibiting higher affinity interactions. The introduction of a negative charge on the host structure is shown to decrease anion affinity, whilst still allowing for high stability host-GD complex formation. Importantly, the affinity of the host for the neutral CWA GD is greater than for anionic guests, thus demonstrating the potential for selectivity reversal based on charge repulsion.

Recognition-Mediated Hydrogel Swelling Controlled by Interaction with a Negative Thermoresponsive LCST Polymer.

Science.gov (United States)

Belal, Khaled; Stoffelbach, François; Lyskawa, Joël; Fumagalli, Matthieu; Hourdet, Dominique; Marcellan, Alba; Smet, Lieselot De; de la Rosa, Victor R; Cooke, Graeme; Hoogenboom, Richard; Woisel, Patrice

2016-11-02

Most polymeric thermoresponsive hydrogels contract upon heating beyond the lower critical solution temperature (LCST) of the polymers used. Herein, we report a supramolecular hydrogel system that shows the opposite temperature dependence. When the non-thermosesponsive hydrogel NaphtGel, containing dialkoxynaphthalene guest molecules, becomes complexed with the tetra cationic macrocyclic host CBPQT 4+ , swelling occurred as a result of host-guest complex formation leading to charge repulsion between the host units, as well as an osmotic contribution of chloride counter-ions embedded in the network. The immersion of NaphtGel in a solution of poly(N-isopropylacrylamide) with tetrathiafulvalene (TTF) end groups complexed with CBPQT 4+ induced positive thermoresponsive behaviour. The LCST-induced dethreading of the polymer-based pseudorotaxane upon heating led to transfer of the CBPQT 4+ host and a concomitant swelling of NaphtGel. Subsequent cooling led to reformation of the TTF-based host-guest complexes in solution and contraction of the hydrogel. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Supramolecular systems chemistry

NARCIS (Netherlands)

Mattia, Elio; Otto, Sijbren

The field of supramolecular chemistry focuses on the non-covalent interactions between molecules that give rise to molecular recognition and self-assembly processes. Since most non-covalent interactions are relatively weak and form and break without significant activation barriers, many

Molecular recognition study of ethosuximide by the supramolecular probe, p-t-butyl calix(8)arene

Energy Technology Data Exchange (ETDEWEB)

Meenakshi, C., E-mail: geethu.laxi@gmail.com [Department of Chemistry, Shri Meenakshi Government College for Women (Autonomous), Madurai 625002 (India); Sangeetha, P.; Ramakrishnan, V. [Department of Laser Studies, School of Physics, Madurai Kamaraj University, Madurai 625021 (India)

2013-06-15

The supramolecule, p-t-Butyl calix(8)arene, forms inclusion complex with the antiseizure drug molecule, ethosuximide. This feature is explained on the basis of optical absorption spectroscopy. Here p-t-Butyl calix(8)arene is the host molecule and ethosuximide is the guest molecule. The stoichiometry of the host–guest complex and the binding constant has been determined using Benesi–Hildebrand plot. Based on the result obtained the structure of the inclusion complex has been proposed. -- Highlights: ► Third generation supramolecule, t-butyl calix (8) arene, is used as a host molecule. ► Anti seizure drug molecule is used as a guest molecule. ► Inclusion complex is formed between the host and guest molecule.

Ficaria verna Huds. extracts and their β-cyclodextrin supramolecular systems

Directory of Open Access Journals (Sweden)

Hădărugă Nicoleta G

2012-03-01

Full Text Available Abstract Background Obtaining new pharmaceutical materials with enhanced properties by using natural compounds and environment-friendly methods is a continuous goal for scientists. Ficaria verna Huds. is a widespread perennial plant with applications in the treat of haemorrhoids and to cure piles; it has also anti-inflammatory, astringent, and antibiotic properties. The goal of the present study is the obtaining and characterization of new F. verna extract/β-cyclodextrin complexes by using only natural compounds, solvents, and environment-friendly methods in order to increase the quality and acceptability versus toxicity indicator. Thus, the flavonoid content (as quercetin of Ficaria verna Huds. flowers and leaves from the West side of Romania was determined and correlated with their antioxidant activity. Further, the possibility of obtaining β-cyclodextrin supramolecular systems was studied. Results F. verna flowers and leaves extracts were obtained by semi-continuous solid-liquid extraction. The raw concentrated extract was spectrophotometrically analyzed in order to quantify the flavonoids from plant parts and to evaluate the antioxidant activity of these extracts. The F. verna extracts were used for obtaining β-cyclodextrin complexes; these were analyzed by scanning electron microscopy and Karl Fischer water titration; spectrophotometry was used in order to quantifying the flavonoids and evaluates the antioxidant activity. A higher concentration of flavonoids of 0.5% was determined in complexes obtained by crystallisation method, while only a half of this value was calculated for kneading method. The antioxidant activity of these complexes was correlated with the flavonoid content and this parameter reveals possible controlled release properties. Conclusions The flavonoid content of F. verna Huds. from the West side of Romania (Banat county is approximately the same in flowers and leaves, being situated at a medium value among other

Recycling Gene Carrier with High Efficiency and Low Toxicity Mediated by L-Cystine-Bridged Bis(β-cyclodextrin)s

Science.gov (United States)

Zhang, Yu-Hui; Chen, Yong; Zhang, Ying-Ming; Yang, Yang; Chen, Jia-Tong; Liu, Yu

2014-12-01

Constructing safe and effective gene delivery carriers is becoming highly desirable for gene therapy. Herein, a series of supramolecular crosslinking system were prepared through host-guest binding of adamantyl-modified low molecular weight of polyethyleneimine with L-cystine-bridged bis(β-cyclodextrin)s and characterized by 1H NMR titration, electron microscopy, zeta potential, dynamic light-scattering, gel electrophoresis, flow cytometry and confocal fluorescence microscopy. The results showed that these nanometersized supramolecular crosslinking systems exhibited higher DNA transfection efficiencies and lower cytotoxicity than the commercial DNA carrier gold standard (25 kDa bPEI) for both normal cells and cancer cells, giving a very high DNA transfection efficiency up to 54% for 293T cells. Significantly, this type of supramolecular crosslinking system possesses a number of enzyme-responsive disulfide bonds, which can be cleaved by reductive enzyme to promote the DNA release but recovered by oxidative enzyme to make the carrier renewable. These results demonstrate that these supramolecular crosslinking systems can be used as promising gene carriers.

Self-assembling supramolecular systems of different symmetry formed by wedged macromolecular dendrons

Energy Technology Data Exchange (ETDEWEB)

Shcherbina, M. A., E-mail: shcherbina@ispm.ru; Bakirov, A. V. [Russian Academy of Sciences, Institute of Synthetic Polymer Materials (Russian Federation); Yakunin, A. N. [Karpov Institute of Physical Chemistry (Russian Federation); Percec, V. [University of Pennsylvania (United States); Beginn, U. [Universitaet Osnabrueck, Institut fuer Chemie (Germany); Moeller, M. [Institute for Technical and Macromolecular Chemistry (Germany); Chvalun, S. N. [Russian Academy of Sciences, Institute of Synthetic Polymer Materials (Russian Federation)

2012-03-15

The main stages of the self-assembling of supramolecular ensembles have been revealed by studying different functional wedged macromolecules: polymethacrylates with tapered side chains based on gallic acid, their macromonomers, and salts of 2,3,4- and 3,4,5-tris(dodecyloxy)benzenesulphonic acid. The first stage is the formation of individual supramolecular aggregates (long cylinders or spherical micelles) due to the weak noncovalent interactions of mesogenic groups and the subsequent ordering in these aggregates, which is accompanied by a decrease in the free energy of the system. Supramolecular aggregates, in turn, form 2D or 3D lattices. The shape of supramolecular aggregates and its change with temperature are delicate functions of the mesogen chemical structure; this circumstance makes it possible to rationally design complex self-assembling systems with the ability to respond smartly to external stimuli. X-ray diffraction analysis allows one to study the structure of supramolecular systems with different degrees of order, determine the type of mesophases formed by these systems, and reveal the phase behavior of the material. Particular attention has been paid to the method for reconstruction of electron density distribution from the relative reflection intensity. The application of a suite of experimental methods, including wide- and small-angle X-ray diffraction, molecular modeling, differential scanning calorimetry, and polarization optical microscopy, allows one to establish the relationship between the shape of the structural unit (molecule or molecular aggregate), the nature of the interaction, and the phase behavior of the material.

Self-assembling supramolecular systems of different symmetry formed by wedged macromolecular dendrons

International Nuclear Information System (INIS)

Shcherbina, M. A.; Bakirov, A. V.; Yakunin, A. N.; Percec, V.; Beginn, U.; Möller, M.; Chvalun, S. N.

2012-01-01

The main stages of the self-assembling of supramolecular ensembles have been revealed by studying different functional wedged macromolecules: polymethacrylates with tapered side chains based on gallic acid, their macromonomers, and salts of 2,3,4- and 3,4,5-tris(dodecyloxy)benzenesulphonic acid. The first stage is the formation of individual supramolecular aggregates (long cylinders or spherical micelles) due to the weak noncovalent interactions of mesogenic groups and the subsequent ordering in these aggregates, which is accompanied by a decrease in the free energy of the system. Supramolecular aggregates, in turn, form 2D or 3D lattices. The shape of supramolecular aggregates and its change with temperature are delicate functions of the mesogen chemical structure; this circumstance makes it possible to rationally design complex self-assembling systems with the ability to respond smartly to external stimuli. X-ray diffraction analysis allows one to study the structure of supramolecular systems with different degrees of order, determine the type of mesophases formed by these systems, and reveal the phase behavior of the material. Particular attention has been paid to the method for reconstruction of electron density distribution from the relative reflection intensity. The application of a suite of experimental methods, including wide- and small-angle X-ray diffraction, molecular modeling, differential scanning calorimetry, and polarization optical microscopy, allows one to establish the relationship between the shape of the structural unit (molecule or molecular aggregate), the nature of the interaction, and the phase behavior of the material.

Colligative thermoelectric transport properties in n-type filled CoSb{sub 3} determined by guest electrons in a host lattice

Energy Technology Data Exchange (ETDEWEB)

Lim, Young Soo, E-mail: yslim@pknu.ac.kr, E-mail: wsseo@kicet.re.kr, E-mail: pmoka@lgchem.com [Department of Materials System Engineering, Pukyong National University, Busan 48547 (Korea, Republic of); Park, Kwan-Ho; Tak, Jang Yeul; Lee, Soonil; Seo, Won-Seon, E-mail: yslim@pknu.ac.kr, E-mail: wsseo@kicet.re.kr, E-mail: pmoka@lgchem.com [Energy and Environmental Division, Korea Institute of Ceramic Engineering and Technology (KICET), Jinju 52851 (Korea, Republic of); Park, Cheol-Hee, E-mail: yslim@pknu.ac.kr, E-mail: wsseo@kicet.re.kr, E-mail: pmoka@lgchem.com; Kim, Tae Hoon; Park, PumSuk [LG Chem/Research Park, Daejeon 34122 (Korea, Republic of); Kim, Il-Ho [Department of Materials Science and Engineering, Korea National University of Transportation, Chungju 27909 (Korea, Republic of); Yang, Jihui [Department of Materials Science and Engineering, University of Washington, Seattle, Washington 98195 (United States)

2016-03-21

Among many kinds of thermoelectric materials, CoSb{sub 3} has received exceptional attention for automotive waste heat recovery. Its cage structure provides an ideal framework for the realization of phonon-glass electron-crystal strategy, and there have been numerous reports on the enhanced thermoelectric performance through the independent control of the thermal and electrical conductivity by introducing fillers into its cage sites. Herein, we report colligative thermoelectric transport properties in n-type CoSb{sub 3} from the viewpoint of “guest electrons in a host lattice.” Both the Seebeck coefficient and the charge transport properties are fundamentally determined by the concentration of the guest electrons, which are mostly donated by the fillers, in the conduction band of the host CoSb{sub 3}. Comparing this observation to our previous results, colligative relations for both the Seebeck coefficient and the mobility were deduced as functions of the carrier concentration, and thermoelectric transport constants were defined to predict the power factor in filled CoSb{sub 3}. This discovery not only increases the degree of freedom for choosing a filler but also provides the predictability of power factor in designing and engineering the n-type filled CoSb{sub 3} materials.

Self-Healing and Thermo-Responsive Dual-Crosslinked Alginate Hydrogels based on Supramolecular Inclusion Complexes

Science.gov (United States)

Miao, Tianxin; Fenn, Spencer L.; Charron, Patrick N.; Oldinski, Rachael A.

2015-01-01

β-cyclodextrin (β-CD), with a lipophilic inner cavity and hydrophilic outer surface, interacts with a large variety of non-polar guest molecules to form non-covalent inclusion complexes. Conjugation of β-CD onto biomacromolecules can form physically-crosslinked hydrogel networks upon mixing with a guest molecule. Herein describes the development and characterization of self-healing, thermo-responsive hydrogels, based on host-guest inclusion complexes between alginate-graft-β-CD and Pluronic® F108 (poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol)). The mechanics, flow characteristics, and thermal response were contingent on the polymer concentrations, and the host-guest molar ratio. Transient and reversible physical crosslinking between host and guest polymers governed self-assembly, allowing flow under shear stress, and facilitating complete recovery of the material properties within a few seconds of unloading. The mechanical properties of the dual-crosslinked, multi-stimuli responsive hydrogels were tuned as high as 30 kPa at body temperature, and are advantageous for biomedical applications such as drug delivery and cell transplantation. PMID:26509214

Molecular boxes on a molecular printboard: encapsulation of anionic dyes in immobilized dendrimers

NARCIS (Netherlands)

Onclin, S.; Huskens, Jurriaan; Ravoo, B.J.; Reinhoudt, David

2005-01-01

Fifth-generation poly(propylene imine) dendrimers, modified with 64 apolar adamantyl groups, have been immobilized on cyclodextrin host monolayers (molecular printboards) on glass by supramolecular microcontact printing. The immobilized dendrimers retain their guest-binding properties and function

Supramolecular luminescence from oligofluorenol-based supramolecular polymer semiconductors.

Science.gov (United States)

Zhang, Guang-Wei; Wang, Long; Xie, Ling-Hai; Lin, Jin-Yi; Huang, Wei

2013-11-13

Supramolecular luminescence stems from non-covalent exciton behaviors of active π-segments in supramolecular entities or aggregates via intermolecular forces. Herein, a π-conjugated oligofluorenol, containing self-complementary double hydrogen bonds, was synthesized using Suzuki coupling as a supramolecular semiconductor. Terfluorenol-based random supramolecular polymers were confirmed via concentration-dependent nuclear magnetic resonance (NMR) and dynamic light scattering (DLS). The photoluminescent spectra of the TFOH-1 solution exhibit a green emission band (g-band) at approximately ~520 nm with reversible features, as confirmed through titration experiments. Supramolecular luminescence of TFOH-1 thin films serves as robust evidence for the aggregates of g-band. Our results suggest that the presence of polyfluorene ketone defects is a sufficient condition, rather than a sufficient-necessary condition for the g-band. Supramolecular electroluminescence will push organic devices into the fields of supramolecular optoelectronics, spintronics, and mechatronics.

Host-Guest Recognition-Assisted Electrochemical Release: Its Reusable Sensing Application Based on DNA Cross Configuration-Fueled Target Cycling and Strand Displacement Reaction Amplification.

Science.gov (United States)

Chang, Yuanyuan; Zhuo, Ying; Chai, Yaqin; Yuan, Ruo

2017-08-15

In this work, an elegantly designed host-guest recognition-assisted electrochemical release was established and applied in a reusable electrochemical biosensor for the detection of microRNA-182-5p (miRNA-182-5p), a prostate cancer biomarker in prostate cancer, based on the DNA cross configuration-fueled target cycling and strand displacement reaction (SDR) amplification. With such a design, the single target miRNA input could be converted to large numbers of single-stranded DNA (S1-Trp and S2-Trp) output, which could be trapped by cucurbit[8]uril methyl viologen (CB-8-MV 2+ ) based on the host-guest recognition, significantly enhancing the sensitivity for miRNA detection. Moreover, the nucleic acids products obtained from the process of cycling amplification could be utilized sufficiently, avoiding the waste and saving the experiment cost. Impressively, by resetting a settled voltage, the proposed biosensor could release S1-Trp and S2-Trp from the electrode surface, attributing that the guest ion methyl viologen (MV 2+ ) was reduced to MV +· under this settled voltage and formed a more-stable CB-8-MV +· -MV +· complex. Once O 2 was introduced in this system, MV +· could be oxidized to MV 2+ , generating the complex of CB-8-MV 2+ for capturing S1-Trp and S2-Trp again in only 5 min. As a result, the simple and fast regeneration of biosensor for target detection was realized on the base of electrochemical redox-driven assembly and release, overcoming the challenges of time-consuming, burdensome operations and expensive experimental cost in traditional reusable biosensors and updating the construction method for a reusable bisensor. Furthermore, the biosensor could be reused for more than 10 times with a regeneration rate of 93.20%-102.24%. After all, the conception of this work provides a novel thought for the construction of effective reusable biosensor to detect miRNA and other biomarkers and has great potential application in the area requiring the release of

An in situ study of the adsorption behavior of functionalized particles on selfassembled monolayers via different chemical interactions

NARCIS (Netherlands)

Ling, X.Y.; Malaquin, Laurent; Reinhoudt, David; Wolf, Heiko; Huskens, Jurriaan

2007-01-01

The formation of particle monolayers by convective assembly was studied in situ with three different kinds of particle-surface interactions: adsorption onto native surfaces, with additional electrostatic interactions, and with supramolecular host-guest interactions. In the first case

Nurses as 'guests'--a study of a concept in light of Jacques Derrida's philosophy of hospitality.

Science.gov (United States)

Oresland, Stina; Lutzén, Kim; Norberg, Astrid; Rasmussen, Birgit H; Määttä, Sylvia

2013-04-01

As revealed in previous empirical research, nurses describe their position in home-based nursing care (HBNC) as that of 'guests' in the patient's home. Such a description is problematic as 'guests' might not be considered to belong to the realm of professionalism. As Jacques Derrida's work on hospitality has received wide publicity, sparking theoretical and philosophical discussion about host and guest, the aim of this study was to explore how the concept 'guests' can be understood in the light of Derrida's philosophy of hospitality. The study revealed that (a) guest must be considered a binary concept; and (b) hospitality should be regarded as an exchange of giving and receiving between a host and a guest. The present study demonstrated that it is important to reflect on the meaning of the concepts used by nurses in HBNC. Further theoretical and empirical exploration of the concept 'hospitality' would be fruitful, i.e. what is patients' understanding of 'hospitality' and 'hostility' related to nurses' descriptions of themselves as 'guests' in the patient's home. © 2013 Blackwell Publishing Ltd.

Rational Design of Multifunctional Gold Nanoparticles via Host-Guest Interaction for Cancer-Targeted Therapy.

Science.gov (United States)

Chen, Wei-Hai; Lei, Qi; Luo, Guo-Feng; Jia, Hui-Zhen; Hong, Sheng; Liu, Yu-Xin; Cheng, Yin-Jia; Zhang, Xian-Zheng

2015-08-12

A versatile gold nanoparticle-based multifunctional nanocomposite AuNP@CD-AD-DOX/RGD was constructed flexibly via host-guest interaction for targeted cancer chemotherapy. The pH-sensitive anticancer prodrug AD-Hyd-DOX and the cancer-targeted peptide AD-PEG8-GRGDS were modified on the surface of AuNP@CD simultaneously, which endowed the resultant nanocomposite with the capability to selectively eliminate cancer cells. In vitro studies indicated that the AuNP@CD-AD-DOX/RGD nanocomposite was preferentially uptaken by cancer cells via receptor-mediated endocytosis. Subsequently, anticancer drug DOX was released rapidly upon the intracellular trigger of the acid microenvirenment of endo/lysosomes, inducing apoptosis in cancer cells. As the ideal drug nanocarrier, the multifunctional gold nanoparticles with the active targeting and controllable intracellular release ability hold the great potential in cancer therapy.

Supramolecular Luminescence from Oligofluorenol-Based Supramolecular Polymer Semiconductors

Directory of Open Access Journals (Sweden)

Guang-Wei Zhang

2013-11-01

Full Text Available Supramolecular luminescence stems from non-covalent exciton behaviors of active π-segments in supramolecular entities or aggregates via intermolecular forces. Herein, a π-conjugated oligofluorenol, containing self-complementary double hydrogen bonds, was synthesized using Suzuki coupling as a supramolecular semiconductor. Terfluorenol-based random supramolecular polymers were confirmed via concentration-dependent nuclear magnetic resonance (NMR and dynamic light scattering (DLS. The photoluminescent spectra of the TFOH-1 solution exhibit a green emission band (g-band at approximately ~520 nm with reversible features, as confirmed through titration experiments. Supramolecular luminescence of TFOH-1 thin films serves as robust evidence for the aggregates of g-band. Our results suggest that the presence of polyfluorene ketone defects is a sufficient condition, rather than a sufficient-necessary condition for the g-band. Supramolecular electroluminescence will push organic devices into the fields of supramolecular optoelectronics, spintronics, and mechatronics.

Phase changes induced by guest orientational ordering of filled ice Ih methane hydrate under high pressure and low temperature

International Nuclear Information System (INIS)

Hirai, H; Tanaka, T; Yagi, T; Matsuoka, T; Ohishi, Y; Ohtake, M; Yamamoto, Y

2014-01-01

Low-temperature and high-pressure experiments were performed with filled ice Ih structure of methane hydrate under pressure and temperature conditions of 2.0 to 77.0 GPa and 30 to 300 K, respectively, using diamond anvil cells and a helium-refrigeration cryostat. Distinct changes in the axial ratios of the host framework were revealed by In-situ X-ray diffractometry. Splitting in the CH vibration modes of the guest methane molecules, which was previously explained by the orientational ordering of the guest molecules, was observed by Raman spectroscopy. The pressure and temperature conditions at the split of the vibration modes agreed well with those of the axial ratio changes. The results indicated that orientational ordering of the guest methane molecules from orientational disordered-state occurred at high pressures and low temperatures, and that this guest ordering led to the axial ratio changes in the host framework. Existing regions of the guest disordered-phase and the guest ordered-phase were roughly estimated by the X-ray data. In addition, above the pressure of the guest-ordered phase, another high pressure phase was developed at a low-temperature region. The deuterated-water host samples were also examined and isotopic effects on the guest ordering and phase changes were observed.

Synthesis, crystal and band structures, and properties of a new supramolecular complex (Hg2As)2(CdI4)

International Nuclear Information System (INIS)

Zou Jianping; Wu Dongsheng; Huang Shuping; Zhu Jing; Guo Guocong; Huang Jinshun

2007-01-01

A new quaternary supramolecular complex (Hg 2 As) 2 (CdI 4 ) (1) has been prepared by the solid-state reaction and structurally characterized by single crystal X-ray diffraction analysis. Compound 1 crystallizes in the space group P2 1 of the monoclinic system with two formula units in a cell: a=7.945(4), b=12.934(6), c=8.094(4) A, β=116.898 o (1), V=741.7(6) A 3 . The structure of 1 is characterized by a tridymite-like three-dimensional cationic framework, which is composed of mercury and arsenic atoms, with the channels being occupied by discrete CdI 4 2- tetrahedral guest-anions. The optical properties were investigated in terms of the diffuse reflectance and Fourier transform infrared spectra. The electronic band structure along with density of states (DOS) calculated by DFT method indicates that the present compound is a semiconductor with a direct band gap, and that the optical absorption is mainly originated from the charge transitions from I-5p and As-4p to Cd-5s and Hg-6s states. - Graphical abstract: A new quaternary supramolecular complex (Hg 2 As) 2 (CdI 4 ) (1) has been prepared by the solid-state reaction, and structurally characterized by single crystal X-ray diffraction analysis. The structure of 1 is characterized by a 3-D tridymite-like cationic framework with the channels being occupied by discrete CdI 4 2- tetrahedral guest-anions

Nanographenes as electron-deficient cores of donor-acceptor systems.

Science.gov (United States)

Liu, Yu-Min; Hou, Hao; Zhou, Yan-Zhen; Zhao, Xin-Jing; Tang, Chun; Tan, Yuan-Zhi; Müllen, Klaus

2018-05-15

Conjugation of nanographenes (NGs) with electro-active molecules can establish donor-acceptor π-systems in which the former generally serve as the electron-donating moieties due to their electronic-rich nature. In contrast, here we report a series of reversed donor-acceptor structures are obtained by C-N coupling of electron-deficient perchlorinated NGs with electron-rich anilines. Selective amination at the vertexes of the NGs is unambiguously shown through X-ray crystallography. By varying the donating ability of the anilino groups, the optical and assembly properties of donor-acceptor NGs can be finely modulated. The electron-deficient concave core of the resulting conjugates can host electron-rich guest molecules by intermolecular donor-acceptor interactions and gives rise to charge-transfer supramolecular architectures.

Guest-responsive structural adaptation of a rationally-designed ...

Indian Academy of Sciences (India)

From molecules and crystals to materials NATO ASI. Series (The Netherlands: Kluwer). 3. Desiraju G R 2007 Angew. Chem. Int. Ed. 46 8342. 4. MacNicol D D 1994 In Inclusion compounds (London: Academic Press). 5. Weber E 1996 In Shape and symmetry in the design of new hosts, in Comprehensive Supramolecular ...

A Dynamic Supramolecular System Exhibiting Substrate Selectivity in the Catalytic Epoxidation of Olefins

DEFF Research Database (Denmark)

Jonsson, Stefan; Odille, Fabrice G. J.; Norrby, Per-Ola

2005-01-01

A dynamic supramolecular system involving hydrogen bonding between a Mn(III) salen catalyst and a Zn(II) porphyrin receptor exhibits selectivity for pyridine appended cis-beta-substituted styrene derivatives over phenyl appended derivatives in a catalytic epoxidation reaction.......A dynamic supramolecular system involving hydrogen bonding between a Mn(III) salen catalyst and a Zn(II) porphyrin receptor exhibits selectivity for pyridine appended cis-beta-substituted styrene derivatives over phenyl appended derivatives in a catalytic epoxidation reaction....

Strong supramolecular control over protein self-assembly using a polyamine decorated β-cyclodextrin as synthetic recognition element

NARCIS (Netherlands)

Uhlenheuer, D.A.; Milroy, L.G.; Neirynck, P.; Brunsveld, L.

2011-01-01

The supramolecular host molecule heptakis-[6-deoxy-6-(2-aminoethylsulfanyl)]-ß-cyclodextrin provides strong control over protein self-assembly in synthetic supramolecular protein constructs. Mono-functionalization of this modified ß-cyclodextrin with a cysteine residue allows for site-selective

New Horizons Pluto Flyby Guest Operations

Science.gov (United States)

Simon, M.; Turney, D.; Fisher, S.; Carr, S. S.

2015-12-01

On July 14, 2015, after 9.5 years of cruise, NASA's New Horizons spacecraft flew past the Pluto system to gather first images humankind had ever seen on Pluto and its five moons. While much has been discovered about the Pluto system since New Horizons launch in 2006, the system has never been imaged at high resolution and anticipation of the "First Light" of the Pluto system had been anticipated by planetary enthusiasts for decades. The Johns Hopkins Applied Physics Laboratory (APL), which built and operates New Horizons, was the focal point for gathering three distinct groups: science and engineering team members; media and public affairs representatives; and invited public, including VIP's. Guest operations activities were focused on providing information primarily to the invited public and VIP's. High level objectives for the Guest Operations team was set to entertain and inform the general public, offer media reaction shots, and to deconflict activities for the guests from media activities wherever possible. Over 2000 people arrived at APL in the days surrounding closest approach for guest, science or media operations tracks. Reaction and coverage of the Guest Operations events was universally positive and global in impact: iconic pictures of the auditorium waving flags during the moment of closest approach were published in media outlets on every continent. Media relations activities ensured coverage in all key media publications targeted for release, such as the New York Times, Science, Le Monde, and Nature. Social and traditional media coverage of the events spanned the globe. Guest operations activities are designed to ensure that a guest has a memorable experience and leaves with a lifelong memory of the mission and their partnership in the activity. Results, lessons learned, and other data from the New Horizons guest operations activity will be presented and analyzed.

Binding of chemical warfare agent simulants as guests in a coordination cage: contributions to binding and a fluorescence-based response.

Science.gov (United States)

Taylor, Christopher G P; Piper, Jerico R; Ward, Michael D

2016-05-07

Cubic coordination cages act as competent hosts for several alkyl phosphonates used as chemical warfare agent simulants; a range of cage/guest structures have been determined, contributions to guest binding analysed, and a fluorescent response to guest binding demonstrated.

Diffusion as a function of guest molecule length and functionalization in flexible metal–organic frameworks

KAUST Repository

Zheng, B.; Wang, L. L.; Du, L.; Pan, Y.; Lai, Zhiping; Huang, Kuo-Wei; Du, H. L.

2016-01-01

Understanding guest diffusion in nanoporous host-guest systems is crucial in the efficient design of metal-organic frameworks (MOFs) for chemical separation and drug delivery applications. In this work, we investigated the effect of molecule length on the diffusion rate in the zeolitic imidazolate framework 8 (ZIF-8), trying to find a simple and straightforward variable to characterize the complicated guest diffusion. We found that, counter-intuitively, long guest molecules can diffuse as quickly as short molecules; the diffusion coefficient of ethyl acetate for example is of the same order of magnitude as ethane and ethanol, as excludes the existence of a simple relationship between molecule length and diffusion rate. This phenomenon is explained by a study of the contributions of intra- and inter-cage movement to overall transport. Steric confinement limits the degrees of freedom of long guest molecules, shortening their residence time and increasing the efficiency of radial diffusion. In contrast, shorter molecules meander within MOF cages, reducing transport. Furthermore, the energy barrier of inter-cage transport also does not exhibit a simple dependence on a guest molecule length, attributing to the effect of the type of functional group on diffusion. Guests over varying lengths were investigated by using theoretical methods, revealing that the guest diffusion in ZIF-8 depends on the number of contiguous carbon atoms in a molecule, rather than its overall length. Thus, we proposed simple criteria to predict arbitrary guest molecule diffusivity in ZIF-8 without time-consuming experimentation. © 2016 The Royal Society of Chemistry.

Diffusion as a function of guest molecule length and functionalization in flexible metal–organic frameworks

KAUST Repository

Zheng, B.

2016-05-11

Understanding guest diffusion in nanoporous host-guest systems is crucial in the efficient design of metal-organic frameworks (MOFs) for chemical separation and drug delivery applications. In this work, we investigated the effect of molecule length on the diffusion rate in the zeolitic imidazolate framework 8 (ZIF-8), trying to find a simple and straightforward variable to characterize the complicated guest diffusion. We found that, counter-intuitively, long guest molecules can diffuse as quickly as short molecules; the diffusion coefficient of ethyl acetate for example is of the same order of magnitude as ethane and ethanol, as excludes the existence of a simple relationship between molecule length and diffusion rate. This phenomenon is explained by a study of the contributions of intra- and inter-cage movement to overall transport. Steric confinement limits the degrees of freedom of long guest molecules, shortening their residence time and increasing the efficiency of radial diffusion. In contrast, shorter molecules meander within MOF cages, reducing transport. Furthermore, the energy barrier of inter-cage transport also does not exhibit a simple dependence on a guest molecule length, attributing to the effect of the type of functional group on diffusion. Guests over varying lengths were investigated by using theoretical methods, revealing that the guest diffusion in ZIF-8 depends on the number of contiguous carbon atoms in a molecule, rather than its overall length. Thus, we proposed simple criteria to predict arbitrary guest molecule diffusivity in ZIF-8 without time-consuming experimentation. © 2016 The Royal Society of Chemistry.

Host-Guest Engineering of Layered Double Hydroxides towards Efficient Oxygen Evolution Reaction: Recent Advances and Perspectives

Directory of Open Access Journals (Sweden)

Jianming Li

2018-05-01

Full Text Available Electrochemical water splitting has great potential in the storage of intermittent energy from the sun, wind, or other renewable sources for sustainable clean energy applications. However, the anodic oxygen evolution reaction (OER usually determines the efficiency of practical water electrolysis due to its sluggish four-electron process. Layered double hydroxides (LDHs have attracted increasing attention as one of the ideal and promising electrocatalysts for water oxidation due to their excellent activity, high stability in basic conditions, as well as their earth-abundant compositions. In this review, we discuss the recent progress on LDH-based OER electrocatalysts in terms of active sites, host-guest engineering, and catalytic performances. Moreover, further developments and challenges in developing promising electrocatalysts based on LDHs are discussed from the viewpoint of molecular design and engineering.

Motivations of farm tourism hosts and guests in the South West ...

African Journals Online (AJOL)

denise

rich and varied landscape, long tradition of farming and ... of visitors who stay at your farm / establishment? 2 How would .... walks, and the children all loved the animals. .... During the short time .... Guests relive happy memories of past times.

Manipulation of Energy Transfer Processes in Nano channels

International Nuclear Information System (INIS)

Devaux, A.; Calzaferri, G.

2010-01-01

The realisation of molecular assemblies featuring specific macroscopic properties is a prime example for the versatility of supramolecular organisation. Microporous materials such as zeolite L are well suited for the preparation of host-guest composites containing dyes, complexes, or clusters. This short tutorial focuses on the possibilities offered by zeolite L to study and influence Forster resonance energy transfer inside of its nano channels. The highly organised host-guest materials can in turn be structured on a larger scale to form macroscopic patterns, making it possible to create large-scale structures from small, highly organised building blocks for novel optical applications.

Unanticipated guest motion during a phase transition in a ferroelastic inclusion compound.

Science.gov (United States)

Hollingsworth, Mark D; Peterson, Matthew L; Pate, Kevin L; Dinkelmeyer, Brian D; Brown, Michael E

2002-03-13

Urea inclusion compounds (UICs) have been used as tools to understand ferroelastic domain switching and molecular recognition during crystal growth. Although the vast majority of UICs contain helical arrangements of host H-bonds, those containing guests with the formula X(CH(2))(6)Y (X, Y = Br, Cl, CN, NC) adopt an alternative P2(1)/n packing mode in which the host molecules exist as stacked loops of urea hexamers. Such structures may be further separated into two classes, ones distorted away from hexagonal symmetry along [100] (Br(CH(2))(6)Br, Br(CH(2))(6)Cl, and Cl(CH(2))(6)Cl) and those distorted along [001] (e.g. NC(CH(2))(6)CN). In each of these systems, guests exist as equilibrium mixtures of gauche conformers whose populations control the direction and magnitude of the observed distortion. Such UICs are potentially ferroelastic, but the n-glide requires that domains are not related by a simple rotation-translation mechanism as in the helical systems. Ferroelastic (degenerate) domain reorientation would necessitate a large-scale reorganization of the urea framework and rupture of numerous H-bonds. Coupled with distortions of 2 to 10%, this mechanism-based barrier to domain switching has precluded observation of this phenomenon. To prepare ferroelastic UICs with minimal distortions from hexagonal symmetry, attempts were made to form solid solutions of UICs containing guests from the two classes. This failed, however: solid solution formation of the stacked loop form is usually possible within a series (e.g. with Cl(CH(2))(6)Cl and Br(CH(2))(6)Br), but not between series (e.g. Cl(CH(2))(6)Cl and NC(CH(2))(6)CN). Crystals of Cl(CH(2))(6)CN/urea, in which a single guest contains substituents from each class, are distorted along [001] by only 0.5% from hexagonal symmetry at 298 K and exhibit ferroelastic domain reorientation at high forces. At -66 degrees C, Cl(CH(2))(6)CN/urea undergoes a topotactic phase transition that is unexpectedly nontopochemical. The

Calixarene capped ZnS quantum dots as an optical nanoprobe for detection and determination of menadione.

Science.gov (United States)

Joshi, Kuldeep V; Joshi, Bhoomika K; Pandya, Alok; Sutariya, Pinkesh G; Menon, Shobhana K

2012-10-21

In this communication we report a p-sulfonatocalix[4]arene coated ZnS quantum dots "cup type" highly stable optical probe for the detection and determination of menadione (VK(3)) with high sensitivity and selectivity. The detection of VK(3) depends on supramolecular host-guest chemistry.

Rheology of Supramolecular Polymers

DEFF Research Database (Denmark)

Shabbir, Aamir

Supramolecular polymers are a broad class of materials that include all polymerscapable of associating via secondary interactions. These materials represent an emerging class of systems with superior versatility compared to classical polymers with applications in food stuff, coatings, cost...... efficient processes or biomedical areas. Design and development of supramolecular polymers using ionic, hydrogen bonding or transition metal complexes with tailored properties requires deep understanding of dynamics both in linear and non-linear deformations. While linear rheology is important to understand...... the dynamics under equilibrium conditions, extensional rheology is relevant during the processing or in the usage of polymers utilizing supramolecular associations for example, acrylic based pressure sensitive adhesives are subjected to extensional deformations during the peeling where strain hardening...

Multivalency in supramolecular chemistry and nanofabrication

NARCIS (Netherlands)

Mulder, A.; Huskens, Jurriaan; Reinhoudt, David

2004-01-01

Multivalency is a powerful and versatile self-assembly pathway that confers unique thermodynamic and kinetic behavior onto supramolecular complexes. The diversity of the examples of supramolecular multivalent systems discussed in this perspective shows that the concept of multivalency is a general

Photoactive assemblies of organic compounds and biomolecules: drug-protein supramolecular systems.

Science.gov (United States)

Vayá, Ignacio; Lhiaubet-Vallet, Virginie; Jiménez, M Consuelo; Miranda, Miguel A

2014-06-21

The properties of singlet and triplet excited states are strongly medium-dependent. Hence, these species constitute valuable tools as reporters to probe compartmentalised microenvironments, including drug@protein supramolecular systems. In the present review, the attention is focused on the photophysical properties of the probe drugs (rather than those of the protein chromophores) using transport proteins (serum albumins and α1-acid glycoproteins) as hosts. Specifically, fluorescence measurements allow investigation of the structural and dynamic properties of biomolecules or their complexes. Thus, the emission quantum yields and the decay kinetics of the drug singlet excited states provide key information to determine important parameters such as the stoichiometry of the complex, the binding constant, the relative degrees of occupancy of the different compartments, etc. Application of the FRET concept allows determination of donor-acceptor interchromophoric distances. In addition, anisotropy measurements can be related to the orientation of the drug within the binding sites, where the degrees of freedom for conformational relaxation are restricted. Transient absorption spectroscopy is also a potentially powerful tool to investigate the binding of drugs to proteins, where formation of encapsulated triplet excited states is favoured over other possible processes leading to ionic species (i.e. radical ions), and their photophysical properties are markedly sensitive to the microenvironment experienced within the protein binding sites. Even under aerobic conditions, the triplet lifetimes of protein-complexed drugs are remarkably long, which provides a broad dynamic range for identification of distinct triplet populations or for chiral discrimination. Specific applications of the laser flash photolysis technique include the determination of drug distribution among the bulk solution and the protein binding sites, competition of two types of proteins to bind a drug

Supra-molecular Association and Polymorphic Behaviour In Systems Containing Bile Acid Salts

Directory of Open Access Journals (Sweden)

Camillo La Mesa

2007-08-01

Full Text Available A wide number of supra-molecular association modes are observed in mixtures containing water and bile salts, BS, (with, eventually, other components. Molecular or micellar solutions transform into hydrated solids, fibres, lyotropic liquid crystals and/or gels by raising the concentration, the temperature, adding electrolytes, surfactants, lipids and proteins. Amorphous or ordered phases may be formed accordingly. The forces responsible for this very rich polymorphism presumably arise from the unusual combination of electrostatic, hydrophobic and hydrogen-bond contributions to the system stability, with subsequent control of the supra-molecular organisation modes. The stabilising effect due to hydrogen bonds does not occur in almost all surfactants or lipids and is peculiar to bile acids and salts. Some supra-molecular organisation modes, supposed to be related to malfunctions and dis-metabolic diseases in vivo, are briefly reported and discussed.

Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production

Science.gov (United States)

Tian, Jia; Xu, Zi-Yue; Zhang, Dan-Wei; Wang, Hui; Xie, Song-Hai; Xu, Da-Wen; Ren, Yuan-Hang; Wang, Hao; Liu, Yi; Li, Zhan-Ting

2016-05-01

Self-assembly has a unique presence when it comes to creating complicated, ordered supramolecular architectures from simple components under mild conditions. Here, we describe a self-assembly strategy for the generation of the first homogeneous supramolecular metal-organic framework (SMOF-1) in water at room temperature from a hexaarmed [Ru(bpy)3]2+-based precursor and cucurbit[8]uril (CB[8]). The solution-phase periodicity of this cubic transition metal-cored supramolecular organic framework (MSOF) is confirmed by small-angle X-ray scattering and diffraction experiments, which, as supported by TEM imaging, is commensurate with the periodicity in the solid state. We further demonstrate that SMOF-1 adsorbs anionic Wells-Dawson-type polyoxometalates (WD-POMs) in a one-cage-one-guest manner to give WD-POM@SMOF-1 hybrid assemblies. Upon visible-light (500 nm) irradiation, such hybrids enable fast multi-electron injection from photosensitive [Ru(bpy)3]2+ units to redox-active WD-POM units, leading to efficient hydrogen production in aqueous media and in organic media. The demonstrated strategy opens the door for the development of new classes of liquid-phase and solid-phase ordered porous materials.

Molecular binding thermodynamics of spherical guests by β-cyclodextrins bearing aromatic substituents

Energy Technology Data Exchange (ETDEWEB)

Li, Nan; Chen, Yong; Zhang, Ying-Ming; Wang, Li-Hua; Mao, Wen-Zhao; Liu, Yu, E-mail: yuliu@nankai.edu.cn

2014-01-20

Graphical abstract: - Highlights: • Different conformation of β-CD derivatives. • Enthalpy gain. • High binding ability. - Abstract: The molecular binding behaviors of two β-cyclodextrin (β-CD) derivatives bearing 1,2,3-triazole moieties, i.e. mono-6-deoxy-6-{4-(8-oxymethylquinolino)[1,2,3]triazolyl}-β-CD (1) and mono-6-deoxy-6-{4-(8-oxymethylnaphthol)[1,2,3]triazolyl}-β-CD (3), and their analogs without 1,2,3-triazole moieties, i.e. mono-6-deoxy-6-(8-oxymethylquinolino)-β-CD (2) and mono-6-deoxy-6-(8-oxymethylnaphthol)-β-CD (4) toward spherical guests (±)-borneol and (±)-camphor were investigated to elucidate how substituent moiety of host affects the binding abilities by 2D NMR as well as microcalorimetric titrations in aqueous phosphate buffer solution (pH 7.20) at 298.15 K. The binding modes of host–guest interactions obtained from 2D NMR displayed that host CDs without triazole moieties gave better induce-fit efficiency between hosts and guests, leading to stronger binding abilities. Thermodynamically, the inclusion complexation was driven by enthalpy with the stoichiometry of 1:1. Another factor contributed to the enhanced binding abilities was the enthalpy gain with the smaller entropy loss.

Design of Molecular Materials: Supramolecular Engineering

Science.gov (United States)

Simon, Jacques; Bassoul, Pierre

2001-02-01

This timely and fascinating book is destined to be recognised as THE book on supramolecular engineering protocols. It covers this sometimes difficult subject in an approachable form, gathering together information from many sources. Supramolecular chemistry, which links organic chemistry to materials science, is one of the fastest growth areas of chemistry research. This book creates a correlation between the structure of single molecules and the physical and chemical properties of the resulting materials. By making systematic changes to the component molecules, the resulting solid can be engineered for optimum performance. There is a clearly written development from synthesis of designer molecules to properties of solids and further on to devices and complex materials systems, providing guidelines for mastering the organisation of these systems. Topics covered include: Systemic chemistry Molecular assemblies Notions of symmetry Supramolecular engineering Principe de Curie Organisation in molecular media Molecular semiconductors Industrial applications of molecular materials This superb book will be invaluable to researchers in the field of supramolecular materials and also to students and teachers of the subject.

Characterization of the host–guest complex of a curcumin analog with β-cyclodextrin and β-cyclodextrin–gemini surfactant and evaluation of its anticancer activity

Directory of Open Access Journals (Sweden)

Poorghorban M

2015-01-01

Full Text Available Masoomeh Poorghorban,1 Umashankar Das,2 Osama Alaidi,1 Jackson M Chitanda,2 Deborah Michel,1 Jonathan Dimmock,1 Ronald Verrall,3 Pawel Grochulski,1,4 Ildiko Badea1 1Drug Discovery and Development Research Group, College of Pharmacy and Nutrition, 2Department of Chemical and Biological Engineering, 3Department of Chemistry, University of Saskatchewan, Saskatoon, SK, Canada; 4Canadian Light Source, Saskatoon, SK, Canada Background: Curcumin analogs, including the novel compound NC 2067, are potent cytotoxic agents that suffer from poor solubility, and hence, low bioavailability. Cyclodextrin-based carriers can be used to encapsulate such agents. In order to understand the interaction between the two molecules, the physicochemical properties of the host–guest complexes of NC 2067 with β-cyclodextrin (CD or β-cyclodextrin–gemini surfactant (CDgemini surfactant were investigated for the first time. Moreover, possible supramolecular structures were examined in order to aid the development of new drug delivery systems. Furthermore, the in vitro anticancer activity of the complex of NC 2067 with CDgemini surfactant nanoparticles was demonstrated in the A375 melanoma cell line.Methods: Physicochemical properties of the complexes formed of NC 2067 with CD or CDgemini surfactant were investigated by synchrotron-based powder X-ray diffraction, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. Synchrotron-based small- and wide-angle X-ray scattering and size measurements were employed to assess the supramolecular morphology of the complex formed by NC 2067 with CDgemini surfactant. Lastly, the in vitro cell toxicity of the formulations toward A375 melanoma cells at various drug-to-carrier mole ratios were measured by cell viability assay.Results: Physical mixtures of NC 2067 and CD or CDgemini surfactant showed characteristics of the individual components, whereas the complex of NC 2067 and CD or CDgemini surfactant presented new

Supra-molecular networks for CO2 capture

Science.gov (United States)

Sadowski, Jerzy; Kestell, John

Utilizing capabilities of low-energy electron microscopy (LEEM) for non-destructive interrogation of the real-time molecular self-assembly, we have investigated supramolecular systems based on carboxylic acid-metal complexes, such as trimesic and mellitic acid, doped with transition metals. Such 2D networks can act as host systems for transition-metal phthalocyanines (MPc; M = Fe, Ti, Sc). The electrostatic interactions of CO2 molecules with transition metal ions can be tuned by controlling the type of TM ion and the size of the pore in the host network. We further applied infrared reflection-absorption spectroscopy (IRRAS) to determine of the molecular orientation of the functional groups and the whole molecule in the 2D monolayers of carboxylic acid. The kinetics and mechanism of the CO2 adsorption/desorption on the 2D molecular network, with and without the TM ion doping, have been also investigated. This research used resources of the Center for Functional Nanomaterials, which is the U.S. DOE Office of Science User Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704.

Encapsulation of Protonated Diamines in a Water-Soluble Chiral, Supramolecular Assembly Allows for Measurement of Hydrogen-Bond Breaking Followed by Nitrogen Inversion/Rotation (NIR)

Energy Technology Data Exchange (ETDEWEB)

Meux, Susan C.; Pluth, Michael D.; Bergman, Robert G.; Raymond, Kenneth N.

2007-09-19

Amine nitrogen inversion, difficult to observe in aqueous solution, is followed in a chiral, supramolecular host molecule with purely-rotational T-symmetry that reduces the local symmetry of encapsulated monoprotonated diamines and enables the observation and quantification of {Delta}G{double_dagger} for the combined hydrogen-bond breaking and nitrogen inversion rotation (NIR) process. Free energies of activation for the combined hydrogen-bond breaking and NIR process inside of the chiral assembly were determined by the NMR coalescence method. Activation parameters for ejection of the protonated amines from the assembly confirm that the NIR process responsible for the coalescence behavior occurs inside of the assembly rather than by a guest ejection/NIR/re-encapsulation mechanism. For one of the diamines, N,N,N{prime},N{prime}-tetramethylethylenediamine (TMEDA), the relative energy barriers for the hydrogen-bond breaking and NIR process were calculated at the G3(MP2)//B3LYP/6-31++G(d,p) level of theory, and these agreed well with the experimental data.

Supramolecular Properties of Triazole-containing Two Armed Peptidomimetics: From Organogelators to Nucleotide-binding Tweezers

Science.gov (United States)

Chui, Tin Ki

of hydrogen bonds involved in the binding between the nucleotide phosphate moiety and the tweezer amides, triazole protons and guanidinium groups. In summary, this thesis reported a new class of branched peptidomimetics that were constructed from conventional peptide and non-classical triazole linkages. The resulting peptidomimetics exhibited very rich supramolecular chemistry, ranging from gel formation, self-association, host.guest complexation and anion recognition. All these properties were due to the presence of multiple hydrogen bonding units in the form of amide and triazole units along the tweezer backbone. Through hydrogen bonding interaction with various guest molecules, the multiple-arm architecture could fold itself into a complementary conformation that could bind to the guest molecules in a much more efficient manner.

Nano-Saturn: Experimental Evidence of Complex Formation of an Anthracene Cyclic Ring with C60.

Science.gov (United States)

Yamamoto, Yuta; Tsurumaki, Eiji; Wakamatsu, Kan; Toyota, Shinji

2018-05-30

An anthracene cyclic hexamer was synthesized by the coupling reaction as a macrocyclic hydrocarbon host. This disk-shaped host included a C 60 guest in 1:1 ratio to form a Saturn-type supramolecular complex in solution and in crystals. X-ray analysis unambiguously revealed that the guest molecule was accommodated in the middle of the host cavity with several CH⋅⋅⋅π contacts. The association constant K a determined by NMR titration measurements was 2.3×10 3  L mol -1 at 298 K in toluene. The structural features and the role of CH⋅⋅⋅π interactions are discussed with the aid of DFT calculations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamic reciprocity in bio-inspired supramolecular materials

NARCIS (Netherlands)

Bastings, M.M.C.

2012-01-01

Dynamic reciprocity, the spatio-temporal bidirectional process between evolving partners in a functional system is not only found in nature, but also applies to supramolecularly assembling architectures. In this thesis, the focus was on the understanding of nature-inspired supramolecular

Preparation of 5-benzotriazolyl-4-hydroxy-3- sec-butylbenzenesulfonate anion-intercalated layered double hydroxide and its photostabilizing effect on polypropylene

Science.gov (United States)

Li, Dianqing; Tuo, Zhenjun; Evans, David G.; Duan, Xue

2006-10-01

An organic UV absorber has been intercalated into a layered double hydroxide (LDH) host by ion-exchange method using ZnAl-NO 3-LDH as a precursor with an aqueous solution of the sodium salt of 5-benzotriazolyl-4-hydroxy-3- sec-butylbenzenesulfonic acid (BZO). After intercalation of the UV absorber, the interlayer distance in the LDHs increases from 0.89 to 2.32 nm. Infrared spectra and thermogravimetry and differential thermal analysis (TG-DTA) curves reveal the presence of a complex system of supramolecular host-guest interactions. The thermostability of BZO is markedly enhanced by intercalation in the LDH host. ZnAl-BZO-LDHs/polypropylene composite materials exhibit excellent UV photostability.

Guest loyalty in hospitality industry

Directory of Open Access Journals (Sweden)

Gagić Snježana

2015-01-01

Full Text Available The continuous growth of competition in the hospitality sector has created the need to retain guests and prevent them from switching company due to better offer or saturation. Loyal customers are a valuable asset for catering companies, not only because of the awareness of the effects of customer loyalty. They tend to spread word-of-mouth advertising, more tolerant to price changes, as well as they casually create a linkage to their friends, relatives, colleagues, and other probable consumers and thus enable businesses to uphold a guest's base. By recognizing loyalty guests' importance, the global hospitality industry created monetary and non-monetary rewards for loyal visitors, delayed gratification (points collection and immediate rewards, as well as numerous other reward systems that try to keep them. To win customer loyalty, together with all benefits arising from it, caterers need to become familiar with factors, which determine guests' loyalty. The paper will show the results of research regarding the impact of the service quality and guests' satisfaction to their loyalty. Many authors have confirmed that employees' satisfaction affected customers' satisfaction, so this paper will give an answer does it influence on customers' loyalty as well.

Rodlike Supramolecular Nanoassemblies of Degradable Poly(Aspartic Acid) Derivatives and Hydroxyl-Rich Polycations for Effective Delivery of Versatile Tumor-Suppressive ncRNAs.

Science.gov (United States)

Song, Hai-Qing; Pan, Wenting; Li, Rui-Quan; Yu, Bingran; Liu, Wenjuan; Yang, Ming; Xu, Fu-Jian

2018-03-01

The delivery of tumor-suppressive noncoding RNAs (ncRNAs) including short ncRNAs (i.e., miRNAs) and long ncRNAs (lncRNAs) is put forward to treat tumors. In this work, novel rodlike supramolecular nanoassemblies (CNC @CB[8] @ PGEA) of degradable poly(aspartic acid) (PAsp) derivatives-grafted cellulose nanocrystals (CNCs) and hydroxyl-rich polycations (ethanolamine-functionalized poly(glycidyl methacrylate), PGEA) are proposed via typical cucurbit[8]uril (CB[8])-based host-guest interactions for delivery of different ncRNAs to treat hepatocellular carcinoma (HCC). Spindly CNCs, one kind of natural polysaccharide nanoparticles, possess good biocompatibility and unique physico-chemical properties. PGEA with abundant hydroxyl groups is one promising gene carrier with low cytotoxicity. PAsp can benefit the disassembly and degradability of nanoassemblies within cells. CNC @ CB[8]@PGEA combines the different unique properties of CNC, PGEA, and PAsp. CNC @ CB[8] @ PGEA effectively complexes the expression constructs of miR-101 (plasmid pc3.0-miR-101) and lncRNA MEG3 (plasmid pc3.0-MEG3). CNC @ CB[8] @ PGEA produces much better transfection performances than PGEA-containing assembly units. In addition, the codelivery system of CNC @ CB[8] @ PGEA/(pc3.0-MEG3+pc3.0-miR-101) nanocomplexes demonstrates better efficacy in suppressing HCC than CNC @ CB[8] @ PGEA/pc3.0-MEG3 or CNC @ CB[8] @ PGEA/pc3.0-miR-101 nanocomplexes alone. Such rodlike supramolecular nanoassemblies will provide a promising means to produce efficient delivery vectors of versatile tumor-suppressive nucleic acids. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

EPR of divalent manganese in non-Kramers hosts

Energy Technology Data Exchange (ETDEWEB)

Lech, J.; Slezak, A. [Institute of Physics, Technical University of Czestochowa, Czestochowa (Poland)

1997-12-31

Various interactions which lead to the observation of sharp EPR spectra of the high half-integer spin impurity Mn{sup 2+} (S=5/2) in paramagnetic hosts with integer spins S=1 and S=2 have been studied. Studies have been carried out on the basis of data extracted from experimental EPR spectra of Mn{sup 2+} in single crystal of divalent nickel Ni{sup 2+} (S=1) and Fe{sup 2+} (S=1) perchlorate hexahydrates. It has been shown that dipolar host-host and host-guest couplings broaden resonance lines of Mn{sup 2+}. Narrowing of the lines in the both crystals can be mainly attributed to the host-guest exchange interactions and quenching of the host spins. 19 refs, 3 figs, 1 tab.

Chemistry of supramolecular systems containing porphyrins and metal complexes

OpenAIRE

Araki, Koiti; Toma, Henrique Eisi

2002-01-01

Supramolecular chemistry is expected to keep a high developing pace in the next years, giving support to the advancement of molecular devices and nanotechnology. In this sense, porphyrins and their analogues should play a significant role as a consequence of their catalytic, electrocatalytic, photochemical and photoelectrochemical properties. In this review we focused on our own strategy based on coordination chemistry for the design and build-up of supermolecules and supramolecular structure...

A concept for the removal of microplastics from the marine environment with innovative host-guest relationships.

Science.gov (United States)

Herbort, Adrian Frank; Schuhen, Katrin

2017-04-01

Environmental pollution caused by inert anthropogenic stressors such as microplastics in aquatic media is constantly increasing. Through the proliferating use of plastic products in daily life, more and more plastic particles enter waters as primary microplastics. Even though large scale plastic items such as plastic bottles and bags represent the highest percentage of plastic waste, their degeneration also generates microparticles and nanoparticles (secondary microplastics). Modern sewage treatment plants require innovative ideas in order to deal with this man-made problem. State-of-the-art technology offers approaches to minimise the amount of microplastics in aquatic systems. These technologies, however, are either insufficient or very costly, as well as time-consuming in both cases. The conceptual idea presented here is to apply innovative inorganic-organic hybrid silica gels which provide a cost-effective and straightforward approach. Currently, the synthesis of preorganised bioinspired compounds is advancing in order to produce functionalised hybrid silica gels in a further step. These gels have the ability to remove stressors such as microplastics from waste water. By means of the sol-gel process, bioinspired silane compounds are currently being permuted to macromolecules and examined with respect to their properties as fixation and filter material in order to remove the hydrophobic anthropogenic stressors sustainably. Here, the reproduction of biological systems plays a significant role. In particular in material sciences, this approach is becoming increasingly important. Among other concepts, new biomimetic molecules form the basis for the investigation of innovative host-guest relationships for anthropogenic stressors in the environment and their implementation in technical processes.

Magnetism: a supramolecular function

International Nuclear Information System (INIS)

Decurtins, S.; Pellaux, R.; Schmalle, H.W.

1996-01-01

The field of molecule-based magnetism has developed tremendously in the last few years. Two different extended molecular - hence supramolecular -systems are presented. The Prussian-blue analogues show some of the highest magnetic ordering temperature of any class of molecular magnets, T c = 315 K, whereas the class of transition-metal oxalate-bridged compounds exhibits a diversity of magnetic phenomena. Especially for the latter compounds, the elastic neutron scattering technique has successfully been proven to trace the magnetic structure of these supramolecular and chiral compounds. (author) 18 figs., 25 refs

Magnetism: a supramolecular function

Energy Technology Data Exchange (ETDEWEB)

Decurtins, S; Pellaux, R; Schmalle, H W [Zurich Univ., Inst. fuer Anorganische Chemie, Zurich (Switzerland)

1996-11-01

The field of molecule-based magnetism has developed tremendously in the last few years. Two different extended molecular - hence supramolecular -systems are presented. The Prussian-blue analogues show some of the highest magnetic ordering temperature of any class of molecular magnets, T{sub c} = 315 K, whereas the class of transition-metal oxalate-bridged compounds exhibits a diversity of magnetic phenomena. Especially for the latter compounds, the elastic neutron scattering technique has successfully been proven to trace the magnetic structure of these supramolecular and chiral compounds. (author) 18 figs., 25 refs.

The effect of host relaxation and dynamics on guest molecule dynamics in H2/tetrahydrofuranhydrate.

Science.gov (United States)

Peterson, Vanessa K; Shoko, Elvis; Kearley, Gordon J

2011-01-01

We use ab initio molecular dynamics simulations to obtain classically the effects of H2O cage motions on the potential-energy surface (PES) of encapsulated H2 in the H2/tetrahydrofuran-hydrate system. The significant differences between the PES for the H2 in rigid and flexible cages that we find will influence calculation of the quantum dynamics of the H2. Part of these differences arises from the relaxation of the H2O cage around the classical H2, with a second part arising from the coupling of both translational and rotational motions of H2 with the H20 cage. We find that isotopic substitution of 2H for 1H of the H2O cage affects the coupling, which has implications for experiments that require the use of 2H2O, including inelastic neutron scattering that uses 2H2O cages in order to focus on the H2 guest dynamics. Overall, this work emphasizes the importance of taking into account cage dynamics in any approach used to understand the dynamics of H2 guests in porous framework materials.

Photocaged Competitor Guests: A General Approach Toward Light-Activated Cargo Release From Cucurbiturils.

Science.gov (United States)

Romero, Miguel A; Basílio, Nuno; Moro, Artur J; Domingues, Mara; González-Delgado, José A; Arteaga, Jesús F; Pischel, Uwe

2017-09-21

A general approach toward the light-induced guest release from cucurbit[7]uril by means of a photoactivatable competitor was devised. An o-nitrobenzyl-caged competitor is photolyzed to generate a competitive guest that can displace cargo from the host macrocycle solely based on considerations of chemical equilibrium. With this method the release of terpene guests from inclusion complexes with cucurbit[7]uril was demonstrated. The binding of the herein investigated terpenes, all being lead fragrant components in essential oils, has been characterized for the first time. They feature binding constants of up to 10 8  L mol -1 and a high differential binding selectivity (spanning four orders of magnitude for the binding constants for the particular set of terpenes). By fine-tuning the photoactivatable competitor guest, selective and also sequential release of the terpenes was achieved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Different Guest Worker Story: Roma Guest Workers – a Transnational Minority in Transmigration

Directory of Open Access Journals (Sweden)

Ana Banić-Grubišić

2016-03-01

Full Text Available he paper considers the ambiguity of the term ‘guest worker’, based on the example of economic migrants who belong to the Roma population. Over the last fifty years, members of the Roma minority have migrated to Western European countries for different reasons (economic, political and social reasons, and there is no official data on the precise number of Roma who have migrated abroad, whether permanently or temporarily. It is possible to establish a number of categories of Roma immigrants who reside permanently or temporarily in Western European countries. These are: the so-called “classic guest workers” who, through legal or illegal means went to work abroad in the 60’s and 70’s, and mostly settled permanently in the host countries; Roma refugees from Kosovo and/or asylum seekers who left the country during the wars in the 90’s, and who were returned to Serbia after the signing of the Readmission treaty; and those Roma who represent occasional economic migrants: people who, after Serbia was put on the white Schengen list (the liberalization of the visa policy for citizens of Serbia, spend three months at a time working abroad. Even though these three categories of Roma workers have different reasons for migrating from and returning to Serbia, the majority of the population perceives them as a unified, distinct whole – as guest workers. The paper is the result of fieldwork conducted in South-Eastern Serbia, in the village of Minicevo.

Penerapan Aplikasi Web Di Hotel Arinda Guest House Bandung

Directory of Open Access Journals (Sweden)

Ade Mubarok

2017-09-01

Abstract Hotel was a thriving industry very fast with the advent of the information technology. One factor that can provide comfort is the existence of the information rapid to a reservation hotel. Several problems that ordinarily encountered hotel management and customers as it tough for rapid information, do check in and the payment of requiring guests come to the hotel, include families in village records the guest log and make a report manually.In writing thesis this, writer build a application of hotel by adopting information technology. The model used to the development of software is the method waterfall, which begins with analysis needs adapted to systems are go at the hotel arinda guest house, design system and software, coding, testing, and implementation.So that this research produce information system a reservation hotel web-based. Of interface ease of use user and showing functionality that can be used to at the check in , the hotel , faster information and save time prospective guest on do reservations , efficient in recording the guest log and reports.   Keywords: Website, Aplication, Hotel Arinda Guest House, checked in, Waterfall.

Separation of radionuclides using host-guest materials

International Nuclear Information System (INIS)

Drabova, V.

2014-01-01

This thesis is focused on the development of complex procedure with using commercially available sorbents to separate anthropogenic actinides 237 Np, 241 Am, 238 Pu and 239 , 240 Pu and their determination in the liquid radioactive wastes by using alpha spectrometry. Abilities of using commercially available sorbent AnaLig(R)Pu-02 gel from IBC Advanced Technologies, Inc. were tested, this product belongs to host-guest materials based on molecular recognition technology. This material is capable of selectively capturing actinides in oxidation state IV. To adjust the oxidation state of 238 Pu and 239 , 240 Pu was used NaNO 2 . Pu(IV) forms in the medium of nitric acid complexes, [Np(NO 3 ) 6 ] - , which are captured on the column. For the second monitored radionuclide, neptunium is typical valence V, Np(V) in the concentrated nitric acid produces strong complexes, [Np(NO 3 ) 6 ] - , which are capable of the sorption on the column of AnaLig(R)Pu-02 gel. The most common state of americium in aqueous solutions is III. Whereas in this oxidation state, americium do not form complexes in 8 mol·dm -3 nitric acid is the result of the flow-through. On the base of experimental obtained results, solution of 0.1 mol·dm -3 NH 4 I in 9 mol·dm -3 HCl was selected for elution of plutonium. Neptunium was eluted from the column using 9 mol·dm -3 of HCl with addition of 0.5 cm 3 TiCl 3 . Optimizing conditions for the separation procedure was performed by using model solution of radioactive waste which was prepared according to the chemical composition of radioactive concentrate from NPP Mochovce and NPP Bohunice. The effect of the concentration of Fe 3+ , the effect of the concentration of the HCl, the effect of the concentration of the solution of NH 4 I and the effect of the volume of this solution to the yields of 238 Pu were studied. And also was studied the effect of 9 mol·dm -3 of HCl and the effect of volume of 15 % TiCl 3 to the yields of 237 Np. Sorbent DGA(R) Resin from

Quantum-Chemical Insights into the Self-Assembly of Carbon-Based Supramolecular Complexes

Directory of Open Access Journals (Sweden)

Joaquín Calbo

2018-01-01

Full Text Available Understanding how molecular systems self-assemble to form well-organized superstructures governed by noncovalent interactions is essential in the field of supramolecular chemistry. In the nanoscience context, the self-assembly of different carbon-based nanoforms (fullerenes, carbon nanotubes and graphene with, in general, electron-donor molecular systems, has received increasing attention as a means of generating potential candidates for technological applications. In these carbon-based systems, a deep characterization of the supramolecular organization is crucial to establish an intimate relation between supramolecular structure and functionality. Detailed structural information on the self-assembly of these carbon-based nanoforms is however not always accessible from experimental techniques. In this regard, quantum chemistry has demonstrated to be key to gain a deep insight into the supramolecular organization of molecular systems of high interest. In this review, we intend to highlight the fundamental role that quantum-chemical calculations can play to understand the supramolecular self-assembly of carbon-based nanoforms through a limited selection of supramolecular assemblies involving fullerene, fullerene fragments, nanotubes and graphene with several electron-rich π-conjugated systems.

Supramolecular Complexes Formed in Systems Bile Salt-Bilirubin-Silica

Science.gov (United States)

Vlasova, N. N.; Severinovskaya, O. V.; Golovkova, L. P.

The formation of supramolecular complexes between bilirubin and primary micelles of bile salts has been studied. The association constants of bile salts and binding of bilirubin with these associates have been determined. The adsorption of bilirubin and bile salts from individual and mixed aqueous solutions onto hydrophobic silica surfaces has been investigated. The interaction of bilirubin with primary bile salt micelles and the strong retention in mixed micelles, which are supramolecular complexes, result in the adsorption of bilirubin in free state only.

Molecular Recognition of Vesicles : Host-Guest Interactions Combined with Specific Dimerization of Zwitterions

NARCIS (Netherlands)

Voskuhl, Jens; Fenske, Tassilo; Stuart, Marc C. A.; Wibbeling, Birgit; Schmuck, Carsten; Ravoo, Bart Jan

2010-01-01

The aggregation of beta-cyclodextrin vesicles can be induced by an adamantyl-substituted zwitterionic guanidiniocarbonylpyrrole carboxylate guest molecule (1). Upon addition of 1 to the cyclodextrin vesicles at neutral pH, the vesicles aggregate (but do not fuse), as shown by using UV/Vis and

Non-equilibrium supramolecular polymerization.

Science.gov (United States)

Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

2017-09-18

Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

Constitutional dynamic chemistry: bridge from supramolecular chemistry to adaptive chemistry.

Science.gov (United States)

Lehn, Jean-Marie

2012-01-01

Supramolecular chemistry aims at implementing highly complex chemical systems from molecular components held together by non-covalent intermolecular forces and effecting molecular recognition, catalysis and transport processes. A further step consists in the investigation of chemical systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, thus behaving as programmed chemical systems. Supramolecular chemistry is intrinsically a dynamic chemistry in view of the lability of the interactions connecting the molecular components of a supramolecular entity and the resulting ability of supramolecular species to exchange their constituents. The same holds for molecular chemistry when the molecular entity contains covalent bonds that may form and break reversibility, so as to allow a continuous change in constitution by reorganization and exchange of building blocks. These features define a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels.CDC introduces a paradigm shift with respect to constitutionally static chemistry. The latter relies on design for the generation of a target entity, whereas CDC takes advantage of dynamic diversity to allow variation and selection. The implementation of selection in chemistry introduces a fundamental change in outlook. Whereas self-organization by design strives to achieve full control over the output molecular or supramolecular entity by explicit programming, self-organization with selection operates on dynamic constitutional diversity in response to either internal or external factors to achieve adaptation.The merging of the features: -information and programmability, -dynamics and reversibility, -constitution and structural diversity, points to the emergence of adaptive and evolutive chemistry, towards a chemistry of complex matter.

Spectro-microscopic study of the formation of supramolecular networks

Science.gov (United States)

Sadowski, Jerzy T.

2015-03-01

Metal-organic frameworks (MOFs) are emerging as a new class of materials for CO2 capture. There are many fundamental questions, including the optimum pore size and arrangement of the molecules in the structure to achieve highest CO2 uptake. As only the surface is of interest for potential applications such as heterogeneous catalysis, nano-templating, and sensing, 2D analogs of MOFs can serve as good model systems. Utilizing capabilities of LEEM/PEEM for non-destructive interrogation of the real-time molecular self-assembly, we investigated supramolecular systems based on carboxylic acid-metal complexes, such as trimesic and mellitic acid, doped with transition metals. Such 2D networks act as host systems for transition-metal phthalocyanines (MPc; M = Fe, Ti, Sc) and the electrostatic interactions of CO2 molecules with transition metal ions, can be tuned by controlling the type of TM ion and the size of the pore in the host network. The understanding of directed self-assembly by controlling the molecule-substrate interaction can enable us to engineer the pore size and density, and thus tune the host's chemical activity. Research carried out at the Center for Functional Nanomaterials and National Synchrotron Light Source, Brookhaven National Laboratory, which are supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10.

Engineering responsive supramolecular biomaterials: Toward smart therapeutics.

Science.gov (United States)

Webber, Matthew J

2016-09-01

Engineering materials using supramolecular principles enables generalizable and modular platforms that have tunable chemical, mechanical, and biological properties. Applying this bottom-up, molecular engineering-based approach to therapeutic design affords unmatched control of emergent properties and functionalities. In preparing responsive materials for biomedical applications, the dynamic character of typical supramolecular interactions facilitates systems that can more rapidly sense and respond to specific stimuli through a fundamental change in material properties or characteristics, as compared to cases where covalent bonds must be overcome. Several supramolecular motifs have been evaluated toward the preparation of "smart" materials capable of sensing and responding to stimuli. Triggers of interest in designing materials for therapeutic use include applied external fields, environmental changes, biological actuators, applied mechanical loading, and modulation of relative binding affinities. In addition, multistimuli-responsive routes can be realized that capture combinations of triggers for increased functionality. In sum, supramolecular engineering offers a highly functional strategy to prepare responsive materials. Future development and refinement of these approaches will improve precision in material formation and responsiveness, seek dynamic reciprocity in interactions with living biological systems, and improve spatiotemporal sensing of disease for better therapeutic deployment.

Capturing the guest experience in hotels phase one : theoretical background and development of the guest experience scan

NARCIS (Netherlands)

Marle, van R.S.F. (Rienk); Pijls, R. (Ruth); Schreiber, G.H. (Gerrit)

2011-01-01

The goal for the coming years is to get insight in the guest experience in hotels. What is guest experience? How to measure guest experience? What is the relation between guest experience and guest loyalty? And finally, what tangible elements in the physical environment of hotels and the contact

Supramolecular chemistry: from molecular information towards self-organization and complex matter

International Nuclear Information System (INIS)

Lehn, Jean-Marie

2004-01-01

Molecular chemistry has developed a wide range of very powerful procedures for constructing ever more sophisticated molecules from atoms linked by covalent bonds. Beyond molecular chemistry lies supramolecular chemistry, which aims at developing highly complex chemical systems from components interacting via non-covalent intermolecular forces. By the appropriate manipulation of these interactions, supramolecular chemistry became progressively the chemistry of molecular information, involving the storage of information at the molecular level, in the structural features, and its retrieval, transfer, and processing at the supramolecular level, through molecular recognition processes operating via specific interactional algorithms. This has paved the way towards apprehending chemistry also as an information science. Numerous receptors capable of recognizing, i.e. selectively binding, specific substrates have been developed, based on the molecular information stored in the interacting species. Suitably functionalized receptors may perform supramolecular catalysis and selective transport processes. In combination with polymolecular organization, recognition opens ways towards the design of molecular and supramolecular devices based on functional (photoactive, electroactive, ionoactive, etc) components. A step beyond preorganization consists in the design of systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined supramolecular architectures by self-assembly from their components. Self-organization processes, directed by the molecular information stored in the components and read out at the supramolecular level through specific interactions, represent the operation of programmed chemical systems. They have been implemented for the generation of a variety of discrete functional architectures of either organic or inorganic nature. Self-organization processes also give access to advanced supramolecular materials, such as

Host–Guest Chirality Interplay: A Mutually Induced Formation of a Chiral ZMOF and Its Double-Helix Polymer Guests

KAUST Repository

Luo, Xiaolong

2016-01-12

A novel homochiral zeolite-like metal-organic framework (ZMOF), [(Cu4I4) (dabco)2]·[Cu2(bbimb)]·3DMF (JLU-Liu23, dabco =1,4-diazabicyclo[2.2.2]-octane, H2bbimb =1,3-bis(2-benzimidazol)benzene, DMF = N,N-dimethylformamide), has been successfully constructed to host unprecedented DNA-like [Cu2(bbimb)]n polymers with double-helicity. The host-guest chirality interplay permitted the induced formation of an unusual gyroid MOF with homochirality and helical channels in the framework for the first time, JLU-Liu23. Importantly, the enantiomeric pairs (23P, 23M) can be promoted and isolated in the presence of appropriate chiral inducing agents, affording enantioselective separation of chiral molecules as well as small gas molecules. © 2016 American Chemical Society.

Thermal degradation features of peppermint oil in a binary system with Β- cyclodextrin

Directory of Open Access Journals (Sweden)

I. A. Omelchenko

2016-04-01

Full Text Available Aim. One of the most promising ways of changing physical and chemical properties of the active pharmaceutical ingredient is an encapsulation on a molecular level with the use of cyclodextrins. This makes it possible to create products with the desired activity and controlled distribution in the body. Methods and results. We have studied the thermal decomposition of peppermint oil in binary systems with β-cyclodextrin. It has been found that the thermal degradation of mechanical mixture and inclusion complex of the «host-guest» with the composition of 1:1 passes through different mechanisms. Conclusions. It is shown that the given data of thermal stability are useful for the identification of an inclusion complex «β-CD – peppermint oil» and assessing its complexation, and for the development of technology of medicinal forms of supramolecular complex of β-cyclodextrin and peppermint oil

Gelation induced supramolecular chirality: chirality transfer, amplification and application.

Science.gov (United States)

Duan, Pengfei; Cao, Hai; Zhang, Li; Liu, Minghua

2014-08-14

Supramolecular chirality defines chirality at the supramolecular level, and is generated from the spatial arrangement of component molecules assembling through non-covalent interactions such as hydrogen bonding, van der Waals interactions, π-π stacking, hydrophobic interactions and so on. During the formation of low molecular weight gels (LMWGs), one kind of fascinating soft material, one frequently encounters the phenomenon of chirality as well as chiral nanostructures, either from chiral gelators or even achiral gelators. A view of gelation-induced supramolecular chirality will be very helpful to understand the self-assembly process of the gelator molecules as well as the chiral structures, the regulation of the chirality in the gels and the development of the "smart" chiral materials such as chiroptical devices, catalysts and chiral sensors. It necessitates fundamental understanding of chirality transfer and amplification in these supramolecular systems. In this review, recent progress in gelation-induced supramolecular chirality is discussed.

Topological dynamics in supramolecular rotors.

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Palma, Carlos-Andres; Björk, Jonas; Rao, Francesco; Kühne, Dirk; Klappenberger, Florian; Barth, Johannes V

2014-08-13

Artificial molecular switches, rotors, and machines are set to establish design rules and applications beyond their biological counterparts. Herein we exemplify the role of noncovalent interactions and transient rearrangements in the complex behavior of supramolecular rotors caged in a 2D metal-organic coordination network. Combined scanning tunneling microscopy experiments and molecular dynamics modeling of a supramolecular rotor with respective rotation rates matching with 0.2 kcal mol(-1) (9 meV) precision, identify key steps in collective rotation events and reconfigurations. We notably reveal that stereoisomerization of the chiral trimeric units entails topological isomerization whereas rotation occurs in a topology conserving, two-step asynchronous process. In supramolecular constructs, distinct displacements of subunits occur inducing a markedly lower rotation barrier as compared to synchronous mechanisms of rigid rotors. Moreover, the chemical environment can be instructed to control the system dynamics. Our observations allow for a definition of mechanical cooperativity based on a significant reduction of free energy barriers in supramolecules compared to rigid molecules.

The guest-worker in Western Europe--an obituary.

Science.gov (United States)

Castles, S

1986-01-01

The significance of guest workers is examined for six Western European countries. It is found that "the dynamics of the migratory process led to family reunification and settlement, against the original intentions of the workers, employers and states concerned. The recruitment of guest-workers stopped after 1974, but many migrants stayed on, becoming permanent ethnic minorities, in a situation of economic and social crisis. It is argued that guest-worker systems inevitably lead to permanent migration in the long run, and that it is better to plan for orderly settlement through appropriate policies." excerpt

Supramolecular Nanoparticles for Molecular Diagnostics and Therapeutics

Science.gov (United States)

Chen, Kuan-Ju

Over the past decades, significant efforts have been devoted to explore the use of various nanoparticle-based systems in the field of nanomedicine, including molecular imaging and therapy. Supramolecular synthetic approaches have attracted lots of attention due to their flexibility, convenience, and modularity for producing nanoparticles. In this dissertation, the developmental story of our size-controllable supramolecular nanoparticles (SNPs) will be discussed, as well as their use in specific biomedical applications. To achieve the self-assembly of SNPs, the well-characterized molecular recognition system (i.e., cyclodextrin/adamantane recognition) was employed. The resulting SNPs, which were assembled from three molecular building blocks, possess incredible stability in various physiological conditions, reversible size-controllability and dynamic disassembly that were exploited for various in vitro and in vivo applications. An advantage of using the supramolecular approach is that it enables the convenient incorporation of functional ligands onto SNP surface that confers functionality ( e.g., targeting, cell penetration) to SNPs. We utilized SNPs for molecular imaging such as magnetic resonance imaging (MRI) and positron emission tomography (PET) by introducing reporter systems (i.e., radio-isotopes, MR contrast agents, and fluorophores) into SNPs. On the other hand, the incorporation of various payloads, including drugs, genes and proteins, into SNPs showed improved delivery performance and enhanced therapeutic efficacy for these therapeutic agents. Leveraging the powers of (i) a combinatorial synthetic approach based on supramolecular assembly and (ii) a digital microreactor, a rapid developmental pathway was developed that is capable of screening SNP candidates for the ideal structural and functional properties that deliver optimal performance. Moreover, SNP-based theranostic delivery systems that combine reporter systems and therapeutic payloads into a

Preparation of 5-benzotriazolyl-4-hydroxy-3-sec-butylbenzenesulfonate anion-intercalated layered double hydroxide and its photostabilizing effect on polypropylene

International Nuclear Information System (INIS)

Li Dianqing; Tuo Zhenjun; Evans, David G.; Duan Xue

2006-01-01

An organic UV absorber has been intercalated into a layered double hydroxide (LDH) host by ion-exchange method using ZnAl-NO 3 -LDH as a precursor with an aqueous solution of the sodium salt of 5-benzotriazolyl-4-hydroxy-3-sec-butylbenzenesulfonic acid (BZO). After intercalation of the UV absorber, the interlayer distance in the LDHs increases from 0.89 to 2.32 nm. Infrared spectra and thermogravimetry and differential thermal analysis (TG-DTA) curves reveal the presence of a complex system of supramolecular host-guest interactions. The thermostability of BZO is markedly enhanced by intercalation in the LDH host. ZnAl-BZO-LDHs/polypropylene composite materials exhibit excellent UV photostability. - Graphical abstract: Intercalation of an organic UV absorber in a layered double hydroxide host leads to an enhancement of its photo- and thermal stability

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer.

Science.gov (United States)

Baker, Matthew B; Albertazzi, Lorenzo; Voets, Ilja K; Leenders, Christianus M A; Palmans, Anja R A; Pavan, Giovanni M; Meijer, E W

2015-02-20

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers: one with and one without a stereogenic methyl. Initially aiming simply to understand the molecular behaviour of these systems in water, we find that while the fibres may look identical, the introduction of homochirality imparts a higher level of internal order to the supramolecular polymer. Although this increased order does not seem to affect the basic dimensions of the supramolecular fibres, the equilibrium dynamics of the polymers differ by almost an order of magnitude. This report represents the first observation of a structure/property relationship with regard to equilibrium dynamics in water-soluble supramolecular polymers.

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer

Science.gov (United States)

Baker, Matthew B.; Albertazzi, Lorenzo; Voets, Ilja K.; Leenders, Christianus M. A.; Palmans, Anja R. A.; Pavan, Giovanni M.; Meijer, E. W.

2015-02-01

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers: one with and one without a stereogenic methyl. Initially aiming simply to understand the molecular behaviour of these systems in water, we find that while the fibres may look identical, the introduction of homochirality imparts a higher level of internal order to the supramolecular polymer. Although this increased order does not seem to affect the basic dimensions of the supramolecular fibres, the equilibrium dynamics of the polymers differ by almost an order of magnitude. This report represents the first observation of a structure/property relationship with regard to equilibrium dynamics in water-soluble supramolecular polymers.

Supramolecular interactions of oxidative stress biomarker glutathione with fluorone black

Science.gov (United States)

Hepel, Maria; Stobiecka, Magdalena

2018-03-01

Oxidative stress biomarkers, including glutathione (GSH) and related compounds, are involved in a variety of interactions enabling redox potential maintenance in living cells and protection against radicals. Since the oxidative stress is promoting and, in many cases, inducing serious illnesses, monitoring of GSH levels can aid in diagnostics and disease prevention. Herein, we report on the discovery of the formation of a supramolecular ensemble of GSH with fluorone black (9-phenyl fluorone, FB) which is optically active and enables sensitive determination of GSH by resonance elastic light scattering (RELS). We have found that supramolecular interactions of GSH with FB can be probed with spectroscopic, RELS, and electrochemical methods. Our investigations show that RELS intensity for FB solutions increases with GSH concentration while fluorescence emission of FB is not affected, as quenching begins only above 0.8 mM GSH. The UV-Vis difference spectra show a positive peak at 383 nm and a negative peak at 458 nm, indicating a higher-energy absorbing complex in comparison to the non-bonded FB host. Supramolecular interactions of FB with GSH have also been corroborated by electrochemical measurements involving two configurations of FB-GSH ensembles on electrodes: (i) an inverted orientation on Au-coated quartz crystal piezoelectrode (Au@SG-FB), with strong thiolate bonding to gold, and (ii) a non-inverted orientation on glassy carbon electrode (GCE@FB-GS), with weak π-π stacking attachment and efficient charge mediation through the ensemble. The formation of a supramolecular ensemble with hydrogen bonding has also been confirmed by quantum mechanical calculations. The discovery of supramolecular FB-GSH ensemble formation enables elucidating the mechanisms of strong RELS responses, changes in UV-Vis absorption spectra, and the electrochemical reactivity. Also, it provides new insights to the understanding of the efficient charge-transfer in redox potential homeostasis

Supramolecular interactions of oxidative stress biomarker glutathione with fluorone black.

Science.gov (United States)

Hepel, Maria; Stobiecka, Magdalena

2018-03-05

Oxidative stress biomarkers, including glutathione (GSH) and related compounds, are involved in a variety of interactions enabling redox potential maintenance in living cells and protection against radicals. Since the oxidative stress is promoting and, in many cases, inducing serious illnesses, monitoring of GSH levels can aid in diagnostics and disease prevention. Herein, we report on the discovery of the formation of a supramolecular ensemble of GSH with fluorone black (9-phenyl fluorone, FB) which is optically active and enables sensitive determination of GSH by resonance elastic light scattering (RELS). We have found that supramolecular interactions of GSH with FB can be probed with spectroscopic, RELS, and electrochemical methods. Our investigations show that RELS intensity for FB solutions increases with GSH concentration while fluorescence emission of FB is not affected, as quenching begins only above 0.8mM GSH. The UV-Vis difference spectra show a positive peak at 383nm and a negative peak at 458nm, indicating a higher-energy absorbing complex in comparison to the non-bonded FB host. Supramolecular interactions of FB with GSH have also been corroborated by electrochemical measurements involving two configurations of FB-GSH ensembles on electrodes: (i) an inverted orientation on Au-coated quartz crystal piezoelectrode (Au@SG-FB), with strong thiolate bonding to gold, and (ii) a non-inverted orientation on glassy carbon electrode (GCE@FB-GS), with weak π-π stacking attachment and efficient charge mediation through the ensemble. The formation of a supramolecular ensemble with hydrogen bonding has also been confirmed by quantum mechanical calculations. The discovery of supramolecular FB-GSH ensemble formation enables elucidating the mechanisms of strong RELS responses, changes in UV-Vis absorption spectra, and the electrochemical reactivity. Also, it provides new insights to the understanding of the efficient charge-transfer in redox potential homeostasis

From supramolecular electrochemistry to molecular-level devices

Energy Technology Data Exchange (ETDEWEB)

Credi, Alberto; Ferrer Ribera, Belen; Venturi, Margherita

2004-09-15

Supramolecular (multi-component) systems can perform complex functions which result from the cooperation of actions performed by suitably selected molecular components. Looking at supramolecular systems, from the viewpoint of the functions, shows that the concept of macroscopic device can be extended to molecular level. Nature exploits very complex molecular-level devices to substain life, and, in the last twenty years, the development of supramolecular chemistry has allowed the construction of simple molecular-level devices, that are of interest not only for basic research, but also for the growth of nanoscience and nanotechnology. Molecular-level devices operate via electronic and/or nuclear rearrangements, and like macroscopic devices, they need energy to operate and signals to communicate with the operator. Electrochemistry can provide the answer to this dual requirement, since electrons/holes, besides supplying the energy needed to make a devices work, can also be useful to 'read' the state of the system and thus to control and monitor the operation of the device. In this article, some examples of molecular-level devices investigated in our laboratory will be reviewed.

Synthesis and Guest Recognition of Switchable Pt-Salphen Based Molecular Tweezers

Directory of Open Access Journals (Sweden)

Lorien Benda

2018-04-01

Full Text Available Molecular tweezers are artificial receptors that have an open cavity generated by two recognition units pre-organized by a spacer. Switchable molecular tweezers, using a stimuli-responsive spacer, are particularly appealing as prototypes of the molecular machines that combine mechanical motion and allosteric recognition properties. In this present study, the synthesis of switchable molecular tweezers composed of a central terpyridine unit substituted in 4,4″ positions by two Pt(II-salphen complexes is reported. The terpyridine ligand can be reversibly converted upon Zn(II coordination from a free ‘U’-shaped closed form to a coordinated ‘W’ open form. This new substitution pattern enables a reverse control of the mechanical motion compared to the previously reported 6,6″ substituted terpyridine-based tweezers. Guest binding studies with aromatic guests showed an intercalation of coronene in the cavity created by the Pt-salphen moieties in the closed conformation. The formation of 1:1 host-guest complex was investigated by a combination of NMR studies and DFT calculations.

Complexation of imidazopyridine-based cations with a 24-crown-8 ether host: [2]pseudorotaxane and partially threaded structures.

Science.gov (United States)

Moreno-Olivares, Surisadai I; Cervantes, Ruy; Tiburcio, Jorge

2013-11-01

A new series of linear molecules derived from 1,2-bis(imidazopyridin-2-yl)ethane can fully or partially penetrate the cavity of the dibenzo-24-crown-8 macrocycle to produce a new family of host-guest complexes. Protonation or alkylation of the nitrogen atoms on the pyridine rings led to an increase in the guest total positive charge up to 4+ and simultaneously generated two new recognition sites (pyridinium motifs) that are in competition with the 1,2-bis(benzimidazole)ethane motif for the crown ether. The relative position of the pyridine ring and the chemical nature of the N-substituent determined the preferred motif and the host-guest complex geometry: (i) for linear guests with relatively bulky groups (i.e., a benzyl substituent), the 1,2-bis(benzimidazole)ethane motif is favored, leading to a fully threaded complex with a [2]pseudorotaxane geometry; (ii) for small substituents, such as -H and -CH3 groups, regardless of the guest shape, the pyridinium motifs are preferred, leading to external partially threaded complexes in a 2:1 host to guest stoichiometry.

A Nexus between Theory and Experiment: Non-Empirical Quantum Mechanical Computational Methodology Applied to Cucurbit[n]urilGuest Binding Interactions

Czech Academy of Sciences Publication Activity Database

Hostaš, Jiří; Sigwalt, D.; Šekutor, M.; Ajani, Haresh; Dubecký, M.; Řezáč, Jan; Zavalij, P. Y.; Cao, L.; Wohlschlager, Ch.; Mlinaric-Majerski, K.; Isaacs, L.; Glaser, R.; Hobza, Pavel

2016-01-01

Roč. 22, č. 48 (2016), s. 17226-17238 ISSN 0947-6539 R&D Projects: GA ČR(CZ) GBP208/12/G016 Institutional support: RVO:61388963 Keywords : adamantane-/diamantane-skeleton guests * biomimetic complexes * BLYP-D3 quantum mechanical calculations * cucurbit[n]uril * host-guest complexes * primary ammonium loops Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.317, year: 2016

Time-resolved monitoring of enzyme activity with ultrafast Hyper-CEST spectroscopy.

Science.gov (United States)

Döpfert, Jörg; Schnurr, Matthias; Kunth, Martin; Rose, Honor May; Hennig, Andreas; Schröder, Leif

2017-12-23

We propose a method to dynamically monitor the progress of an enzymatic reaction using NMR of hyperpolarized 129 Xe in a host-guest system. It is based on a displacement assay originally designed for fluorescence experiments that exploits the competitive binding of the enzymatic product on the one hand and a reporter dye on the other hand to a supramolecular host. Recently, this assay has been successfully transferred to NMR, using xenon as a reporter, cucurbit[6]uril as supramolecular host, and chemical exchange saturation transfer with hyperpolarized Xe (Hyper-CEST) as detection technique. Its advantage is that the enzyme acts on the unmodified substrate and that only the product is detected through immediate inclusion into the host. We here apply a method that drastically accelerates the acquisition of Hyper-CEST spectra in vitro using magnetic field gradients. This allows monitoring the dynamic progress of the conversion of lysine to cadaverine with a temporal resolution of ~30 s. Moreover, the method only requires to sample the very early onset of the reaction (Hyper-CEST results correlate with xenon T 2 measurements performed during the enzymatic reaction. This suggests that ultrafast Hyper-CEST spectroscopy can be used for dynamically monitoring enzymatic activity with NMR. Copyright © 2017 John Wiley & Sons, Ltd.

Application of the principle of supramolecular chemistry in the fields of radiochemistry and radiation chemistry

International Nuclear Information System (INIS)

Shen Xinghai; Chen Qingde; Gao Hongcheng

2008-01-01

Supramolecular chemistry, one of the front fields in chemistry, is defined as 'chemistry beyond the molecule', bearing on the organized entities of higher complexity that result from the association of two or more chemical species held together by intermolecular forces. This article focuses on the application of the principle of supramolecular chemistry in the fields of radiochemistry and radiation chemistry. The following aspects are concerned: (1) the recent progress of supramolecular chemistry; (2) the application of the principle of supramolecular chemistry and the functions of supramolecular system, i.e., recognition, assembly and translocation, in the extraction of nuclides; (3) the application of microemulsion, ionic imprinted polymers, ionic liquids and cloud point extraction in the enrichment of nuclides; (4) the radiation effect of supramolecular systems. (authors)

Host-guest chemistry of dendrimer-drug complexes. 6. Fully acetylated dendrimers as biocompatible drug vehicles using dexamethasone 21-phosphate as a model drug.

Science.gov (United States)

Yang, Kun; Weng, Liang; Cheng, Yiyun; Zhang, Hongfeng; Zhang, Jiahai; Wu, Qinglin; Xu, Tongwen

2011-03-17

Fully acetylated poly(amidoamine) (PAMAM) dendrimer was proposed as a biocompatible drug vehicle using dexamethasone 21-phosphate (Dp21) as a model drug. NMR techniques including (1)H NMR and 2D NOE NMR were used to characterize the host-guest chemistry of acetylated dendrimer/Dp21 and cationic dendrimer/Dp21 complexes. The pH-dependent micellization, complexation, and inclusion behaviors of Dp21 were observed in the presence of acetylated and cationic PAMAM dendrimers. Acetylated dendrimer only encapsulates Dp21 at acidic conditions, while cationic dendrimer can host Dp21 at both acidic and neutral conditions. The orientation of Dp21 molecules in the dendrimer cavities depends on the quaternization degree of tertiary amine groups of dendrimer and the protonation ratio of phosphate group of Dp21. A distinctive pH-dependent release behavior of Dp21 from the acetylated and nonacetylated dendritic matrix was observed: Dp21 exhibits a much slower release rate from acetylated dendrimer at lower pH conditions and a much faster release rate from nonacetylated dendrimer with decreasing pH values. Cytotoxicity studies further confirmed the biocompatibility of acetylated dendrimers, which are much safer in the delivery of therapeutics for the treatment of various diseases than nonacetylated dendrimers. The dendrimer-drug binding and release mechanisms provide a new insight for the design and optimization of biocompatible dendrimer-based drug delivery systems. © 2011 American Chemical Society

From supramolecular polymers to multi-component biomaterials.

Science.gov (United States)

Goor, Olga J G M; Hendrikse, Simone I S; Dankers, Patricia Y W; Meijer, E W

2017-10-30

The most striking and general property of the biological fibrous architectures in the extracellular matrix (ECM) is the strong and directional interaction between biologically active protein subunits. These fibers display rich dynamic behavior without losing their architectural integrity. The complexity of the ECM taking care of many essential properties has inspired synthetic chemists to mimic these properties in artificial one-dimensional fibrous structures with the aim to arrive at multi-component biomaterials. Due to the dynamic character required for interaction with natural tissue, supramolecular biomaterials are promising candidates for regenerative medicine. Depending on the application area, and thereby the design criteria of these multi-component fibrous biomaterials, they are used as elastomeric materials or hydrogel systems. Elastomeric materials are designed to have load bearing properties whereas hydrogels are proposed to support in vitro cell culture. Although the chemical structures and systems designed and studied today are rather simple compared to the complexity of the ECM, the first examples of these functional supramolecular biomaterials reaching the clinic have been reported. The basic concept of many of these supramolecular biomaterials is based on their ability to adapt to cell behavior as a result of dynamic non-covalent interactions. In this review, we show the translation of one-dimensional supramolecular polymers into multi-component functional biomaterials for regenerative medicine applications.

Structural elucidation of dendritic host-guest complexes by X-ray crystallography and molecular dynamics simulations

NARCIS (Netherlands)

Chang, T.; Pieterse, K.; Broeren, M.A.C.; Kooijman, H.; Spek, A.L.; Hilbers, P.A.J.; Meijer, E.W.

2007-01-01

The multiple monovalent binding of adamantyl-urea poly(propyleneimine) dendrimers with carboxylic acid-urea guests was investigated using molecular dynamics simulations and X-ray crystallography to better understand the structure and behavior of the dynamic multivalent complex in solution. The

Facile modification of nanodiamonds with hyperbranched polymers based on supramolecular chemistry and their potential for drug delivery.

Science.gov (United States)

Huang, Hongye; Liu, Meiying; Jiang, Ruming; Chen, Junyu; Mao, Liucheng; Wen, Yuanqing; Tian, Jianwen; Zhou, Naigen; Zhang, Xiaoyong; Wei, Yen

2018-03-01

Due to their excellent chemical stability and remarkable biocompatibility, nanodiamonds (NDs) have received widespread research attention by the biomedical field. The excellent water dispersibility of NDs has significant importance for biomedical applications. Therefore, surface modification of NDs with hydrophilic polymers has been extensively investigated over the past few decades. In this study, we synthesize β-CD containing hyperbranched polymer functionalized ND (ND-β-CD-HPG) composites with high water dispersibility via supramolecular chemistry based on the host-guest interactions between β-Cyclodextrin (β-CD) and adamantine (Ad). The hydroxyl groups of NDs first reacted with 1, 1-adamantanecarbonyl chloride to obtain ND-Ad, which was further functionalized with β-CD containing hyperbranched polymers to form the final ND-β-CD-HPG composites. The successful preparation of ND-β-CD-HPG composites was confirmed by several characterization techniques. Furthermore, the loading and release of the anticancer agent doxorubicin hydrochloride (DOX) on ND-β-CD-HPG composites was also examined to explore its potential in drug delivery. When compared with traditional methods of surface modification of NDs, this method was convenient, fast and efficient. We demonstrated that ND-β-CD-HPG composites have great water dispersibility, low toxicity, high drug-loading capacity and controlled drug-release behavior. Based on these characteristics, ND-β-CD-HPG composites are expected to have high potential for biomedical applications. Copyright © 2017 Elsevier Inc. All rights reserved.

Computational Calorimetry: High-Precision Calculation of Host–Guest Binding Thermodynamics

Science.gov (United States)

2015-01-01

We present a strategy for carrying out high-precision calculations of binding free energy and binding enthalpy values from molecular dynamics simulations with explicit solvent. The approach is used to calculate the thermodynamic profiles for binding of nine small molecule guests to either the cucurbit[7]uril (CB7) or β-cyclodextrin (βCD) host. For these systems, calculations using commodity hardware can yield binding free energy and binding enthalpy values with a precision of ∼0.5 kcal/mol (95% CI) in a matter of days. Crucially, the self-consistency of the approach is established by calculating the binding enthalpy directly, via end point potential energy calculations, and indirectly, via the temperature dependence of the binding free energy, i.e., by the van’t Hoff equation. Excellent agreement between the direct and van’t Hoff methods is demonstrated for both host–guest systems and an ion-pair model system for which particularly well-converged results are attainable. Additionally, we find that hydrogen mass repartitioning allows marked acceleration of the calculations with no discernible cost in precision or accuracy. Finally, we provide guidance for accurately assessing numerical uncertainty of the results in settings where complex correlations in the time series can pose challenges to statistical analysis. The routine nature and high precision of these binding calculations opens the possibility of including measured binding thermodynamics as target data in force field optimization so that simulations may be used to reliably interpret experimental data and guide molecular design. PMID:26523125

Self-Assembly of Supramolecular Aggregates Based on Sector- and Cone-Shaped Dendrons and Bolaamphiphiles

Science.gov (United States)

Shcherbina, M. A.; Chvalun, S. N.

2018-06-01

Using a number of classes of such sector-shaped macromolecules as derivatives of 2,3,4- and 3,4,5- tri(dodecyloxy)benzenesulfonic acid and dendrimers based on gallic acid as an example, the main stages in the formation of supramolecular ensembles are considered: the formation of individual supramolecular aggregates due to the weak noncovalent interactions of mesogenic groups, and the subsequent ordering within these aggregates, which lowers the free energy of a system. Supramolecular aggregates are in turn organized into two- or three-dimensional supramolecular lattices. It is shown that the shape of the supramolecular aggregates and its change along with temperature are functions of the chemical structure of the mesogenic group (resulting in the controlled design of complex self-organizing systems with a given response to external stimuli).

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

Directory of Open Access Journals (Sweden)

Hans-Jörg Schneider

2015-03-01

Full Text Available 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.

A Nexus between Theory and Experiment: Non-Empirical Quantum Mechanical Computational Methodology Applied to Cucurbit[n]uril⋅Guest Binding Interactions.

Science.gov (United States)

Hostaš, Jiří; Sigwalt, David; Šekutor, Marina; Ajani, Haresh; Dubecký, Matúš; Řezáč, Jan; Zavalij, Peter Y; Cao, Liping; Wohlschlager, Christian; Mlinarić-Majerski, Kata; Isaacs, Lyle; Glaser, Robert; Hobza, Pavel

2016-11-21

A training set of eleven X-ray structures determined for biomimetic complexes between cucurbit[n]uril (CB[7 or 8]) hosts and adamantane-/diamantane ammonium/aminium guests were studied with DFT-D3 quantum mechanical computational methods to afford ΔG calcd binding energies. A novel feature of this work is that the fidelity of the BLYP-D3/def2-TZVPP choice of DFT functional was proven by comparison with more accurate methods. For the first time, the CB[n]⋅guest complex binding energy subcomponents [for example, ΔE dispersion , ΔE electrostatic , ΔG solvation , binding entropy (-TΔS), and induced fit E deformation(host) , E deformation(guest) ] were calculated. Only a few weeks of computation time per complex were required by using this protocol. The deformation (stiffness) and solvation properties (with emphasis on cavity desolvation) of cucurbit[n]uril (n=5, 6, 7, 8) isolated host molecules were also explored by means of the DFT-D3 method. A high ρ 2 =0.84 correlation coefficient between ΔG exptl and ΔG calcd was achieved without any scaling of the calculated terms (at 298 K). This linear dependence was utilized for ΔG calcd predictions of new complexes. The nature of binding, including the role of high energy water molecules, was also studied. The utility of introduction of tethered [-(CH 2 ) n NH 3 ] + amino loops attached to N,N-dimethyl-adamantane-1-amine and N,N,N',N'-tetramethyl diamantane-4,9-diamine skeletons (both from an experimental and a theoretical perspective) is presented here as a promising tool for the achievement of new ultra-high binding guests to CB[7] hosts. Predictions of not yet measured equilibrium constants are presented herein. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Total Quality Management Implementation and Guest Satisfaction in Hospitality

Directory of Open Access Journals (Sweden)

Miroslav Knežević

2017-02-01

Full Text Available Total quality management (TQM has become a modern system of constant improvement of the quality of all company activities. The purpose of this study is to measure the expectations and satisfaction of the guests concerning the attribute quality of the hotel product. Furthermore obtained results were compared in such a way as to analyse particularly the reviews of hotels which have implemented TQM and have the ISO 9001 certificates with reviews from hotels which have not implemented TQM and do not have the ISO 9001 certificates. The conducted analysis included 55 hotels in Serbia belonging to the 4- and 5-star categories, i.e. 1308 guests who have stayed in them. The results show that between the observed groups of guests there are fewer differences in expectations than in perception, and that generally speaking guests who have stayed in the hotels that have implemented TQM are more satisfied. The biggest difference concerning the guest satisfaction with the quality of service in the observed hotels is noticeable in relation to the employees and the value-for-money.

Revolving supramolecular chiral structures powered by light in nanomotor-doped liquid crystals

Science.gov (United States)

Orlova, Tetiana; Lancia, Federico; Loussert, Charles; Iamsaard, Supitchaya; Katsonis, Nathalie; Brasselet, Etienne

2018-04-01

Molecular machines operated by light have been recently shown to be able to produce oriented motion at the molecular scale1,2 as well as do macroscopic work when embedded in supramolecular structures3-5. However, any supramolecular movement irremediably ceases as soon as the concentration of the interconverting molecular motors or switches reaches a photo-stationary state6,7. To circumvent this limitation, researchers have typically relied on establishing oscillating illumination conditions—either by modulating the source intensity8,9 or by using bespoke illumination arrangements10-13. In contrast, here we report a supramolecular system in which the emergence of oscillating patterns is encoded at the molecular level. Our system comprises chiral liquid crystal structures that revolve continuously when illuminated, under the action of embedded light-driven molecular motors. The rotation at the supramolecular level is sustained by the diffusion of the motors away from a localized illumination area. Above a critical irradiation power, we observe a spontaneous symmetry breaking that dictates the directionality of the supramolecular rotation. The interplay between the twist of the supramolecular structure and the diffusion14 of the chiral molecular motors creates continuous, regular and unidirectional rotation of the liquid crystal structure under non-equilibrium conditions.

The use of supramolecular chemistry in dye delivery systems

International Nuclear Information System (INIS)

Merckel, Daniel Andrew Sturton

2002-01-01

This thesis reports an investigation into supramolecular recognition of the sulfate/ sulfonate oxoanionic group, a moiety present in the majority of reactive dyes. In the first section the problems associated with the use of reactive dyes in dyeing cotton fabrics together with a literature review of supramolecular approaches to anion recognition are discussed. Drawing on the current literature concerning anion recognition (in particular the recognition of phosphates), the main body of the thesis concerns the design and synthesis of several series ofC-shaped (tweezer) and tripodal potential sulfate/ sulfonate receptors. These receptors incorporate the H-bond donor groups guanidine and thiourea and to a lesser extent urea and amide functionalities. In addition the behaviour of potential tweezer-like receptor molecules based on s-triazine (derived from cyanuric chloride) has also been investigated. The sulfate/ sulfonate and related phosphonate association properties of these potential receptors have been studied. Particular emphasis has been placed on the solid-state supramolecular structures formed by these complexes as determined by single crystal X-ray structural studies, and several novel and revealing examples have been analysed in detail. NMR titration binding studies have also been undertaken in order to investigate the complexation behaviour of several receptors with ''model dye'' phosphonates and sulfonates in solution. In addition a number of single crystal X-ray crystallographic studies were undertaken for other members of the Grossel research group during the course of this work, and the results of these structural studies are also reported. (author)

Complexation of triptycene-derived macrotricyclic polyether with paraquat derivatives, diquat, and a 2,7-diazapyrenium salt: guest-induced conformational changes of the host.

Science.gov (United States)

Han, Ying; Cao, Jing; Li, Peng-Fei; Zong, Qian-Shou; Zhao, Jian-Min; Guo, Jia-Bin; Xiang, Jun-Feng; Chen, Chuan-Feng

2013-04-05

Complexation between a triptycene-derived macrotricyclic polyether containing two dibenzo-[30]-crown-10 cavities and different functionalized paraquat derivatives, diquat, and a 2,7-diazapyrenium salt in both solution and solid state was investigated in detail. It was found that depending on the guests with different terminal functional groups and structures, the macrotricyclic polyether could form 1:1 or 1:2 complexes with the guests in different complexation modes in solution and also in the solid state. Especially, the conformation of the macrotricyclic polyether was efficiently adjusted by the encapsulated guests, which was to some extent similar to substrate-induced fit of enzymes. Moreover, the binding and releasing of the guests in the complexes could be controlled by potassium ions.

Supramolecular gel electrophoresis of large DNA fragments.

Science.gov (United States)

Tazawa, Shohei; Kobayashi, Kazuhiro; Oyoshi, Takanori; Yamanaka, Masamichi

2017-10-01

Pulsed-field gel electrophoresis is a frequent technique used to separate exceptionally large DNA fragments. In a typical continuous field electrophoresis, it is challenging to separate DNA fragments larger than 20 kbp because they migrate at a comparable rate. To overcome this challenge, it is necessary to develop a novel matrix for the electrophoresis. Here, we describe the electrophoresis of large DNA fragments up to 166 kbp using a supramolecular gel matrix and a typical continuous field electrophoresis system. C 3 -symmetric tris-urea self-assembled into a supramolecular hydrogel in tris-boric acid-EDTA buffer, a typical buffer for DNA electrophoresis, and the supramolecular hydrogel was used as a matrix for electrophoresis to separate large DNA fragments. Three types of DNA marker, the λ-Hind III digest (2 to 23 kbp), Lambda DNA-Mono Cut Mix (10 to 49 kbp), and Marker 7 GT (10 to 165 kbp), were analyzed in this study. Large DNA fragments of greater than 100 kbp showed distinct mobility using a typical continuous field electrophoresis system. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combining supramolecular chemistry with biology

NARCIS (Netherlands)

Uhlenheuer, D.A.; Petkau - Milroy, K.; Brunsveld, L.

2010-01-01

Supramolecular chemistry has primarily found its inspiration in biological molecules, such as proteins and lipids, and their interactions. Currently the supramolecular assembly of designed compounds can be controlled to great extent. This provides the opportunity to combine these synthetic

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer

NARCIS (Netherlands)

Baker, M.B.; Albertazzi, L.; Voets, Ilja K.; Leenders, C.M.A.; Palmans, A.R.A.; Pavan, G.M.; Meijer, E. W.

2015-01-01

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers:

Metallo-supramolecular block copolymer micelles

NARCIS (Netherlands)

Gohy, J.M.W.

2009-01-01

Supramolecular copolymers have become of increasing interest in recent years in the search for new materials with tunable properties. In particular, metallo-supramolecular block copolymers in which metal-ligand complexes are introduced in block copolymer architectures, have known important progress,

Influence of the preparation route on the supramolecular organization of lipids in a vesicular system

DEFF Research Database (Denmark)

Elizondo, Elisa; Larsen, Jannik; Hatzakis, Nikos

2012-01-01

A confocal fluorescence microscopy-based assay was used for studying the influence of the preparation route on the supramolecular organization of lipids in a vesicular system. In this work, vesicles composed of cholesterol and CTAB (1/1 mol %) or cholesterol and DOPC (2/8 mol %) and incorporating...

Painting Supramolecular Polymers in Organic Solvents by Super-resolution Microscopy

Science.gov (United States)

2018-01-01

Despite the rapid development of complex functional supramolecular systems, visualization of these architectures under native conditions at high resolution has remained a challenging endeavor. Super-resolution microscopy was recently proposed as an effective tool to unveil one-dimensional nanoscale structures in aqueous media upon chemical functionalization with suitable fluorescent probes. Building upon our previous work, which enabled photoactivation localization microscopy in organic solvents, herein, we present the imaging of one-dimensional supramolecular polymers in their native environment by interface point accumulation for imaging in nanoscale topography (iPAINT). The noncovalent staining, typical of iPAINT, allows the investigation of supramolecular polymers’ structure in situ without any chemical modification. The quasi-permanent adsorption of the dye to the polymer is exploited to identify block-like arrangements within supramolecular fibers, which were obtained upon mixing homopolymers that were prestained with different colors. The staining of the blocks, maintained by the lack of exchange of the dyes, permits the imaging of complex structures for multiple days. This study showcases the potential of PAINT-like strategies such as iPAINT to visualize multicomponent dynamic systems in their native environment with an easy, synthesis-free approach and high spatial resolution. PMID:29697958

Supramolecular chemistry - interdisciplinary branch of science

International Nuclear Information System (INIS)

Radecka-Paryzek, W.

1997-01-01

The scientific problems connected with supramolecular chemistry have been reviewed. The basic concepts have been defined as well as rules governed of macromolecules formation. The special emphasize has been put on present and possible in future application of such systems

Main-chain supramolecular block copolymers.

Science.gov (United States)

Yang, Si Kyung; Ambade, Ashootosh V; Weck, Marcus

2011-01-01

Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers. Such materials combine the microphase separation behavior inherent to block copolymers with the responsiveness of supramolecular materials thereby affording dynamic and reversible materials. This tutorial review covers recent advances in main-chain supramolecular block copolymers and describes the design principles, synthetic approaches, advantages, and potential applications.

Structural aspects, thermal behavior, and stability of a self-assembled supramolecular polymer derived from flunixin-meglumine supramolecular adducts

Energy Technology Data Exchange (ETDEWEB)

Cassimiro, Douglas L.; Kobelnik, Marcelo [Institute of Chemistry, Paulista State University, Av. Prof. Francisco Degni, s/n, 14800-900 Araraquara, Sao Paulo (Brazil); Ribeiro, Clovis A., E-mail: ribeiroc@iq.unesp.br [Institute of Chemistry, Paulista State University, Av. Prof. Francisco Degni, s/n, 14800-900 Araraquara, Sao Paulo (Brazil); Crespi, Marisa S.; Boralle, Nivaldo [Institute of Chemistry, Paulista State University, Av. Prof. Francisco Degni, s/n, 14800-900 Araraquara, Sao Paulo (Brazil)

2012-02-10

Highlights: Black-Right-Pointing-Pointer The thermal behavior of flunixin-meglumine, a potent NSAID, was investigated. Black-Right-Pointing-Pointer This supramolecular adduct self-assembled resulting in a polymer-like material. Black-Right-Pointing-Pointer The supramolecular polymer showed a high molecular weight around 290 {+-} 88 MDa. Black-Right-Pointing-Pointer NMR and FT-IR showed that hydrogen bonding can be responsible for the self-assembly. Black-Right-Pointing-Pointer The stability of the supramolecular polymer was also studied and presented here. - Abstract: Flunixin-meglumine, a potent non-steroidal anti-inflammatory drug (NSAID) and a cyclo-oxygenase inhibitor for Veterinary use, is a hydrogen-bonded supramolecular adduct. Two monotropically related crystalline modifications (Forms I and II) were observed for a flunixin-meglumine sample. During the melt of form I, flunixin-meglumine adducts self-assembled by hydrogen bonds involving the hydroxyl groups from meglumine, resulting in an amorphous rigid glassy supramolecular polymer, which showed a high molecular weight around 290 {+-} 88 MDa and a glass transition around 49.5 Degree-Sign C. Both the adduct and the resulting supramolecular polymer were characterized by differential scanning calorimetry (DSC), nuclear magnetic resonance spectroscopy (NMR), Fourier transform-infrared spectroscopy (FT-IR), and weight-average molecular weight determination by light scattering. The chemical stability and morphological changes of the depolymerization process were also investigated for the supramolecular polymer, by DSC and scanning electron microscopy (SEM), respectively.

Easily Processed Host-Guest Polymer Systems with High-Tg Characteristics (First-year Report)

Science.gov (United States)

2012-05-01

manner such that the effective electro- optical coefficient is maximized. Unfortunately, relaxation of the chromophore in the host polymer leads to...polished stainless steel facing plates (0.25 in thickness, McMaster ) and window molds cut from aluminum stock (1 mm thickness, McMaster ). Both facing...plasticization from the chromophore. Both chromophores resulted in substantial red-shifted absorption compared to a sample prepared in virgin PMMA. We expect

Sensitive and Specific Guest Recognition through Pyridinium-Modification in Spindle-Like Coordination Containers.

Science.gov (United States)

Bhuvaneswari, Nagarajan; Dai, Feng-Rong; Chen, Zhong-Ning

2018-05-02

An elaborately designed pyridinium-functionalized octanuclear zinc(II) coordination container 1-Zn was prepared through the self-assembly of Zn 2+ , p-tert-butylsulfonylcalix[4]arene, and pyridinium-functionalized angular flexible dicarboxylate linker (H 2 BrL1). The structure was determined by a single-crystal X-ray diffractometer. 1-Zn displays highly sensitive and specific recognition to 2-picolylamine as revealed by drastic blueshifts of the absorption and emission spectra, ascribed to the decrease of intramolecular charge transfer (ICT) character of the container and the occurrence of intermolecular charge transfer between the host and guest molecules. The intramolecular charge transfer plays a key role in the modulation of the electronic properties and is tunable through endo-encapsulation of specific guest molecules. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Neutral Guest Capture via Lewis Acid/Base Molecular Square Receptors. X-ray Crystal Structure of {Cyclobis[(cis-(dppp)Pt(4-ethynylpyridyl)(2))(cis- (PEt(3))(2)Pt)]Ag(2)}(+6)(phenazine)- ((-)OSO(2)CF(3))(6).

Science.gov (United States)

Whiteford, Jeffery A.; Stang, Peter J.; Huang, Songping D.

1998-10-19

Interaction of {cyclobis[(cis-(dppp)Pt(4-ethynylpyridyl)(2))(cis-(L)M)]Ag(2)}(+6)((-)OSO(2)CF(3))(6), where M = Pt(II) or Pd(II) and L = dppp or 2PEt(3), with pyridine, pyrazine, phenazine, or 4,4'-dipyridyl ketone results in coordination Lewis acid/base host-guest assemblies via the "pi-tweezer effect" and mono or bis neutral guest coordination. All host-guest complexes are air stable microcrystalline solids with decomposition points greater than 170 degrees C. The homometallic Pt(II) receptors are more stable than the heteroaromatic Pt(II)-Pd(II) receptors toward heteratom-containing aromatic guests. The X-ray crystal structure of the host-guest complex {cyclobis[(cis-(dppp)Pt(4-ethynylpyridyl)(2))(cis-(PEt(3))(2)Pt)]Ag(2)}(+6)(phenazine)((-)OSO(2)CF(3))(6) is reported. The crystals with the empirical formula C(62)H(68)AgF(9)N(3)O(9)P(4)Pt(2)S(3) are triclinic P&onemacr; with a = 12.3919(8) Å, b = 17.160(1) Å, c = 18.932(1) Å, alpha = 90.892(1) degrees, beta = 97.127(1) degrees, gamma = 89.969(1) degrees, and Z = 2.

Using Gas-Phase Guest-Host Chemistry to Probe the Structures of b Ions of Peptides

Science.gov (United States)

Somogyi, Árpád; Harrison, Alex G.; Paizs, Béla

2012-12-01

Middle-sized b n ( n ≥ 5) fragments of protonated peptides undergo selective complex formation with ammonia under experimental conditions typically used to probe hydrogen-deuterium exchange in Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Other usual peptide fragments like y, a, a*, etc., and small b n ( n ≤ 4) fragments do not form stable ammonia adducts. We propose that complex formation of b n ions with ammonia is characteristic to macrocyclic isomers of these fragments. Experiments on a protonated cyclic peptide and N-terminal acetylated peptides fully support this hypothesis; the protonated cyclic peptide does form ammonia adducts while linear b n ions of acetylated peptides do not undergo complexation. Density functional theory (DFT) calculations on the proton-bound dimers of all-Ala b 4 , b 5 , and b 7 ions and ammonia indicate that the ionizing proton initially located on the peptide fragment transfers to ammonia upon adduct formation. The ammonium ion is then solvated by N+-H…O H-bonds; this stabilization is much stronger for macrocyclic b n isomers due to the stable cage-like structure formed and entropy effects. The present study demonstrates that gas-phase guest-host chemistry can be used to selectively probe structural features (i.e., macrocyclic or linear) of fragments of protonated peptides. Stable ammonia adducts of b 9 , b 9 -A, and b 9 -2A of A8YA, and b 13 of A20YVFL are observed indicating that even these large b-type ions form macrocyclic structures.

Have the Guests Perceived Superior Value?

Directory of Open Access Journals (Sweden)

Levyda Levyda

2017-11-01

Full Text Available This research aimed to describe guests’ perceived value by using a multidimensional approach. From previous research, guests’ perceived value consisted of some functional value, emotional value, and social value. Based on guest experience, and functional value consisted of physical evidence, guest room, food and beverage, hotel staff, and price. This research was conducted in four-star hotels in Jakarta. The respondents were the guests who had stayed in four-star hotels. The number of the respondent was 405. The data were obtained by using self-administered questionnaires. This research shows that guests have not perceived superior value. Some of the values and the necessary efforts need to be improved.

Immobilization of ferrocene-modified SNAP-fusion proteins

NARCIS (Netherlands)

Wasserberg, D.; Uhlenheuer, D.; Neirynck, P.; Neirynck, Pauline; Cabanas Danés, Jordi; Schenkel, J.H.; Ravoo, B.J.; An, Q.; Huskens, Jurriaan; Milroy, L.G.; Brunsveld, Luc; Jonkheijm, Pascal

2013-01-01

The supramolecular assembly of proteins on surfaces has been investigated via the site-selective incorporation of a supramolecular moiety on proteins. To this end, fluorescent proteins have been site-selectively labeled with ferrocenes, as supramolecular guest moieties, via SNAP-tag technology. The

Host-free, yellow phosphorescent material in white organic light-emitting diodes

Energy Technology Data Exchange (ETDEWEB)

Lee, Meng-Ting; Chu, Miao-Tsai; Lin, Jin-Sheng; Tseng, Mei-Rurng, E-mail: osolomio.ac89g@nctu.edu.t [Material and Chemical Research Laboratories, Industrial Technology Research Institute (ITRI), Hsinchu, Taiwan 310 (China)

2010-11-10

A white organic light-emitting diode (WOLED) with a high power efficiency has been demonstrated by dispersing a host-free, yellow phosphorescent material in between double blue phosphorescent emitters. The device performance achieved a comparable value to that of using a complicated host-guest doping system to form the yellow emitter in WOLEDs. Based on this device concept as well as the molecular engineering of blue phosphorescent host material and light-extraction film, a WOLED with a power efficiency of 65 lm W{sup -1} at a practical brightness of 1000 cd m{sup -2} with Commission Internationale d'Echariage coordinates (CIE{sub x,y}) of (0.37, 0.47) was achieved. (fast track communication)

A systematic structural study of halogen bonding versus hydrogen bonding within competitive supramolecular systems

Directory of Open Access Journals (Sweden)

Christer B. Aakeröy

2015-09-01

Full Text Available As halogen bonds gain prevalence in supramolecular synthesis and materials chemistry, it has become necessary to examine more closely how such interactions compete with or complement hydrogen bonds whenever both are present within the same system. As hydrogen and halogen bonds have several fundamental features in common, it is often difficult to predict which will be the primary interaction in a supramolecular system, especially as they have comparable strength and geometric requirements. To address this challenge, a series of molecules containing both hydrogen- and halogen-bond donors were co-crystallized with various monotopic, ditopic symmetric and ditopic asymmetric acceptor molecules. The outcome of each reaction was examined using IR spectroscopy and, whenever possible, single-crystal X-ray diffraction. 24 crystal structures were obtained and subsequently analyzed, and the synthon preferences of the competing hydrogen- and halogen-bond donors were rationalized against a background of calculated molecular electrostatic potential values. It has been shown that readily accessible electrostatic potentials can offer useful practical guidelines for predicting the most likely primary synthons in these co-crystals as long as the potential differences are weighted appropriately.

A COOPERATIVE ASSISTANCE SYSTEM BETWEEN VEHICLES FOR ELDERLY DRIVERS

Directory of Open Access Journals (Sweden)

Naohisa HASHIMOTO

2009-01-01

Full Text Available This paper proposes a new concept of elderly driver assistance systems, which performs the assistance by cooperative driving between two vehicles, and describes some experiments with elderly drivers. The assistance consists of one vehicle driven by an elderly driver called a guest vehicle and the other driven by a assisting driver called a host vehicle, and the host vehicle assists or escorts the guest vehicle through the inter-vehicle communications. The functions of the systems installed on a single-seat electric vehicle are highly evaluated by subjects of elderly drivers in virtual streets on a test track.

Encoding complexity within supramolecular analogues of frustrated magnets

Science.gov (United States)

Cairns, Andrew B.; Cliffe, Matthew J.; Paddison, Joseph A. M.; Daisenberger, Dominik; Tucker, Matthew G.; Coudert, François-Xavier; Goodwin, Andrew L.

2016-05-01

The solid phases of gold(I) and/or silver(I) cyanides are supramolecular assemblies of inorganic polymer chains in which the key structural degrees of freedom—namely, the relative vertical shifts of neighbouring chains—are mathematically equivalent to the phase angles of rotating planar (‘XY’) spins. Here, we show how the supramolecular interactions between chains can be tuned to mimic different magnetic interactions. In this way, the structures of gold(I) and/or silver(I) cyanides reflect the phase behaviour of triangular XY magnets. Complex magnetic states predicted for this family of magnets—including collective spin-vortices of relevance to data storage applications—are realized in the structural chemistry of these cyanide polymers. Our results demonstrate how chemically simple inorganic materials can behave as structural analogues of otherwise inaccessible ‘toy’ spin models and also how the theoretical understanding of those models allows control over collective (‘emergent’) phenomena in supramolecular systems.

Supramolecular Pharmaceutical Sciences: A Novel Concept Combining Pharmaceutical Sciences and Supramolecular Chemistry with a Focus on Cyclodextrin-Based Supermolecules.

Science.gov (United States)

Higashi, Taishi; Iohara, Daisuke; Motoyama, Keiichi; Arima, Hidetoshi

2018-01-01

Supramolecular chemistry is an extremely useful and important domain for understanding pharmaceutical sciences because various physiological reactions and drug activities are based on supramolecular chemistry. However, it is not a major domain in the pharmaceutical field. In this review, we propose a new concept in pharmaceutical sciences termed "supramolecular pharmaceutical sciences," which combines pharmaceutical sciences and supramolecular chemistry. This concept could be useful for developing new ideas, methods, hypotheses, strategies, materials, and mechanisms in pharmaceutical sciences. Herein, we focus on cyclodextrin (CyD)-based supermolecules, because CyDs have been used not only as pharmaceutical excipients or active pharmaceutical ingredients but also as components of supermolecules.

Nanoparticle guests in lyotropic liquid crystals

Science.gov (United States)

Dölle, Sarah; Park, Ji Hyun; Schymura, Stefan; Jo, Hyeran; Scalia, Giusy; Lagerwall, Jan P. F.

In this chapter we discuss the benefits, peculiarities and main challenges related to nanoparticle templating in lyotropic liquid crystals. We first give a brief bird's-eye view of the field, discussing different nanoparticles as well as different lyotropic hosts that have been explored, but then quickly focus on the dispersion of carbon nanotubes in surfactant-based lyotropic nematic phases. We discuss in some detail how the transfer of orientational order from liquid crystal host to nanoparticle guest can be verified and which degree of ordering can be expected, as well as the importance of choosing the right surfactant and its concentration for the stability of the nanoparticle suspension. We introduce a method for dispersing nanoparticles with an absolute minimum of stabilizing surfactant, based on dispersion below the Krafft temperature, and we discuss the peculiar phenomenon of filament formation in lyotropic nematic phases with a sufficient concentration of well-dispersed carbon nanotubes. Finally, we describe how the total surfactant concentration in micellar nematics can be greatly reduced by combining cat- and anionic surfactants, and we discuss how nanotubes can help in inducing the liquid crystal phase close to the isotropic-nematic boundary.

Diversity oriented high-throughput screening of 1,3,4-oxadiazole modified chlorophenylureas and halogenobenzamides by HPLC with peptidomimetic calixarene-bonded stationary phases.

Science.gov (United States)

Bazylak, Grzegorz; Malak, Anna; Ali, Imran; Borowiak, Teresa; Dutkiewicz, Grzegorz

2008-06-01

Retention profiles in series of the neutral and highly hydrophobic 1,3,4-oxadiazoles containing chlorophenylurea and halogenobenzamide moiety and indicating analgesic activity were determined in the isocratic standard- and narrow-bore HPLC systems employing, respectively, various octadecylsilica and different calixarene bonded stationary phases. When acetonitrile - 2.65 mM phosphoric acid (55 : 45, %, v/v), pH* 3.25, mobile phase was applied retention of these compounds increased with decline of their overall hydrophobicity according to the general preference of more polar compounds by calixarene cavity in time of its non-specific host-guest supramolecular interactions with halogenated substances. The size of calixarene nanocavity and its upper-rim substitution did not change the observed retention order, resolution and selectivity of separation for oxadiazoles. Compared to the retention on the non-end-capped and the highly-end-capped octadecylsilica HPLC column a most improved separation of some regioisomers of halogenated 1,3,4-oxadiazoles were observed on both used calixarene-type HPLC supports. In addition, preliminary data on the self-assembled supramolecular crystal structure of exemplary 1,3,4-oxadiazolchlorophenylurea with cis-elongated conformation was reported and formation of the monovalent inclusion host-guest complexes between 1,3,4-oxadiazoles and each calixarene-type stationary phase was studied with molecular modelling MM+ and AM1 methods. The structural, isomeric and energetic factors leading to the hydrogen bond stabilized inclusion complexes between these species were considered and used for explanation of observed retention sequence and selectivity of 1,3,4-oxadiazoles separation in applied calixarene-based HPLC systems. All these data would be useful in future development of optimized procedures enabling encapsulation of 1,3,4-oxadiazolurea-type drugs with calixarenes.

Beta-Cyclodextrin Duplexes That Are Connected through Two Disulfide Bonds: Potent Hosts for the Complexation of Organic Molecules

Czech Academy of Sciences Publication Activity Database

Grishina, Anastasia; Stanchev, Stancho; Kumprecht, Lukáš; Buděšínský, Miloš; Pojarová, Michaela; Dušek, Michal; Rumlová, Michaela; Křížová, Ivana; Rulíšek, Lubomír; Kraus, Tomáš

2012-01-01

Roč. 18, č. 39 (2012), s. 12292-12304 ISSN 0947-6539 Grant - others:AV ČR(CZ) M200550904 Institutional support: RVO:61388963 ; RVO:68378271 Keywords : cucurbiturils * cyclodextrins * duplexes * host-guest systems * sulfur Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.831, year: 2012

Supramolecular assembly/reassembly processes: molecular motors and dynamers operating at surfaces.

Science.gov (United States)

Ciesielski, Artur; Samorì, Paolo

2011-04-01

Among the many significant advances within the field of supramolecular chemistry over the past decades, the development of the so-called "dynamers" features a direct relevance to materials science. Defined as "combinatorial dynamic polymers", dynamers are constitutional dynamic systems and materials resulting from the application of the principles of supramolecular chemistry to polymer science. Like supramolecular materials in general, dynamers are reversible dynamic multifunctional architectures, capable of modifying their constitution by exchanging, recombining, incorporating components. They may exhibit a variety of novel properties and behave as adaptive materials. In this review we focus on the design of responsive switchable monolayers, i.e. monolayers capable to undergo significant changes in their physical or chemical properties as a result of external stimuli. Scanning tunneling microscopy studies provide direct evidence with a sub-nanometre resolution, on the formation and dynamic response of these self-assembled systems featuring controlled geometries and properties.

Functional supramolecular polymers for biomedical applications.

Science.gov (United States)

Dong, Ruijiao; Zhou, Yongfeng; Huang, Xiaohua; Zhu, Xinyuan; Lu, Yunfeng; Shen, Jian

2015-01-21

As a novel class of dynamic and non-covalent polymers, supramolecular polymers not only display specific structural and physicochemical properties, but also have the ability to undergo reversible changes of structure, shape, and function in response to diverse external stimuli, making them promising candidates for widespread applications ranging from academic research to industrial fields. By an elegant combination of dynamic/reversible structures with exceptional functions, functional supramolecular polymers are attracting increasing attention in various fields. In particular, functional supramolecular polymers offer several unique advantages, including inherent degradable polymer backbones, smart responsiveness to various biological stimuli, and the ease for the incorporation of multiple biofunctionalities (e.g., targeting and bioactivity), thereby showing great potential for a wide range of applications in the biomedical field. In this Review, the trends and representative achievements in the design and synthesis of supramolecular polymers with specific functions are summarized, as well as their wide-ranging biomedical applications such as drug delivery, gene transfection, protein delivery, bio-imaging and diagnosis, tissue engineering, and biomimetic chemistry. These achievements further inspire persistent efforts in an emerging interdisciplin-ary research area of supramolecular chemistry, polymer science, material science, biomedical engineering, and nanotechnology. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen bonded supramolecular materials

CERN Document Server

Li, Zhan-Ting

2015-01-01

This book is an up-to-date text covering topics in utilizing hydrogen bonding for constructing functional architectures and supramolecular materials. The first chapter addresses the control of photo-induced electron and energy transfer. The second chapter summarizes the formation of nano-porous materials. The following two chapters introduce self-assembled gels, many of which exhibit unique functions. Other chapters cover the advances in supramolecular liquid crystals and the versatility of hydrogen bonding in tuning/improving the properties and performance of materials. This book is designed

An enhanced cerium(IV)-rhodamine 6G chemiluminescence system using guest-host interactions in a lab-on-a-chip platform for estimating the total phenolic content in food samples.

Science.gov (United States)

Al Haddabi, Buthaina; Al Lawati, Haider A J; Suliman, FakhrEldin O

2016-04-01

Two chemiluminescence-microfluidic (CL-MF) systems, e.g., Ce(IV)-rhodamine B (RB) and Ce(IV)-rhodamine 6G (R6G), for the determination of the total phenolic content in teas and some sweeteners were evaluated. The results indicated that the Ce(IV)-R6G system was more sensitive in comparison to the Ce(IV)-RB CL system. Therefore, a simple (CL-MF) method based on the CL of Ce(IV)-R6G was developed, and the sensitivity, selectivity and stability of this system were evaluated. Selected phenolic compounds (PCs), such as quercetin (QRC), catechin (CAT), rutin (RUT), gallic acid (GA), caffeic acid (CA) and syringic acid (SA), produced analytically useful chemiluminescence signals with low detection limits ranging from 0.35 nmol L(-1) for QRC to 11.31 nmol L(-1) for SA. The mixing sequence and the chip design were crucial, as the sensitivity and reproducibility could be substantially affected by these two factors. In addition, the anionic surfactant (i.e., sodium dodecyl sulfate (SDS)) can significantly enhance the CL signal intensity by as much as 300% for the QRC solution. Spectroscopic studies indicated that the enhancement was due to a strong guest-host interaction between the cationic R6G molecules and the anionic amphiphilic environment. Other parameters that could affect the CL intensities of the PCs were carefully optimized. Finally, the method was successfully applied to tea and sweetener samples. Six different tea samples exhibited total phenolic/antioxidant levels from 7.32 to 13.5 g per 100g of sample with respect to GA. Four different sweetener samples were also analyzed and exhibited total phenolic/antioxidant levels from 500.9 to 3422.9 mg kg(-1) with respect to GA. The method was selective, rapid and sensitive when used to estimate the total phenolic/antioxidant level, and the results were in good agreement with those reported for honey and tea samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Supramolecular Systems and Chemical Reactions in Single-Molecule Break Junctions.

Science.gov (United States)

Li, Xiaohui; Hu, Duan; Tan, Zhibing; Bai, Jie; Xiao, Zongyuan; Yang, Yang; Shi, Jia; Hong, Wenjing

2017-04-01

The major challenges of molecular electronics are the understanding and manipulation of the electron transport through the single-molecule junction. With the single-molecule break junction techniques, including scanning tunneling microscope break junction technique and mechanically controllable break junction technique, the charge transport through various single-molecule and supramolecular junctions has been studied during the dynamic fabrication and continuous characterization of molecular junctions. This review starts from the charge transport characterization of supramolecular junctions through a variety of noncovalent interactions, such as hydrogen bond, π-π interaction, and electrostatic force. We further review the recent progress in constructing highly conductive molecular junctions via chemical reactions, the response of molecular junctions to external stimuli, as well as the application of break junction techniques in controlling and monitoring chemical reactions in situ. We suggest that beyond the measurement of single molecular conductance, the single-molecule break junction techniques provide a promising access to study molecular assembly and chemical reactions at the single-molecule scale.

Critical guest concentration and complete tuning pattern appearing in the binary clathrate hydrates

Energy Technology Data Exchange (ETDEWEB)

Cha, J.H.; Lee, H. [Korea Advanced Inst. of Science and Technology, Yuseong-gu, Daejeon (Korea, Republic of). Dept. of Chemical and Biomolecular Engineering; Kim, D.Y. [SK Engineering and Construction, Jongno-gu, Seoul (Korea, Republic of); Park, J. [Hanwha Chemical R and D Center, Yuseong-gu, Daejeon (Korea, Republic of); Lee, J.W. [Kongju National Univ., Cheonan, Chungnam (Korea, Republic of); Ripmeester, J.A. [National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences

2008-07-01

Clathrate hydrates, or gas hydrates, are stabilized by van der Waals interaction between a guest molecule and a host framework. Because of their property, they are a potential resource in the exploitation of natural gas hydrates, as a material for the sequestration of carbon dioxide (CO{sub 2}), as a means of storage and transportation of natural gas, as well as hydrogen storage. Clathrate hydrate research can be divided into two categories that emphasize either macroscopic or microscopic approaches. However, these two approaches need to be closely linked for a better understanding of the structures and processes involving both natural phenomena and hydrates for industrial processes. Details on the molecular scale that concern the less usual properties of clathrate hydrates remain unknown. This paper presented the results of a study that reported on the existence of a critical guest concentration (CGC) and established the complete tuning pattern that occurred in the binary hydrates, including water-soluble hydrate formers (promoters) and water-insoluble guests. The paper presented the experimental procedures, including formation of the methane (CH{sub 4}) and tetrahydrofuran (THF) binary hydrate; a schematic diagram of the experimental apparatus; and formation of the CH{sub 4} and t-BuNH{sub 2} binary hydrate. Nuclear magnetic resonance (NMR) spectroscopic measurements and thermodynamic measurements were also presented. It was concluded that the CGC value appeared to primarily depend on the chemical nature of a liquid guest component participating in the binary hydrate formation. 10 refs., 2 tabs., 9 figs.

Controlling the photochemical reaction of an azastilbene derivative in water using a water-soluble pillar[6]arene.

Science.gov (United States)

Xia, Danyu; Wang, Pi; Shi, Bingbing

2017-09-20

Photochemistry plays an important role in our lives. It has also been a common tool in the laboratory to construct complicated systems from small molecules. Supramolecular chemistry provides an opportunity to solve some of the problems in controlling photochemical reactions via non-covalent interactions. By using confining media and weak interactions between the medium and the reactant molecule, the excited state behavior of molecules has been successfully manipulated. Pillararenes, a new class of macrocyclic hosts, have rarely been used in the field of photochemical investigations, such as the controlling of photo-induced reactions. Herein, we explore a synthetic macrocyclic host, a water-soluble pillar[6]arene, as a controlling tool to manipulate the photo-induced reactions (hydration) in water. A host-guest system in water based on a water-soluble pillar[6]arene and an azastilbene derivative, (E)-4,4'-dimethyl-4,4'-diazoniastilbene diiodide, has been constructed. Then this water-soluble pillar[6]arene was successfully employed to control the photohydration of the azastilbene derivative in water as a "protective agent".

Effects of electron blocking and hole trapping of the red guest emitter materials on hybrid white organic light emitting diodes

International Nuclear Information System (INIS)

Hong, Lin-Ann; Vu, Hoang-Tuan; Juang, Fuh-Shyang; Lai, Yun-Jr; Yeh, Pei-Hsun; Tsai, Yu-Sheng

2013-01-01

Hybrid white organic light emitting diodes (HWOLEDs) with fluorescence and phosphorescence hybrid structures are studied in this work. HWOLEDs were fabricated with blue/red emitting layers: fluorescent host material doped with sky blue material, and bipolar phosphorescent host emitting material doped with red dopant material. An electron blocking layer is applied that provides hole red guest emitter hole trapping effects, increases the charge carrier injection quantity into the emitting layers and controls the recombination zone (RZ) that helps balance the device color. Spacer layers were also inserted to expand the RZ, increase efficiency and reduce energy quenching along with roll-off effects. The resulting high efficiency warm white OLED device has the lower highest occupied molecule orbital level red guest material, current efficiency of 15.9 cd/A at current density of 20 mA/cm 2 , and Commission Internationale de L'Eclairage coordinates of (0.34, 0.39)

Effects of electron blocking and hole trapping of the red guest emitter materials on hybrid white organic light emitting diodes

Energy Technology Data Exchange (ETDEWEB)

Hong, Lin-Ann; Vu, Hoang-Tuan [National Formosa University, Institute of Electro-Optical and Materials Science, Huwei, Yunlin County, Taiwan (China); Juang, Fuh-Shyang, E-mail: fsjuang@seed.net.tw [National Formosa University, Institute of Electro-Optical and Materials Science, Huwei, Yunlin County, Taiwan (China); Lai, Yun-Jr [National Formosa University, Institute of Electro-Optical and Materials Science, Huwei, Yunlin County, Taiwan (China); Yeh, Pei-Hsun [Raystar Optronics, Inc., 5F No. 25, Keya Rd. Daya Township, Taichung County, Taiwan (China); Tsai, Yu-Sheng [National Formosa University, Institute of Electro-Optical and Materials Science, Huwei, Yunlin County, Taiwan (China)

2013-10-01

Hybrid white organic light emitting diodes (HWOLEDs) with fluorescence and phosphorescence hybrid structures are studied in this work. HWOLEDs were fabricated with blue/red emitting layers: fluorescent host material doped with sky blue material, and bipolar phosphorescent host emitting material doped with red dopant material. An electron blocking layer is applied that provides hole red guest emitter hole trapping effects, increases the charge carrier injection quantity into the emitting layers and controls the recombination zone (RZ) that helps balance the device color. Spacer layers were also inserted to expand the RZ, increase efficiency and reduce energy quenching along with roll-off effects. The resulting high efficiency warm white OLED device has the lower highest occupied molecule orbital level red guest material, current efficiency of 15.9 cd/A at current density of 20 mA/cm{sup 2}, and Commission Internationale de L'Eclairage coordinates of (0.34, 0.39)

Art, auto-mechanics, and supramolecular chemistry. A merging of hobbies and career.

Science.gov (United States)

Anslyn, Eric V

2016-01-01

While the strict definition of supramolecular chemistry is "chemistry beyond the molecule", meaning having a focus on non-covalent interactions, the field is primarily associated with the creation of synthetic receptors and self-assembly. For synthetic ease, the receptors and assemblies routinely possess a high degree of symmetry, which lends them an aspect of aesthetic beauty. Pictures of electron orbitals similarly can be seen as akin to works of art. This similarity was an early draw for me to the fields of supramolecular chemistry and molecular orbital theory, because I grew up in a household filled with art. In addition to art, my childhood was filled with repairing and constructing mechanical entities, such as internal combustion motors, where many components work together to achieve a function. Analogously, the field of supramolecular chemistry creates systems of high complexity that achieve functions or perform tasks. Therefore, in retrospect a career in supramolecular chemistry appears to be simply an extension of childhood hobbies involving art and auto-mechanics.

Supramolecular materials based on hydrogen-bonded polymers

NARCIS (Netherlands)

ten Brinke, Gerrit; Ruokolainen, Janne; Ikkala, Olli; Binder, W

2007-01-01

Combining supramolecular principles with block copolymer self-assembly offers unique possibilities to create materials with responsive and/or tunable properties. The present chapter focuses on supramolecular materials based on hydrogen bonding and (block co-) polymers. Several cases will be

Supramolecular coordination polymer formed from artificial light-harvesting dendrimer.

Science.gov (United States)

Lee, Hosoowi; Jeong, Young-Hwan; Kim, Joo-Ho; Kim, Inhye; Lee, Eunji; Jang, Woo-Dong

2015-09-30

We report the formation of supramolecular coordination polymers formed from multiporphyrin dendrimers (PZnPM; M = FB or Cu), composed of the focal freebase porphyrin (PFB) or cupper porphyrin (PCu) with eight zinc porphyrin (PZn) wings, and multipyridyl porphyrins (PyPM; M = FB or Cu), PFB or PCu with eight pyridyl groups, through multiple axial coordination interactions of pyridyl groups to PZns. UV-vis absorption spectra were recorded upon titration of PyPFB to PZnPFB. Differential spectra, obtained by subtracting the absorption of PZnPFB without guest addition as well as the absorption of PyPFB, exhibited clear isosbestic points with saturation binding at 1 equiv addition of PyPFB to PZnPFB. Job's plot analysis also indicated 1:1 stoichiometry for the saturation binding. The apparent association constant between PZnPFB and PyPFB (2.91 × 10(6) M(-1)), estimated by isothermal titration calorimetry, was high enough for fibrous assemblies to form at micromolar concentrations. The formation of a fibrous assembly from PZnPFB and PyPFB was visualized by atomic force microscopy and transmission electron microscopy (TEM). When a 1:1 mixture solution of PZnPFB and PyPFB (20 μM) in toluene was cast onto mica, fibrous assemblies with regular height (ca. 2 nm) were observed. TEM images obtained from 1:1 mixture solution of PZnPFB and PyPFB (0.1 wt %) in toluene clearly showed the formation of nanofibers with a regular diameter of ca. 6 nm. Fluorescence emission measurement of PZnPM indicated efficient intramolecular energy transfer from PZn to the focal PFB or PCu. By the formation of supramolecular coordination polymers, the intramolecular energy transfer changed to intermolecular energy transfer from PZnPM to PyPM. When the nonfluorescent PyPCu was titrated to fluorescent PZnPFB, fluorescence emission from the focal PFB was gradually decreased. By the titration of fluorescent PyPFB to nonfluorescent PZnPCu, fluorescence emission from PFB in PyPFB was gradually increased

Distribution of metal and adsorbed guest species in zeolites

Energy Technology Data Exchange (ETDEWEB)

Chmelka, B.F.

1989-12-01

Because of their high internal surface areas and molecular-size cavity dimensions, zeolites are used widely as catalysts, shape- selective supports, or adsorbents in a variety of important chemical processes. For metal-catalyzed reactions, active metal species must be dispersed to sites within the zeolite pores that are accessible to diffusing reactant molecules. The distribution of the metal, together with transport and adsorption of reactant molecules in zeolite powders, are crucial to ultimate catalyst performance. The nature of the metal or adsorbed guest distribution is known, however, to be dramatically dependent upon preparatory conditions. Our objective is to understand, at the molecular level, how preparatory treatments influence the distribution of guest species in zeolites, in order that macroscopic adsorption and reaction properties of these materials may be better understood. The sensitivity of xenon to its adsorption environment makes {sup 129}Xe NMR spectroscopy an important diagnostic probe of metal clustering and adsorbate distribution processes in zeolites. The utility of {sup 129}Xe NMR depends on the mobility of the xenon atoms within the zeolite-guest system, together with the length scale of the sample heterogeneity being studied. In large pore zeolites containing dispersed guest species, such as Pt--NaY, {sup 129}Xe NMR is insensitive to fine structural details at room temperature.

Distribution of metal and adsorbed guest species in zeolites

International Nuclear Information System (INIS)

Chmelka, B.F.

1989-12-01

Because of their high internal surface areas and molecular-size cavity dimensions, zeolites are used widely as catalysts, shape- selective supports, or adsorbents in a variety of important chemical processes. For metal-catalyzed reactions, active metal species must be dispersed to sites within the zeolite pores that are accessible to diffusing reactant molecules. The distribution of the metal, together with transport and adsorption of reactant molecules in zeolite powders, are crucial to ultimate catalyst performance. The nature of the metal or adsorbed guest distribution is known, however, to be dramatically dependent upon preparatory conditions. Our objective is to understand, at the molecular level, how preparatory treatments influence the distribution of guest species in zeolites, in order that macroscopic adsorption and reaction properties of these materials may be better understood. The sensitivity of xenon to its adsorption environment makes 129 Xe NMR spectroscopy an important diagnostic probe of metal clustering and adsorbate distribution processes in zeolites. The utility of 129 Xe NMR depends on the mobility of the xenon atoms within the zeolite-guest system, together with the length scale of the sample heterogeneity being studied. In large pore zeolites containing dispersed guest species, such as Pt--NaY, 129 Xe NMR is insensitive to fine structural details at room temperature

Osprey: Operating system for predictable clouds

NARCIS (Netherlands)

Sacha, Jan; Napper, Jeff; Mullender, Sape J.; McKie, Jim

2012-01-01

Cloud computing is currently based on hardware virtualization wherein a host operating system provides a virtual machine interface nearly identical to that of physical hardware to guest operating systems. Full transparency allows backward compatibility with legacy software but introduces

Usability of Security Management:Defining the Permissions of Guests

Science.gov (United States)

Johnson, Matthew; Stajano, Frank

Within the scenario of a Smart Home, we discuss the issues involved in allowing limited interaction with the environment for unidentified principals, or guests. The challenges include identifying and authenticating guests on one hand and delegating authorization to them on the other. While the technical mechanisms for doing so in generic distributed systems have been around for decades, existing solutions are in general not applicable to the smart home because they are too complex to manage. We focus on providing both security and usability; we therefore seek simple and easy to understand approaches that can be used by a normal computer-illiterate home owner, not just by a trained system administrator. This position paper describes ongoing research and does not claim to have all the answers.

Enhanced intermolecular forces in supramolecular polymer nanocomposites

Directory of Open Access Journals (Sweden)

F. Lin

2017-09-01

Full Text Available Ureido-pyrimidone (Upy can dimerize in a self-complementary array of quadruple hydrogen bonds. In this paper, supramolecular polymer composites were prepared by blending Upy functionalized nanosilica with Upy end-capped polycarbonatediol. Surface characteristics of Upy functionalized nanosilica and influences of supramolecular forces on interfacial binding were researched. Fourier transform infrared spectroscopy (FTIR, Nuclear magnetic resonance (NMR and Gel permeation chromatography (GPC were used to characterize the synthesized molecules. Grafting ratio of Upy segments on the surface of nanosilica was analysed by Thermogravimetic analysis (TGA. Hydrophobicity and morphology of Upy modified nanosilica were analysed by Contact angle tester and Scanning electron microscope (SEM. Furthermore, dynamic thermo mechanical properties, mechanical properties and distribution of nanosilica in supramolecular polymer composites were also researched. Compared with the matrix resin, tensile stress and young's modulus of supramolecular polymer composites containing 5 wt% modified nanosilica were increased by 292 and 198% respectively.

Stepwise observation and quantification and mixed matrix membrane separation of CO2 within a hydroxy-decorated porous host.

Science.gov (United States)

Morris, Christopher G; Jacques, Nicholas M; Godfrey, Harry G W; Mitra, Tamoghna; Fritsch, Detlev; Lu, Zhenzhong; Murray, Claire A; Potter, Jonathan; Cobb, Tom M; Yuan, Fajin; Tang, Chiu C; Yang, Sihai; Schröder, Martin

2017-04-01

The identification of preferred binding domains within a host structure provides important insights into the function of materials. State-of-the-art reports mostly focus on crystallographic studies of empty and single component guest-loaded host structures to determine the location of guests. However, measurements of material properties ( e.g. , adsorption and breakthrough of substrates) are usually performed for a wide range of pressure (guest coverage) and/or using multi-component gas mixtures. Here we report the development of a multifunctional gas dosing system for use in X-ray powder diffraction studies on Beamline I11 at Diamond Light Source. This facility is fully automated and enables in situ crystallographic studies of host structures under (i) unlimited target gas loadings and (ii) loading of multi-component gas mixtures. A proof-of-concept study was conducted on a hydroxyl-decorated porous material MFM-300(V III ) under (i) five different CO 2 pressures covering the isotherm range and (ii) the loading of equimolar mixtures of CO 2 /N 2 . The study has successfully captured the structural dynamics underpinning CO 2 uptake as a function of surface coverage. Moreover, MFM-300(V III ) was incorporated in a mixed matrix membrane (MMM) with PIM-1 in order to evaluate the CO 2 /N 2 separation potential of this material. Gas permeation measurements on the MMM show a great improvement over the bare PIM-1 polymer for CO 2 /N 2 separation based on the ideal selectivity.

The metaphor of nurse as guest with ethical implications for nursing and healthcare.

Science.gov (United States)

Milton, Constance L

2005-10-01

Current healthcare advertising and customer relations terminology acknowledge that healthcare providers, including nurses, are to act as hosts for persons who enter into healthcare agencies and institutions. Indeed, much has been written aligning nursing and other healthcare services with consumer-oriented roles of the hospitality service industry commonly associated with hotels and restaurants. From a human becoming perspective, this article discusses possible ethical, administrative, and practice implications of nurses acting as guests entering into the lives of those we serve.

TOPICAL REVIEW: Metallo-supramolecular modules as a paradigm for materials science

Directory of Open Access Journals (Sweden)

Dirk G Kurth

2008-01-01

Full Text Available Metal ion coordination in discrete or extended metallo-supramolecular assemblies offers ample opportunity to fabricate and study devices and materials that are equally important for fundamental research and new technologies. Metal ions embedded in a specific ligand field offer diverse thermodynamic, kinetic, chemical, physical and structural properties that make these systems promising candidates for active components in functional materials. A key challenge is to improve and develop methodologies for placing these active modules in suitable device architectures, such as thin films or mesophases. This review highlights recent developments in extended, polymeric metallo-supramolecular systems and discrete polyoxometalates with an emphasis on materials science.

A Supramolecular Approach to Medicinal Chemistry: Medicine Beyond the Molecule

Science.gov (United States)

Smith, David K.

2005-03-01

This article focuses on the essential roles played by intermolecular forces in mediating the interactions between chemical molecules and biological systems. Intermolecular forces constitute a key topic in chemistry programs, yet can sometimes seem disconnected from real-life applications. However, by taking a "supramolecular" view of medicinal chemistry and focusing on interactions between molecules, it is possible to come to a deeper understanding of recent developments in medicine. This allows us to gain a real insight into the interface between biology and chemistry—an interdisciplinary area that is crucial for the development of modern medicinal products. This article emphasizes a conceptual view of medicinal chemistry, which has important implications for the future, as the supramolecular approach to medicinal-chemistry products outlined here is rapidly allowing nanotechnology to converge with medicine. In particular, this article discusses recent developments including the rational design of drugs such as Relenza and Tamiflu, the mode of action of vancomycin, and the mechanism by which bacteria develop resistance, drug delivery using cyclodextrins, and the importance of supramolecular chemistry in understanding protein aggregation diseases such as Alzheimer's and Creutzfield Jacob. The article also indicates how taking a supramolecular approach will enable the development of new nanoscale medicines.

Solvent induced supramolecular anisotropy in molecular gels

Energy Technology Data Exchange (ETDEWEB)

Rogers, Michael A., E-mail: mroger09@uoguelph.ca [Department of Food Science, University of Guelph, Guelph, Ontario, N3C3X9 (Canada); Corradini, Maria G. [Department of Food Science, University of Massachusetts Amherst, Amherst, MA, 01003 (United States); Emge, Thomas [Department of Chemistry and Biochemistry, Rutgers University, New Brunswick, NJ, 08901 (United States)

2017-06-15

Herein is the first report of solvent induced anisotropy in 12-hydroxystearic acid self-assembled fibrillar networks. Increasing the chain length of polar solvent, such as nitriles and ketones, tailored the anisotropy of the fibrillar aggregates. 12HSA molecular gels, comprised of alkanes, exhibited an isotropic fibrillar network irrespective of the alkane chain length. In polar solvents, anisotropy, observed using 2D powder x-ray diffraction profiles, is correlated to a fibrillar supramolecular morphologies in long chain nitriles and ketones while sphereulitic crystals are correlated to x-ray diffraction patterns with an isotropic scatter intensity in short chain ketones and nitriles. These changes directly modify the final physical properties of the gels. - Highlights: • 12-HSA self-assembles into crystalline supramolecular morphologies depending on the solvent. • Alkanes, short chain nitriles and ketones led to 12-HSA displaying supramolecular isotropy. • In long chain nitriles and ketones, 12-HSA displays supramolecular anisotropy.

Solvent induced supramolecular anisotropy in molecular gels

International Nuclear Information System (INIS)

Rogers, Michael A.; Corradini, Maria G.; Emge, Thomas

2017-01-01

Herein is the first report of solvent induced anisotropy in 12-hydroxystearic acid self-assembled fibrillar networks. Increasing the chain length of polar solvent, such as nitriles and ketones, tailored the anisotropy of the fibrillar aggregates. 12HSA molecular gels, comprised of alkanes, exhibited an isotropic fibrillar network irrespective of the alkane chain length. In polar solvents, anisotropy, observed using 2D powder x-ray diffraction profiles, is correlated to a fibrillar supramolecular morphologies in long chain nitriles and ketones while sphereulitic crystals are correlated to x-ray diffraction patterns with an isotropic scatter intensity in short chain ketones and nitriles. These changes directly modify the final physical properties of the gels. - Highlights: • 12-HSA self-assembles into crystalline supramolecular morphologies depending on the solvent. • Alkanes, short chain nitriles and ketones led to 12-HSA displaying supramolecular isotropy. • In long chain nitriles and ketones, 12-HSA displays supramolecular anisotropy.

Art, auto-mechanics, and supramolecular chemistry. A merging of hobbies and career

Directory of Open Access Journals (Sweden)

Eric V. Anslyn

2016-02-01

Full Text Available While the strict definition of supramolecular chemistry is “chemistry beyond the molecule”, meaning having a focus on non-covalent interactions, the field is primarily associated with the creation of synthetic receptors and self-assembly. For synthetic ease, the receptors and assemblies routinely possess a high degree of symmetry, which lends them an aspect of aesthetic beauty. Pictures of electron orbitals similarly can be seen as akin to works of art. This similarity was an early draw for me to the fields of supramolecular chemistry and molecular orbital theory, because I grew up in a household filled with art. In addition to art, my childhood was filled with repairing and constructing mechanical entities, such as internal combustion motors, where many components work together to achieve a function. Analogously, the field of supramolecular chemistry creates systems of high complexity that achieve functions or perform tasks. Therefore, in retrospect a career in supramolecular chemistry appears to be simply an extension of childhood hobbies involving art and auto-mechanics.

Fulltext PDF

Indian Academy of Sciences (India)

0001195

molybdate solution leads to the formation of ion pair compounds having supramolecular framework structures. These organic amines are trapped as guest or as part of the framework making the present system ... Evaluation of micellar properties of sodium dodecylbenzene ... In addition, the direct pseudo multicomponent.

Guest driven structural transformation studies of a luminescent metal ...

Indian Academy of Sciences (India)

at room temperature often render MOFs which gener- ally encapsulate low boiling solvents as free guests in the pores. These MOFs generally exhibit flexible char- acter because they often lose those trapped guests upon air drying of the MOFs crystals and undergo struc- tural variations, often termed as guest induced ...

Incorporation and Effects of Nanoparticles in a Supramolecular Polymer

Science.gov (United States)

2016-05-01

polymerizations and main-chain supramolecular polymers . Macromolecules. 2009;42:6823–6835. 17. Wojtecki RJ, Meador MA, Rowan SJ. Using the dynamic bond...ARL-TR-7687 ● MAY 2016 US Army Research Laboratory Incorporation and Effects of Nanoparticles in a Supramolecular Polymer by...Laboratory Incorporation and Effects of Nanoparticles in a Supramolecular Polymer by Alice M Savage Oak Ridge Institute of Science and Education

Construction of diverse supramolecular assemblies of dimetal ...

Indian Academy of Sciences (India)

presence or absence of the lattice water molecules are the keys to forming the diverse supramolecular assem- blies. In 1 and 3, ... Supramolecular; hydrogen bonding; flexible ligand; dicarboxylates. 1. ... The reaction mixture was stirred for another 3 to 4 hours at room ..... Funding for this work was provided by IISER, Mohali.

Supracolloidal Architectures Self-Assembled in Microdroplets.

Science.gov (United States)

Xu, Xuejiao; Tian, Feng; Liu, Xin; Parker, Richard M; Lan, Yang; Wu, Yuchao; Yu, Ziyi; Scherman, Oren A; Abell, Chris

2015-10-26

We demonstrate a novel method for the formation of a library of structured colloidal assemblies by exploiting the supramolecular heteroternary host-guest interaction between cucurbit[8]uril (CB[8]) and methyl viologen- and naphthalene-functionalised particles. The approach is dependent upon compartmentalisation in microdroplets generated by a microfluidic platform. Though the distribution of colloidal particles encapsulated within each microdroplet followed a Poisson distribution, tuning the concentration of the initial colloidal particle suspensions provided some level of control over the structure of the formed colloidal assemblies. This ability to direct the assembly of complementarily-functionalised colloids through a supramolecular interaction, without the need for complex modification of the colloidal surface or external stimuli, presents an exciting new approach towards the design of structured colloidal materials with the potential to produce many challenging structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microfluidic Droplet-Facilitated Hierarchical Assembly for Dual Cargo Loading and Synergistic Delivery.

Science.gov (United States)

Yu, Ziyi; Zheng, Yu; Parker, Richard M; Lan, Yang; Wu, Yuchao; Coulston, Roger J; Zhang, Jing; Scherman, Oren A; Abell, Chris

2016-04-06

Bottom-up hierarchical assembly has emerged as an elaborate and energy-efficient strategy for the fabrication of smart materials. Herein, we present a hierarchical assembly process, whereby linear amphiphilic block copolymers are self-assembled into micelles, which in turn are accommodated at the interface of microfluidic droplets via cucurbit[8]uril-mediated host-guest chemistry to form supramolecular microcapsules. The monodisperse microcapsules can be used for simultaneous carriage of both organic (Nile Red) and aqueous-soluble (fluorescein isothiocyanate-dextran) cargo. Furthermore, the well-defined compartmentalized structure benefits from the dynamic nature of the supramolecular interaction and offers synergistic delivery of cargos with triggered release or through photocontrolled porosity. This demonstration of premeditated hierarchical assembly, where interactions from the molecular to microscale are designed, illustrates the power of this route toward accessing the next generation of functional materials and encapsulation strategies.

Amides Do Not Always Work: Observation of Guest Binding in an Amide-Functionalized Porous Metal-Organic Framework.

Science.gov (United States)

Benson, Oguarabau; da Silva, Ivan; Argent, Stephen P; Cabot, Rafel; Savage, Mathew; Godfrey, Harry G W; Yan, Yong; Parker, Stewart F; Manuel, Pascal; Lennox, Matthew J; Mitra, Tamoghna; Easun, Timothy L; Lewis, William; Blake, Alexander J; Besley, Elena; Yang, Sihai; Schröder, Martin

2016-11-16

An amide-functionalized metal organic framework (MOF) material, MFM-136, shows a high CO 2 uptake of 12.6 mmol g -1 at 20 bar and 298 K. MFM-136 is the first example of an acylamide pyrimidyl isophthalate MOF without open metal sites and, thus, provides a unique platform to study guest binding, particularly the role of free amides. Neutron diffraction reveals that, surprisingly, there is no direct binding between the adsorbed CO 2 /CH 4 molecules and the pendant amide group in the pore. This observation has been confirmed unambiguously by inelastic neutron spectroscopy. This suggests that introduction of functional groups solely may not necessarily induce specific guest-host binding in porous materials, but it is a combination of pore size, geometry, and functional group that leads to enhanced gas adsorption properties.

Reversible optical transcription of supramolecular chirality into molecular chirality

NARCIS (Netherlands)

Jong, Jaap J.D. de; Lucas, Linda N.; Kellogg, Richard M.; Esch, Jan H. van; Feringa, Bernard

2004-01-01

In nature, key molecular processes such as communication, replication, and enzyme catalysis all rely on a delicate balance between molecular and supramolecular chirality. Here we report the design, synthesis, and operation of a reversible, photoresponsive, self-assembling molecular system in which

Chiral Induction and amplification in supramolecular systems at the liquid-solid interface

NARCIS (Netherlands)

Xu, Hong; Ghijsens, E.; George, S.J.; Wolffs, M.; Tomovic, Z.; Schenning, A.P.H.J.; Feyter, de S.

2013-01-01

Chiral induction and amplification in surface-confined supramolecular monolayers are investigated at the liquid–solid interface. Scanning tunneling microscopy (STM) proves that achiral molecules can self-assemble into globally chiral patterns through a variety of approaches, including induction by

Guest Speakers in School-Based Sexuality Education

Science.gov (United States)

McRee, Annie-Laurie; Madsen, Nikki; Eisenberg, Marla E.

2014-01-01

This study, using data from a statewide survey (n = 332), examined teachers' practices regarding the inclusion of guest speakers to cover sexuality content. More than half of teachers (58%) included guest speakers. In multivariate analyses, teachers who taught high school, had professional preparation in health education, or who received…

Supramolecular biomaterials : a modular approach towards tissue engineering

NARCIS (Netherlands)

Dankers, P.Y.W.; Meijer, E.W.

2007-01-01

Supramolecular chemistry is an exciting area of science that plays a central role in bringing different disciplines together, ranging from molecular medicine to nanotechnology. Materials science based on supramolecular interactions is an emerging field, which has made important steps forward in the

The C-terminal peptide of Aquifex aeolicus riboflavin synthase directs encapsulation of native and foreign guests by a cage-forming lumazine synthase.

Science.gov (United States)

Azuma, Yusuke; Zschoche, Reinhard; Hilvert, Donald

2017-06-23

Encapsulation of specific enzymes in self-assembling protein cages is a hallmark of bacterial compartments that function as counterparts to eukaryotic organelles. The cage-forming enzyme lumazine synthase (LS) from Bacillus subtilis (BsLS), for example, encapsulates riboflavin synthase (BsRS), enabling channeling of lumazine from the site of its generation to the site of its conversion to vitamin B 2 Elucidating the molecular mechanisms underlying the assembly of these supramolecular complexes could help inform new approaches for metabolic engineering, nanotechnology, and drug delivery. To that end, we investigated a thermostable LS from Aquifex aeolicus (AaLS) and found that it also forms cage complexes with the cognate riboflavin synthase (AaRS) when both proteins are co-produced in the cytosol of Escherichia coli A 12-amino acid-long peptide at the C terminus of AaRS serves as a specific localization sequence responsible for targeting the guest to the protein compartment. Sequence comparisons suggested that analogous peptide segments likely direct RS complexation by LS cages in other bacterial species. Covalent fusion of this peptide tag to heterologous guest molecules led to their internalization into AaLS assemblies both in vivo and in vitro , providing a firm foundation for creating tailored biomimetic nanocompartments for medical and biotechnological applications. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Molecular and supramolecular speciation of monoamide extractant systems

International Nuclear Information System (INIS)

Ferru, G.

2012-01-01

DEHiBA (N,N-di-(ethyl-2-hexyl)isobutyramide, a monoamide, was chosen as selective extractant for the recovery of uranium in the first cycle of the GANEX process, which aims to realize the grouped extraction of actinides in the second step of the process. The aim of this work is an improved description of monoamide organic solutions in alkane diluent after solutes extraction: water, nitric acid and uranyl nitrate. A parametric study was undertaken to characterize species at molecular scale (by IR spectroscopy, UV-visible spectroscopy, time-resolved laser-induced fluorescence spectroscopy, and electro-spray ionisation mass spectrometry) and at supramolecular scale (by vapor pressure osmometry and small angle X-ray scattering coupled to molecular dynamic simulations). Extraction isotherms were modelled taking into account the molecular and supramolecular speciation. These works showed that the organization of the organic solution depends on the amide concentration, the nature and the concentration of the extracted solute. Three regimes can be distinguished. 1/For extractant concentration less than 0.5 mol/L, monomers are predominate species. 2/ For extractant concentrations between 0.5 and 1 mol/L, small aggregates are formed containing 2 to 4 molecules of monoamide. 3/ For more concentrated solutions (greater than 1 mol/L), slightly larger species can be formed after water or nitric acid extraction. Concerning uranyl nitrate extraction, an important and strong organization of the organic phase is observed, which no longer allows the formation of well spherical defined aggregates. At molecular scale, complexes are not sensitive to the organization of the solution: the same species are observed, regardless of the solute and extractant concentrations in organic phase. (author) [fr

Supramolecular tunneling junctions

NARCIS (Netherlands)

Wimbush, K.S.

2012-01-01

In this study a variety of supramolecular tunneling junctions were created. The basis of these junctions was a self-assembled monolayer of heptathioether functionalized ß-cyclodextrin (ßCD) formed on an ultra-flat Au surface, i.e., the bottom electrode. This gave a well-defined hexagonally packed

Metal-Ion-Mediated Supramolecular Chirality of l-Phenylalanine Based Hydrogels.

Science.gov (United States)

Wang, Fang; Feng, Chuan-Liang

2018-05-14

For chiral hydrogels and related applications, one of the critical issues is how to control the chirality of supramolecular systems in an efficient way, including easy operation, efficient transfer of chirality, and so on. Herein, supramolecular chirality of l-phenylalanine based hydrogels can be effectively controlled by using a broad range of metal ions. The degree of twisting (twist pitch) and the diameter of the chiral nanostructures can also be efficiently regulated. These are ascribed to the synergic effect of hydrogen bonding and metal ion coordination. This study may develop a method to design a new class of electronically, optically, and biologically active materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of rapidly synthesized guest-filled porous complexes with synchrotron radiation: practical guidelines for the crystalline sponge method

Energy Technology Data Exchange (ETDEWEB)

Ramadhar, Timothy R. [Department of Biological Chemistry and Molecular Pharmacology, Harvard Medical School, 240 Longwood Avenue, Boston, Massachusetts, 02115 (United States); Zheng, Shao-Liang [Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts, 02138 (United States); Chen, Yu-Sheng [ChemMatCARS, Center for Advanced Radiation Sources, The University of Chicago c/o Advanced Photon Source, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois, 60439 (United States); Clardy, Jon, E-mail: jon-clardy@hms.harvard.edu [Department of Biological Chemistry and Molecular Pharmacology, Harvard Medical School, 240 Longwood Avenue, Boston, Massachusetts, 02115 (United States)

2015-01-01

This report describes complete practical guidelines and insights for the crystalline sponge method, which have been derived through the first use of synchrotron radiation on these systems, and includes a procedure for faster synthesis of the sponges. These guidelines will be applicable to crystal sponge data collected at synchrotrons or in-house facilities, and will allow researchers to obtain reliable high-quality data and construct chemically and physically sensible models for guest structural determination. A detailed set of synthetic and crystallographic guidelines for the crystalline sponge method based upon the analysis of expediently synthesized crystal sponges using third-generation synchrotron radiation are reported. The procedure for the synthesis of the zinc-based metal–organic framework used in initial crystal sponge reports has been modified to yield competent crystals in 3 days instead of 2 weeks. These crystal sponges were tested on some small molecules, with two being unexpectedly difficult cases for analysis with in-house diffractometers in regard to data quality and proper space-group determination. These issues were easily resolved by the use of synchrotron radiation using data-collection times of less than an hour. One of these guests induced a single-crystal-to-single-crystal transformation to create a larger unit cell with over 500 non-H atoms in the asymmetric unit. This led to a non-trivial refinement scenario that afforded the best Flack x absolute stereochemical determination parameter to date for these systems. The structures did not require the use of PLATON/SQUEEZE or other solvent-masking programs, and are the highest-quality crystalline sponge systems reported to date where the results are strongly supported by the data. A set of guidelines for the entire crystallographic process were developed through these studies. In particular, the refinement guidelines include strategies to refine the host framework, locate guests and determine

Analysis of rapidly synthesized guest-filled porous complexes with synchrotron radiation: practical guidelines for the crystalline sponge method

International Nuclear Information System (INIS)

Ramadhar, Timothy R.; Zheng, Shao-Liang; Chen, Yu-Sheng; Clardy, Jon

2015-01-01

This report describes complete practical guidelines and insights for the crystalline sponge method, which have been derived through the first use of synchrotron radiation on these systems, and includes a procedure for faster synthesis of the sponges. These guidelines will be applicable to crystal sponge data collected at synchrotrons or in-house facilities, and will allow researchers to obtain reliable high-quality data and construct chemically and physically sensible models for guest structural determination. A detailed set of synthetic and crystallographic guidelines for the crystalline sponge method based upon the analysis of expediently synthesized crystal sponges using third-generation synchrotron radiation are reported. The procedure for the synthesis of the zinc-based metal–organic framework used in initial crystal sponge reports has been modified to yield competent crystals in 3 days instead of 2 weeks. These crystal sponges were tested on some small molecules, with two being unexpectedly difficult cases for analysis with in-house diffractometers in regard to data quality and proper space-group determination. These issues were easily resolved by the use of synchrotron radiation using data-collection times of less than an hour. One of these guests induced a single-crystal-to-single-crystal transformation to create a larger unit cell with over 500 non-H atoms in the asymmetric unit. This led to a non-trivial refinement scenario that afforded the best Flack x absolute stereochemical determination parameter to date for these systems. The structures did not require the use of PLATON/SQUEEZE or other solvent-masking programs, and are the highest-quality crystalline sponge systems reported to date where the results are strongly supported by the data. A set of guidelines for the entire crystallographic process were developed through these studies. In particular, the refinement guidelines include strategies to refine the host framework, locate guests and determine

Theoretical investigation of the degradation mechanisms in host and guest molecules used in OLED active layers

KAUST Repository

Winget, Paul; Hong, Minki; Bredas, Jean-Luc

2014-01-01

systems. We identify degradation pathways and define new strategies to guide the synthesis of stable materials for OLED applications for both phosphorescent emitters and organic host materials. The chemical reactivity of these molecules in the active

Chemical-clathrate hybrid hydrogen storage: storage in both guest and host.

Science.gov (United States)

Strobel, Timothy A; Kim, Yongkwan; Andrews, Gary S; Ferrell, Jack R; Koh, Carolyn A; Herring, Andrew M; Sloan, E Dendy

2008-11-12

Hydrogen storage from two independent sources of the same material represents a novel approach to the hydrogen storage problem, yielding storage capacities greater than either of the individual constituents. Here we report a novel hydrogen storage scheme in which recoverable hydrogen is stored molecularly within clathrate cavities as well as chemically in the clathrate host material. X-ray diffraction and Raman spectroscopic measurements confirm the formation of beta-hydroquinone (beta-HQ) clathrate with molecular hydrogen. Hydrogen within the beta-HQ clathrate vibrates at considerably lower frequency than hydrogen in the free gaseous phase and rotates nondegenerately with splitting comparable to the rotational constant. Compared with water-based clathrate hydrate phases, the beta-HQ+H2 clathrate shows remarkable stability over a range of p-T conditions. Subsequent to clathrate decomposition, the host HQ was used to directly power a PEM fuel cell. With one H2 molecule per cavity, 0.61 wt % hydrogen may be stored in the beta-HQ clathrate cavities. When this amount is combined with complete dehydrogenation of the host hydroxyl hydrogens, the maximum hydrogen storage capacity increases nearly 300% to 2.43 wt %.

Fluorescent supramolecular micelles for imaging-guided cancer therapy

Science.gov (United States)

Sun, Mengmeng; Yin, Wenyan; Dong, Xinghua; Yang, Wantai; Zhao, Yuliang; Yin, Meizhen

2016-02-01

A novel smart fluorescent drug delivery system composed of a perylene diimide (PDI) core and block copolymer poly(d,l-lactide)-b-poly(ethyl ethylene phosphate) is developed and named as PDI-star-(PLA-b-PEEP)8. The biodegradable PDI-star-(PLA-b-PEEP)8 is a unimolecular micelle and can self-assemble into supramolecular micelles, called as fluorescent supramolecular micelles (FSMs), in aqueous media. An insoluble drug camptothecin (CPT) can be effectively loaded into the FSMs and exhibits pH-responsive release. Moreover, the FSMs with good biocompatibility can also be employed as a remarkable fluorescent probe for cell labelling because the maximum emission of PDI is beneficial for bio-imaging. The flow cytometry and confocal laser scanning microscopy analysis demonstrate that the micelles are easily endocytosed by cancer cells. In vitro and in vivo tumor growth-inhibitory studies reveal a better therapeutic effect of FSMs after CPT encapsulation when compared with the free CPT drug. The multifunctional FSM nanomedicine platform as a nanovehicle has great potential for fluorescence imaging-guided cancer therapy.A novel smart fluorescent drug delivery system composed of a perylene diimide (PDI) core and block copolymer poly(d,l-lactide)-b-poly(ethyl ethylene phosphate) is developed and named as PDI-star-(PLA-b-PEEP)8. The biodegradable PDI-star-(PLA-b-PEEP)8 is a unimolecular micelle and can self-assemble into supramolecular micelles, called as fluorescent supramolecular micelles (FSMs), in aqueous media. An insoluble drug camptothecin (CPT) can be effectively loaded into the FSMs and exhibits pH-responsive release. Moreover, the FSMs with good biocompatibility can also be employed as a remarkable fluorescent probe for cell labelling because the maximum emission of PDI is beneficial for bio-imaging. The flow cytometry and confocal laser scanning microscopy analysis demonstrate that the micelles are easily endocytosed by cancer cells. In vitro and in vivo tumor growth

Temperature-Induced, Selective Assembly of Supramolecular Colloids in Water

NARCIS (Netherlands)

Van Ravensteijn, Bas G.P.; Vilanova, Neus; De Feijter, Isja; Kegel, Willem K.; Voets, Ilja K.

2017-01-01

In this article, we report the synthesis and physical characterization of colloidal polystyrene particles that carry water-soluble supramolecular N,N′,N″,-trialkyl-benzene-1,3,5-tricarboxamides (BTAs) on their surface. These molecules are known to assemble into one-dimensional supramolecular

Guest Editorial

OpenAIRE

Tianlong Gu; Shenghui Liu

2011-01-01

This special issue comprises of 14 selected papers from the International Workshop on Computer Science for Environmental Engineering and EcoInformatics (CSEEE 2011). The conferences received 860 paper submissions from 15 countries and regions, of which 450 were selected for presentation after a rigorous review process. From these 450 research papers, through two rounds of reviewing, the guest editors selected 14 as the best papers on the Networking Technologies and Information track of the Co...

Managing Guest as an Asset: a Conceptual Review in the Context of Accommodation Services

Directory of Open Access Journals (Sweden)

Dwi Suhartanto

2015-10-01

Full Text Available This article discusses the concept of a customer as an asset of business in the accommodation industry. The purpose of this article is to examine the value of guests as a firm asset and to propose a model for managing guests as an asset in the context of accommodation services. A guest is considered an asset due to its role in providing revenue to the accommodation firm. Because of this role, the accommodation guest needs to be managed appropriately. This article argues that guest service evaluation (i.e. service quality, perceived value, and guest satisfaction and service loyalty are important factors in the development of guest lifetime value. The proposed model of managing guests as an asset consists of marketing instruments, service evaluation, guest loyalty, and financial outcomes provides a comprehensive guide on how accommodation firms can manage the lifetime value of their guests. Finally, as there are limited studies examining this issue, future research should test the proposed model.

Perception of service quality in agrotourism accommodations: Impact on guest loyalty and re-visit intentions

Directory of Open Access Journals (Sweden)

Chryssoula Chatzigeorgiou

2017-03-01

Full Text Available This study presents the development of a conceptual model that demonstrates the dynamic nature of the relationship between service quality and guest satisfaction in the agrotourism accommodation sector, based on theories derived from social psychology and previous research in the marketing, management, and services literature. The model was tested using sample data from guests of four different agrotourism firms, and was modified because of empirical results. The final model improves understanding of the relationship between service quality and guest satisfaction because these constructs were examined from the process perspective of an agrotourism accommodation experience; it portrays service quality and satisfaction in the context of a complete system.

Functional organic materials based on polymerized liquid-crystal monomers: supramolecular hydrogen-bonded systems

NARCIS (Netherlands)

Broer, D.J.; Bastiaansen, C.W.M.; Debije, M.G.; Schenning, A.P.H.J.

2012-01-01

Functional organic materials are of great interest for a variety of applications. To obtain precise functional properties, well-defined hierarchically ordered supramolecular materials are crucial. The self-assembly of liquid crystals has proven to be an extremely useful tool in the development of

Lattice dynamics study of low energy guest–host coupling in clathrate hydrate

International Nuclear Information System (INIS)

Yang Yuehai; Dong Shunle; Wang Lin

2008-01-01

Our lattice dynamics simulation of Xe-hydrate with four-site TIP4P oxygen-shell model can accurately reproduce each peak position in the inelastic incoherent neutron scattering spectrum at the acoustic band (below 15meV) and yield correct relative intensity. Based on the results, the uncertain profile at ∼6 meV is assigned to anharmonic guest modes coupled strongly to small cages. Blue shift is proposed in phonon dispersion sheet in the case of anticrossing and found to be an evident signal for guest-host coupling that explains the anomalous thermal conductivity of clathrate hydrate

Supramolecular fluorene based materials

NARCIS (Netherlands)

Abbel, R.J.

2008-01-01

This thesis describes the use of noncovalent interactions in order to manipulate and control the self-assembly and morphology of electroactive fluorene-based materials. The supramolecular arrangement of p-conjugated polymers and oligomers can strongly influence their electronic and photophysical

Design and Application of Synthetic Receptors for Recognition of Methylated Lysine and Supramolecular Affinity Labeling

Science.gov (United States)

Gober, Isaiah Nathaniel

This dissertation involves the design and synthesis of new synthetic receptors and their application in the molecular recognition of methylated lysine and their use as tools for chemical biology. The dissertation is divided into four parts. The first section focuses on the development of a novel labeling method that is based on ligand-directed affinity labeling principles. In this labeling method, a synthetic receptor that binds to trimethyl lysine (Kme3) is attached through a linker to an electrophilic tag group that can react with a nucleophilic amine in a histone peptide. This affinity labeling probe, which we called CX4-ONBD, is equipped with an electrophilic tag that allows for turn-on fluorescence labeling of Kme3 histone peitdes. We show that the probe gives a pronounced turn-on fluorescence response when it is incubated with a histone peptide that contains Kme3 and a nearby reactive lysine. This probe also displays >5-fold selectivity in covalent labeling over an unmethylated lysine peptide. This represents the first time a synthetic receptor has been used for affinity labeling purposes, and it also expands on the chemical toolkit that is available for sensing PTMs like lysine methylation. In the second section, the supramolecular affinity labeling method that was optimized using CX4-ONBD was applied to the development of a real-time assay for measuring enzymatic activity. More specifically, the probe was used to create a turn-on fluorescence assay for histone deacetylase (HDAC) activity and for inhibitor screening and IC50 determination. Most commercial kits for HDAC activity have limited substrate scope, and other common methods used for characterizing enzymatic activity often require chromatographic separation and are therefore not high-throughput. This small molecule receptor-mediated affinity labeling strategy allowed for facile readout of HDAC activity and inhibition. Overall, this application of supramolecular affinity labeling expands on the

Molecular dynamics study on the structure I clathrate-hydrate of methane + ethane mixture

International Nuclear Information System (INIS)

Erfan-Niya, Hamid; Modarress, Hamid; Zaminpayma, Esmaeil

2011-01-01

Molecular dynamics (MD) simulations are used to study the structure I stability of methane + ethane clathrate-hydrates at temperatures 273, 275 and 277 K. NVT- and NPT-ensembles are utilized in MD simulation, and each consists of 3 x 3 x 3 replica unit cells containing 46 water molecules which are considered as the host molecules and up to eight methane + ethane molecules considered as the guest molecules. In MD simulations for host-host interactions, the potential model used was a type of simple point charge (SPC) model, and for guest-guest and host-guest interactions the potential used was Lennard-Jones model. In the process of MD simulation, achieving equilibrium of the studied system was recognized by stability in calculated pressure for NVT-ensemble and volume for NPT-ensemble. To understand the characteristic configurations of the structure I hydrate, the radial distribution functions (RDFs) of host-host, host-guest and guest-guest molecules as well as other properties including kinetic energy, potential energy and total energy were calculated. The results show that guest molecules interaction with host molecules cannot decompose the hydrate structure, and these results are consistent with most previous experimental and theoretical investigations that methane + ethane mixtures form structure I hydrates over the entire mixture composition range.

Seasonal forcing in a host-macroparasite system.

Science.gov (United States)

Taylor, Rachel A; White, Andrew; Sherratt, Jonathan A

2015-01-21

Seasonal forcing represents a pervasive source of environmental variability in natural systems. Whilst it is reasonably well understood in interacting populations and host-microparasite systems, it has not been studied in detail for host-macroparasite systems. In this paper we analyse the effect of seasonal forcing in a general host-macroparasite system with explicit inclusion of the parasite larval stage and seasonal forcing applied to the birth rate of the host. We emphasise the importance of the period of the limit cycles in the unforced system on the resulting dynamics in the forced system. In particular, when subject to seasonal forcing host-macroparasite systems are capable of multi-year cycles, multiple solution behaviour, quasi-periodicity and chaos. The host-macroparasite systems show a larger potential for multiple solution behaviour and a wider range of periodic solutions compared to similar interacting population and microparasite systems. By examining the system for parameters that represent red grouse and the macroparasite nematode Trichostrongylus tenuis we highlight how seasonality could be an important factor in explaining the wide range of seemingly uncorrelated cycle periods observed in grouse abundance in England and Scotland. Copyright © 2014 Elsevier Ltd. All rights reserved.

α-Cyclodextrin dimer complexes of dopamine and levodopa derivatives to assess drug delivery to the central nervous system: ADME and molecular docking studies

Science.gov (United States)

Shityakov, Sergey; Broscheit, Jens; Förster, Carola

2012-01-01

This paper attempts to predict and emphasize molecular interactions of dopamine, levodopa, and their derivatives (Dopimid compounds) containing 2-phenyl-imidazopyridine moiety with the α-cyclodextrin dimer in order to assess and improve drug delivery to the central nervous system. The molecular docking method is used to determine the energetic profiles, hydrogen bond formation, and hydrophobic effect of 14 host–guest complexes. The results show that the “chemical branching” represented by additional ethyl-acetate residue is energetically unfavorable and promotes a conformational shift due to the high root mean square deviation levels. This phenomenon is characterized by a low number of H-bonds and a significant decrease of the host–guest hydrophobic potential surface. Finally, the overall docking procedure presents a powerful rationale for screening and analyzing various sets of promising drug-like chemical compounds in the fields of supramolecular chemistry, molecular sensing, synthetic receptors, and nanobiotechnology. PMID:22811606

Multicolor Fluorescence Writing Based on Host-Guest Interactions and Force-Induced Fluorescence-Color Memory.

Science.gov (United States)

Matsunaga, Yuki; Yang, Jye-Shane

2015-06-26

A new strategy is reported for multicolor fluorescence writing on thin solid films with mechanical forces. This concept is illustrated by the use of a green-fluorescent pentiptycene derivative 1, which forms variably colored fluorescent exciplexes: a change from yellow to red was observed with anilines, and fluorescence quenching (a change to black) occurred in the presence of benzoquinone. Mechanical forces, such as grinding and shearing, induced a crystalline-to-amorphous phase transition in both the pristine and guest-adsorbed solids that led to a change in the fluorescence color (mechanofluorochromism) and a memory of the resulting color. Fluorescence drawings of five or more colors were created on glass or paper and could be readily erased by exposure to air and dichloromethane fumes. The structural and mechanistic aspects of the observations are also discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Supramolecular Agents for Theranostics].

Science.gov (United States)

Deyev, S M; Lebedenko, E N

2015-01-01

This mini-review summarizes recent data obtained in the process of creation of a versatile module platform suitable for construction of supramolecular theranostic agents. As an example, we consider multifunctional hybrid agents for imaging and elimination of cancer cells. The use of an adapter protein system barnase:barstar for producing targeted multifunctional hybrid structures on the basis of highly specific peptides and mini-antibodies as addressing modules and recombinant proteins and/or nanoparticles of different nature (quantum dots, nanogold, magnetic nanoparticles, nanodiamonds, upconverting nanophosphores, polymer nanoparticles) as agents visualizing and damaging cancer cells is described. New perspectives for creation of selective and highly effective compounds for theranostics and personified medicine are contemplated.

New dendrimer - Peptide host - Guest complexes: Towards dendrimers as peptide carriers

DEFF Research Database (Denmark)

Boas, Ulrik; Sontjens, S.H.M.; Jensen, Knud Jørgen

2002-01-01

Adamantyl urea and adamantyl thiourea modified poly(propylene imine) dendrimers act as hosts for N-terminal tert-butoxycarbonyl (Boc)-protected peptides and form chloroform-soluble complexes. investigations with NMR spectroscopy show that the peptide is bound to the dendrimer by ionic interactions...... between the dendrimer outer shell tertiary amines and the C-terminal carboxylic acid of the peptide, and also through host-urea to peptide-amide hydrogen bonding. The hydrogen-bonding nature of the peptide dendrimer interactions was further confirmed by using Fourier transform IR spectroscopy, for which...... the NH- and CO-stretch signals of the peptide amide moieties shift towards lower wave-numbers upon complexation with the dendrimer. Spatial analysis of the complexes with NOESY spectroscopy generally shows close proximity of the N-terminal Boc group of the peptide to the peripheral adamantyl groups...

Dynamic and bio-orthogonal protein assembly along a supramolecular polymer

NARCIS (Netherlands)

Petkau - Milroy, K.; Uhlenheuer, D.A.; Spiering, A.J.H.; Vekemans, J.A.J.M.; Brunsveld, L.

2013-01-01

Dynamic protein assembly along supramolecular columnar polymers has been achieved through the site-specific covalent attachment of different SNAP-tag fusion proteins to self-assembled benzylguanine-decorated discotics. The self-assembly of monovalent discotics into supramolecular polymers creates a

Supramolecular chemistry-general principles and selected examples from anion recognition and metallosupramolecular chemistry.

Science.gov (United States)

Albrecht, Markus

2007-12-01

This review gives an introduction into supramolecular chemistry describing in the first part general principles, focusing on terms like noncovalent interaction, molecular recognition, self-assembly, and supramolecular function. In the second part those will be illustrated by simple examples from our laboratories. Supramolecular chemistry is the science that bridges the gap between the world of molecules and nanotechnology. In supramolecular chemistry noncovalent interactions occur between molecular building blocks, which by molecular recognition and self-assembly form (functional) supramolecular entities. It is also termed the "chemistry of the noncovalent bond." Molecular recognition is based on geometrical complementarity based on the "key-and-lock" principle with nonshape-dependent effects, e.g., solvatization, being also highly influential. Self-assembly leads to the formation of well-defined aggregates. Hereby the overall structure of the target ensemble is controlled by the symmetry features of the certain building blocks. Finally, the aggregates can possess special properties or supramolecular functions, which are only found in the ensemble but not in the participating molecules. This review gives an introduction on supramolecular chemistry and illustrates the fundamental principles by recent examples from our group.

Simultaneous Determination of Binding Constants for Multiple Carbohydrate Hosts in Complex Mixtures

DEFF Research Database (Denmark)

Meier, Sebastian; Beeren, Sophie

2014-01-01

We describe a simple method for the simultaneous determination of association constants for a guest binding to seven different hosts in a mixture of more than 20 different oligosaccharides. If the binding parameters are known for one component in the mixture, a single NMR titration suffices...

A Dynamic Combinatorial Approach for Identifying Side Groups that Stabilize DNA-Templated Supramolecular Self-Assemblies

Directory of Open Access Journals (Sweden)

Delphine Paolantoni

2015-02-01

Full Text Available DNA-templated self-assembly is an emerging strategy for generating functional supramolecular systems, which requires the identification of potent multi-point binding ligands. In this line, we recently showed that bis-functionalized guanidinium compounds can interact with ssDNA and generate a supramolecular complex through the recognition of the phosphodiester backbone of DNA. In order to probe the importance of secondary interactions and to identify side groups that stabilize these DNA-templated self-assemblies, we report herein the implementation of a dynamic combinatorial approach. We used an in situ fragment assembly process based on reductive amination and tested various side groups, including amino acids. The results reveal that aromatic and cationic side groups participate in secondary supramolecular interactions that stabilize the complexes formed with ssDNA.

Supramolecular "Big Bang" in a Single-Ionic Surfactant/Water System Driven by Electrostatic Repulsion: From Vesicles to Micelles.

Science.gov (United States)

Leclercq, Loïc; Bauduin, Pierre; Nardello-Rataj, Véronique

2017-04-11

In aqueous solution, dimethyldi-n-octylammonium chloride, [DiC 8 ][Cl], spontaneously forms dimers at low concentrations (1-10 mM) to decrease the strength of the hydrophobic-water contact. Dimers represent ideal building blocks for the abrupt edification of vesicles at 10 mM. These vesicles are fully characterized by dynamic and static light scattering, self-diffusion nuclear magnetic resonance, and freeze-fracture transmission electron microscopy. An increase in concentration leads to electrostatic repulsion between vesicles that explode into small micelles at 30 mM. These transitions are detected by means of surface tension, conductivity, and solubility of hydrophobic solutes as well as by isothermal titration microcalorimetry. These unusual supramolecular transitions emerge from the surfactant chemical structure that combines two contradictory features: (i) the double-chain structure tending to form low planar aggregates with low water solubility and (ii) the relatively short chains giving high hydrophilicity. The well-balanced hydrophilic-hydrophobic character of [DiC 8 ][Cl] is then believed to be at the origin of the unusual supramolecular sequence offering new opportunities for drug delivery systems.

Effects of guest atomic species on the lattice thermal conductivity of type-I silicon clathrate studied via classical molecular dynamics

Energy Technology Data Exchange (ETDEWEB)

Kumagai, Tomohisa, E-mail: kumagai@criepi.denken.or.jp; Nakamura, Kaoru; Yamada, Susumu; Ohnuma, Toshiharu [Materials Science Research Laboratory, Central Research Institute of Electric Power Industry, 2-6-1 Nagasaka, Yokosuka, Kanagawa 240-0196 (Japan)

2016-08-14

The effects of guest atomic species in Si clathrates on the lattice thermal conductivity were studied using classical molecular dynamics calculations. The interaction between a host atom and a guest atom was described by the Morse potential function while that between host atoms was described by the Tersoff potential. The parameters of the potentials were newly determined for this study such that the potential curves obtained from first-principles calculations for the insertion of a guest atom into a Si cage were successfully reproduced. The lattice thermal conductivities were calculated by using the Green-Kubo method. The experimental lattice thermal conductivity of Ba{sub 8}Ga{sub 16}Si{sub 30} can be successfully reproduced using the method. As a result, the lattice thermal conductivities of type-I Si clathrates, M{sub 8}Si{sub 46} (M = Na, Mg, K, Ca Rb, Sr, Cs, or Ba), were obtained. It is found that the lattice thermal conductivities of M{sub 8}Si{sub 46}, where M is IIA elements (i.e., M = Mg, Ca, Sr, or Ba) tend to be lower than those of M{sub 8}Si{sub 46}, where M is IA elements (i.e., M = Na, K, Rb, or Cs). Those of {sup m}M{sub 8}Si{sub 46}, where m was artificially modified atomic weight were also obtained. The obtained lattice thermal conductivity can be regarded as a function of a characteristic frequency, f{sub c}. That indicates minimum values around f{sub c}=2-4 THz, which corresponds to the center of the frequencies of the transverse acoustic phonon modes associated with Si cages.

A novel electrochemical immunosensor using β-cyclodextrins functionalized silver supported adamantine-modified glucose oxidase as labels for ultrasensitive detection of alpha-fetoprotein.

Science.gov (United States)

Gao, Jian; Ma, Hongmin; Lv, Xiaohui; Yan, Tao; Li, Na; Cao, Wei; Wei, Qin

2015-09-17

In this work, a novel sandwich-type electrochemical immunosensor based on host-guest interaction was fabricated for the detection of alpha-fetoprotein (AFP). Due to the large specific surface area of multiwalled carbon nanotubes and the unique supramolecular recognition ability of β-cyclodextrins, ferrocenecarboxylic acid (Fc) was incorporated into this sensor platform by host-guest interaction to generate an electrochemical signal. And β-cyclodextrins functionalized silver supported adamantine-modified glucose oxidase (GOD-CD-Ag), was used as a label to improve the analytical performance of the immunosensor by the dual amplification strategy. The obtained GOD-CD-Ag conjugates could convert glucose into gluconic acid with the formation of hydrogen peroxide (H2O2). And then silver nanoparticles could in situ catalyze the reduction of the generated H2O2, dramatically improving the oxidation reaction of Fc. The developed immunosensor shows a wide linear calibration range from 0.001 to 5.0 ng/mL with a low detection limit (0.2 pg/mL) for the detection of AFP. The method, with ideal reproducibility and selectivity, has a wide application prospect in clinical research. Copyright © 2015 Elsevier B.V. All rights reserved.

New dendrimer - peptide host - guest complexes : towards dendrimers as peptide carriers

NARCIS (Netherlands)

Boas, U.; Sontjens, S.H.M.; Jensen, K.J.; Christensen, J.B.; Meijer, E.W.

2002-01-01

Adamantyl urea and adamantyl thiourea modified poly(propylene imine) dendrimers act as hosts for N-terminal tert-butoxycarbonyl (Boc)-protected peptides and form chloroform-soluble complexes. investigations with NMR spectroscopy show that the peptide is bound to the dendrimer by ionic interactions

Nonlinear optical switching of PDA/Ag hybrid materials based on temperature- and pH-responsive threading and dethreading of cyclodextrin polypseudorotaxane

Energy Technology Data Exchange (ETDEWEB)

Rao, Jinan; Wen, Xiaolei; Leng, Jing; Wang, Jin; Zou, Gang; Zhang, Qijin [University of Science and Technology of China, CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, Key Laboratory of Optoelectronic Science and Technology in Anhui Province, Anhui (China)

2012-11-15

We developed a novel temperature and pH dual-responsive supramolecular system in which the aggregation and disaggregation of polydiacetylene/silver (PDA/Ag) hybrid nanocrystals can be mediated by environmentally responsive threading and dethreading processes of polypseudorotaxane. The PDA/Ag hybrid nanocrystals provide a nonlinear optical (NLO) property. The host-guest interaction between poly(ethylene glycol) (PEG) and cyclodextrin (CD) cavities on the surface of the hybrid nanocrystals causes the PDA/Ag hybrid nanocrystals to be sufficiently close to each other for providing an enhanced surface plasmon resonance and a corresponding NLO effect. NLO switching of the colloidal materials can be easily realized by varying temperature and pH. The facile preparation procedures and their response to the surrounding media render these novel hybrid colloidal materials potential candidates for applications in sensors, catalysis and optical/electronic devices. (orig.)

Experiences and Coping Strategies of Host Families in International Youth Exchange

Science.gov (United States)

Weidemann, Arne; Bluml, Frances

2009-01-01

Twenty narrative interviews were conducted with German host parents between 2006 and 2007 about their experiences with a one-year stay of a guest student in their family. The study took place within the context of a student research project as part of the research-oriented MA course "Intercultural Communication-Intercultural Competence"…

Solvent polarity effects on supramolecular chirality of a polyfluorene-thiophene copolymer.

Science.gov (United States)

Hirahara, Takashi; Yoshizawa-Fujita, Masahiro; Takeoka, Yuko; Rikukawa, Masahiro

2018-06-01

This study demonstrates the supramolecular chirality control of a conjugated polymer via solvent polarity. We designed and synthesized a chiral polyfluorene-thiophene copolymer having two different chiral side chains at the 9-position of the fluorene unit. Chiral cyclic and alkyl ethers with different polarities were selected as the chiral side chains. The sign of the circular dichroism spectra in the visible wavelength region was affected by the solvent system, resulting from the change of supramolecular structure. The estimation of the solubility parameter revealed that the solubility difference of the side chains contributed to the change of the circular dichroism sign, which was also observed in spin-coated films prepared from good solvents having different polarities. © 2018 Wiley Periodicals, Inc.

A Room with a Viewpoint Revisited: Descriptive Norms and Hotel Guests' Towel Reuse Behavior

OpenAIRE

Bohner, Gerd; Schlüter, Lena E.

2014-01-01

Field experiments on descriptive norms as a means to increase hotel guests' towel reuse [1] were replicated and extended. In two hotels in Germany (Study 1: N = 724; Study 2: N = 204), descriptive norm messages suggesting that 75% of guests had reused their towels, or a standard message appealing to environmental concerns, were placed in guests' bathrooms. Descriptive norm messages varied in terms of proximity of the reference group ("hotel guests" vs. "guests in this room") and temporal prox...

Dielectric properties of supramolecular ionic structures obtained from multifunctional carboxylic acids and amines

DEFF Research Database (Denmark)

Gonzalez, Lidia; Yu, Liyun; Hvilsted, Søren

2014-01-01

The dielectric properties of several supramolecular ionic polymers and networks, linked by the ammonium salts of hexamethylene diamine (HMDA), tris(2-aminoethyl)amine (TAEA), poly(propylene imine) (PPI) dendrimers and two short bis carboxymethyl ether-terminated poly(ethylene glycol)s (Di......COOH-PEG), are reported in this paper. All supramolecular ionic polymers and networks exhibit very high relative dielectric permittivities ( 3 0 )( 10 2 – 10 6 ) at low frequencies, and signi fi cantly lower values (from 1 up to 26) at high frequencies. Additionally, the dielectric properties of supramolecular ionic......), are investigated. Here the relative dielectric permittivities of the supramolecular ionic structures formed with the multifunctional carboxylic acids were lower than those from the supramolecular ionic structures formed with the two carboxymethyl ether-terminated poly(ethylene glycol)s....

Tuning of Magnetic Anisotropy in Hexairon(III) Rings by Host-Guest Interactions: An Investigation by High-Field Torque Magnetometry.

Science.gov (United States)

Cornia; Affronte; Jansen; Abbati; Gatteschi

1999-08-01

Full chemical control of magnetic anisotropy in hexairon(III) rings can be achieved by varying the size of the guest alkali metal ion. Dramatically different anisotropies characterize the Li(I) and Na(I) complexes of [Fe(6)(OMe)(12)(L)(6)] (L=1,3-propanedione derivatives; a schematic representation of the Li(I) complex is shown), as revealed by high-field torque magnetometry-Iron: (g), oxygen: o, carbon: o, Li(+): plus sign in circle.

Preparation of an anionic azo pigment-pillared layered double hydroxide and the thermo- and photostability of the resulting intercalated material

Science.gov (United States)

Guo, Shengchang; Li, Dianqing; Zhang, Weifeng; Pu, Min; Evans, David G.; Duan, Xue

2004-12-01

A large anionic pigment has been intercalated into a layered double hydroxide (LDH) host by ion-exchange of an Mg/Al LDH-nitrate precursor with a solution of C.I. Pigment Red 48:2 (the calcium salt of 4-((5-chloro-4-methyl-2-sulfophenyl)azo)-3-hydroxy-2-naphthalene-carboxylic acid), in ethane-1,2-diol. After intercalation of the pigment, the interlayer distance in the LDH increases from 0.86 to 1.72 nm. Infrared spectra and TG-DTA curves reveal the presence of a complex system of supramolecular host-guest interactions. The UV-visible diffuse reflectance spectra of C.I. Pigment Red 48:2 show marked changes after heating at 200 °C and above, whereas there are no significant changes in the spectra of the intercalated pigment after heating at temperatures up to 300 °C, showing that the thermostability is markedly enhanced by intercalation in the LDH host. The pigment-intercalated LDHs exhibits much higher photostability to UV light than the pristine pigment, in the case of both the pure solids and their composites with polypropylene, as shown by measurement of CIE 1976 L*a*b* color difference ( ΔE) values.

Solid-phase based synthesis of ureidopyrimidinone-peptide conjugates for supramolecular biomaterials

NARCIS (Netherlands)

Feijter, de I.; Goor, O.J.G.M.; Hendrikse, S.I.S.; Comellas Aragones, M.; Sontjens, S.H.M.; Zaccaria, S.; Fransen, P.P.K.H.; Peeters, J.W.; Milroy, L.G.; Dankers, P.Y.W.

2015-01-01

Supramolecular polymers have shown to be powerful scaffolds for tissue engineering applications. Supramolecular biomaterials functionalized with ureidopyrimidinone (UPy) moieties, which dimerize via quadruple hydrogen-bond formation, are eminently suitable for this purpose. The conjugation of the

Artificial muscle-like function from hierarchical supramolecular assembly of photoresponsive molecular motors.

Science.gov (United States)

Chen, Jiawen; Leung, Franco King-Chi; Stuart, Marc C A; Kajitani, Takashi; Fukushima, Takanori; van der Giessen, Erik; Feringa, Ben L

2018-02-01

A striking feature of living systems is their ability to produce motility by amplification of collective molecular motion from the nanoscale up to macroscopic dimensions. Some of nature's protein motors, such as myosin in muscle tissue, consist of a hierarchical supramolecular assembly of very large proteins, in which mechanical stress induces a coordinated movement. However, artificial molecular muscles have often relied on covalent polymer-based actuators. Here, we describe the macroscopic contractile muscle-like motion of a supramolecular system (comprising 95% water) formed by the hierarchical self-assembly of a photoresponsive amphiphilic molecular motor. The molecular motor first assembles into nanofibres, which further assemble into aligned bundles that make up centimetre-long strings. Irradiation induces rotary motion of the molecular motors, and propagation and accumulation of this motion lead to contraction of the fibres towards the light source. This system supports large-amplitude motion, fast response, precise control over shape, as well as weight-lifting experiments in water and air.

Artificial muscle-like function from hierarchical supramolecular assembly of photoresponsive molecular motors

Science.gov (United States)

Chen, Jiawen; Leung, Franco King-Chi; Stuart, Marc C. A.; Kajitani, Takashi; Fukushima, Takanori; van der Giessen, Erik; Feringa, Ben L.

2018-02-01

A striking feature of living systems is their ability to produce motility by amplification of collective molecular motion from the nanoscale up to macroscopic dimensions. Some of nature's protein motors, such as myosin in muscle tissue, consist of a hierarchical supramolecular assembly of very large proteins, in which mechanical stress induces a coordinated movement. However, artificial molecular muscles have often relied on covalent polymer-based actuators. Here, we describe the macroscopic contractile muscle-like motion of a supramolecular system (comprising 95% water) formed by the hierarchical self-assembly of a photoresponsive amphiphilic molecular motor. The molecular motor first assembles into nanofibres, which further assemble into aligned bundles that make up centimetre-long strings. Irradiation induces rotary motion of the molecular motors, and propagation and accumulation of this motion lead to contraction of the fibres towards the light source. This system supports large-amplitude motion, fast response, precise control over shape, as well as weight-lifting experiments in water and air.

Supramolecular organization and chiral resolution of p-terphenyl-m-dicarbonitrile on the Ag(111) surface.

Science.gov (United States)

Marschall, Matthias; Reichert, Joachim; Seufert, Knud; Auwärter, Willi; Klappenberger, Florian; Weber-Bargioni, Alexander; Klyatskaya, Svetlana; Zoppellaro, Giorgio; Nefedov, Alexei; Strunskus, Thomas; Wöll, Christof; Ruben, Mario; Barth, Johannes V

2010-05-17

The supramolecular organization and layer formation of the non-linear, prochiral molecule [1, 1';4',1'']-terphenyl-3,3"-dicarbonitrile adsorbed on the Ag(111) surface is investigated by scanning tunneling microscopy (STM) and near-edge X-ray absorption fine-structure spectroscopy (NEXAFS). Upon two-dimensional confinement the molecules are deconvoluted in three stereoisomers, that is, two mirror-symmetric trans- and one cis-species. STM measurements reveal large and regular islands following room temperature deposition, whereby NEXAFS confirms a flat adsorption geometry with the electronic pi-system parallel to the surface plane. The ordering within the expressed supramolecular arrays reflects a substrate templating effect, steric constraints and the operation of weak lateral interactions mainly originating from the carbonitrile endgroups. High-resolution data at room temperature reveal enantiormorphic characteristics of the molecular packing schemes in different domains of the arrays, indicative of chiral resolution during the 2D molecular self-assembly process. At submonolayer coverage supramolecular islands coexist with a disordered fluid phase of highly mobile molecules. Following thermal quenching (down to 6 K) we find extended supramolecular ribbons stabilised again by attractive and directional noncovalent interactions, the formation of which reflects a chiral resolution of trans-species.

Self-Assembled Supramolecular Architectures Lyotropic Liquid Crystals

CERN Document Server

Garti, Nissim

2012-01-01

This book will describe fundamentals and recent developments in the area of Self-Assembled Supramolecular Architecture and their relevance to the  understanding of the functionality of  membranes  as delivery systems for active ingredients. As the heirarchial architectures determine their performance capabilities, attention will be paid to theoretical and design aspects related to the construction of lyotropic liquid crystals: mesophases such as lamellar, hexagonal, cubic, sponge phase micellosomes. The book will bring to the reader mechanistic aspects, compositional c

An organic dye-polymer (phenol red-poly (vinyl alcohol)) composite architecture towards tunable -optical and -saturable absorption characteristics

Energy Technology Data Exchange (ETDEWEB)

Sreedhar, Sreeja, E-mail: sreejasreedhar83@gmail.com; Muneera, C. I., E-mail: drcimuneera@hotmail.com [Department of Physics, University of Kerala, Kariavattom, Thiruvananthapuram 695581, Kerala (India); Illyaskutty, Navas [Institute for Sensorics and Information Systems (ISIS), Karlsruhe University of Applied Sciences, Moltkestr. 30, D-76133 Karlsruhe (Germany); Sreedhanya, S. [School of Chemical Sciences, M. G. University, Kottayam, Kerala 686560 (India); Philip, Reji [Light and Matter Physics Group, Raman Research Institute, Bangalore 560080 (India)

2016-05-21

Herein, we demonstrate that blending an organic dye (guest/filler), with a vinyl polymer (host template), is an inexpensive and simple approach for the fabrication of multifunctional photonic materials which could display an enhancement in the desirable properties of the constituent materials and, at the same time provide novel synergistic properties for the guest-host system. A new guest-host nanocomposite system comprising Phenol Red dye and poly (vinyl alcohol) as guest and host template, respectively, which exhibits tunable optical characteristics and saturable absorption behavior, is introduced. The dependence of local electronic environment provided by the polymer template and the interactions of the polymer molecules with the encapsulated guest molecules on the observed optical/nonlinear absorption behavior is discussed. An understanding of the tunability of the optical/ photophysical processes, with respect to the filler content, as discussed herein could help in the design of improved optical materials for several photonic device applications like organic light emitting diodes and saturable absorbers.

Two different strategies of host manipulation allow parasites to persist in intermediate-definitive host systems

NARCIS (Netherlands)

Vries, de L.J.; Langevelde, van F.

2018-01-01

Trophically transmitted parasites start their development in an intermediate host, before they finish the development in their definitive host when the definitive host preys on the intermediate host. In intermediate-definitive host systems, two strategies of host manipulation have been evolved:

A new configurational bias scheme for sampling supramolecular structures

Energy Technology Data Exchange (ETDEWEB)

De Gernier, Robin; Mognetti, Bortolo M., E-mail: bmognett@ulb.ac.be [Center for Nonlinear Phenomena and Complex Systems, Université Libre de Bruxelles, Code Postal 231, Campus Plaine, B-1050 Brussels (Belgium); Curk, Tine [Department of Chemistry, University of Cambridge, Cambridge CB2 1EW (United Kingdom); Dubacheva, Galina V. [Biosurfaces Unit, CIC biomaGUNE, Paseo Miramon 182, 20009 Donostia - San Sebastian (Spain); Richter, Ralf P. [Biosurfaces Unit, CIC biomaGUNE, Paseo Miramon 182, 20009 Donostia - San Sebastian (Spain); Université Grenoble Alpes, DCM, 38000 Grenoble (France); CNRS, DCM, 38000 Grenoble (France); Max Planck Institute for Intelligent Systems, 70569 Stuttgart (Germany)

2014-12-28

We present a new simulation scheme which allows an efficient sampling of reconfigurable supramolecular structures made of polymeric constructs functionalized by reactive binding sites. The algorithm is based on the configurational bias scheme of Siepmann and Frenkel and is powered by the possibility of changing the topology of the supramolecular network by a non-local Monte Carlo algorithm. Such a plan is accomplished by a multi-scale modelling that merges coarse-grained simulations, describing the typical polymer conformations, with experimental results accounting for free energy terms involved in the reactions of the active sites. We test the new algorithm for a system of DNA coated colloids for which we compute the hybridisation free energy cost associated to the binding of tethered single stranded DNAs terminated by short sequences of complementary nucleotides. In order to demonstrate the versatility of our method, we also consider polymers functionalized by receptors that bind a surface decorated by ligands. In particular, we compute the density of states of adsorbed polymers as a function of the number of ligand–receptor complexes formed. Such a quantity can be used to study the conformational properties of adsorbed polymers useful when engineering adsorption with tailored properties. We successfully compare the results with the predictions of a mean field theory. We believe that the proposed method will be a useful tool to investigate supramolecular structures resulting from direct interactions between functionalized polymers for which efficient numerical methodologies of investigation are still lacking.

Be My Guest: A Survey of Mass Communication Students' Perception of Guest Speakers

Science.gov (United States)

Merle, Patrick F.; Craig, Clay

2017-01-01

The use of guest speakers as a pedagogical technique across disciplines at the college level is hardly novel. However, empirical assessment of journalism and mass communication students' perceptions of this practice has not previously been conducted. To fill this gap, this article presents results from an online survey specifically administered to…

Supramolecular Cocrystals of Gliclazide: Synthesis, Characterization and Evaluation.

Science.gov (United States)

Chadha, Renu; Rani, Dimpy; Goyal, Parnika

2017-03-01

To prepare the supramolecular cocrystals of gliclazide (GL, a BCS class II drug molecule) via mechanochemical route, with the goal of improving physicochemical and biopharmaceutical properties. Two cocrystals of GL with GRAS status coformers, sebacic acid (GL-SB; 1:1) and α-hydroxyacetic acid (GL-HA; 1:1) were screened out using liquid assisted grinding. The prepared cocrystals were characterized using thermal and analytical techniques followed by evaluation of antidiabetic activity and pharmacokinetic parameters. The generation of new, single and pure crystal forms was characterized by DSC and PXRD. The crystal structure determination from PXRD revealed the existence of both cocrystals in triclinic (P-1) crystal system. The hydrogen bonded network, determined by material studio was well supported by shifts in FTIR and SSNMR. Both the new solid forms displayed improved solubility, IDR, antidiabetic activity and pharmacokinetic parameters as compared to GL. The improvement in these physicochemical and biopharmaceutical properties corroborated the fact that the supramolecular cocrystallization may be useful in the development of pharmaceutical crystalline materials with interesting network and properties.

Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly.

Science.gov (United States)

Iyoda, Masahiko; Hasegawa, Masashi

2015-01-01

The construction of redox-active supramolecular assemblies based on star-shaped and radially expanded tetrathiafulvalene (TTF) oligomers with divergent and extended conjugation is summarized. Star-shaped TTF oligomers easily self-aggregate with a nanophase separation to produce supramolecular structures, and their TTF units stack face-to-face to form columnar structures using the fastener effect. Based on redox-active self-organizing supramolecular structures, conducting nanoobjects are constructed by doping of TTF oligomers with oxidants after the formation of such nanostructures. Although radical cations derived from TTF oligomers strongly interact in solution to produce a mixed-valence dimer and π-dimer, it seems to be difficult to produce nanoobjects of radical cations different from those of neutral TTF oligomers. In some cases, however, radical cations form nanostructured fibers and rods by controlling the supramolecular assembly, oxidation states, and counter anions employed.

Supramolecular Organocatalysis in Water Mediated by Macrocyclic Compounds

Directory of Open Access Journals (Sweden)

Margherita De Rosa

2018-04-01

Full Text Available In the last decades many efforts have been devoted to design supramolecular organocatalysts able to work in water as the reaction medium. The use of water as solvent provides promising benefits with respect to environmental impact. In this context, macrocyclic compounds played a role of primary importance thanks to their ease of synthesis and their molecular recognition abilities toward the reactants. The aim of this review is to give an overview of the recent advances in the field of supramolecular organocatalysis in water, focusing the attention on calixarene and cyclodextrins derivatives. Calixarenes and cyclodextrins, thanks to their hydrophobic cavities, are able to host selectively the substrates isolating they from the reaction environment. In addition, the synthetic versatilities of these macrocycles permits to introduce useful functional groups in close proximity of the hydrophobic binding sites. Regarding the cyclodextrins (CDs, we have here reviewed the their most recent uses as organocatalysts for the synthesis of heterocyclic compounds, in multi-component reactions and in carbon-carbon bond forming reactions. Examples have been reported in which CD catalysts are able to drive the regiochemistry of common organic reactions. In addition, cyclodextrins bearing catalytically active chiral groups, have shown excellent enantioselectivity in the catalysis of organic reactions. Recently reported results have shown that calixarene derivatives are able to accelerate organic reaction under “on-water” conditions with a significant selectivity toward the reactants. Under “on-water conditions” the hydrophobic effect, induced by insoluble calixarene derivatives, forces the reactants and the catalyst to aggregate and thus accelerating the reaction between them thanks to an amplification of weak secondary interactions. Regarding the use of water-soluble calixarene organocatalysts, we have here reviewed their role in the acceleration of

Supramolecular Organocatalysis in Water Mediated by Macrocyclic Compounds

Science.gov (United States)

De Rosa, Margherita; La Manna, Pellegrino; Talotta, Carmen; Soriente, Annunziata; Gaeta, Carmine; Neri, Placido

2018-04-01

In the last decades many efforts have been devoted to design supramolecular organocatalysts able to work in water as the reaction medium. The use of water as solvent provides promising benefits with respect to environmental impact. In this context, macrocyclic compounds played a role of primary importance thanks to their ease of synthesis and their molecular recognition abilities toward the reactants. The aim of this review is to give an overview of the recent advances in the field of supramolecular organocatalysis in water, focusing the attention on calixarene and cyclodextrins derivatives. Calixarenes and cyclodextrins, thanks to their hydrophobic cavities, are able to host selectively the substrates isolating they from the reaction environment. In addition, the synthetic versatilities of these macrocycles permits to introduce useful functional groups in close proximity of the hydrophobic binding sites. Regarding the cyclodextrins (CDs), we have here reviewed the their most recent uses as organocatalysts for the synthesis of heterocyclic compounds, in multi-component reactions and in carbon-carbon bond forming reactions. Examples have been reported in which CD catalysts are able to drive the regiochemistry of common organic reactions. In addition, cyclodextrins bearing catalytically active chiral groups, have shown excellent enantioselectivity in the catalysis of organic reactions. Recently reported results have shown that calixarene derivatives are able to accelerate organic reaction under "on-water" conditions with a significant selectivity toward the reactants. Under "on-water conditions" the hydrophobic effect, induced by insoluble calixarene derivatives, forces the reactants and the catalyst to aggregate and thus accelerating the reaction between them thanks to an amplification of weak secondary interactions. Regarding the use of water-soluble calixarene organocatalysts, we have here reviewed their role in the acceleration of common organic reactions.

[Special impact of supramolecular chemistry on Chinese medicine theories].

Science.gov (United States)

He, Fu-Yuan; Zhou, Yi-Qun; Deng, Kai-Wen; Deng, Jun-Lin; Shi, Ji-Lian; Liu, Wen-Long; Yang, Yan-Tao; Tang, Yu; Liu, Zhi-Gang

2014-04-01

The paper aimed to elucidate the specific impact of supramolecular chemistry on the Chinese medicine theories (CMT) in their modernization, after had summarized up the research status of supramolecular chemistry and analyzed the possible supramolecular forms of Chinese medicine (CM), as well as considered the problems in modernization of CM theories. On comparison of the classical chemistry that delt with chemical bonds among atoms, the supramolecular chemistry was rather concerned with varietes of weak noncovalent bonds intermolecules, and reflected the macro-apparent chemical properties of each molecules, and was the most appropriate chemical theories to explain the CMT and microcosmic materials. The molecules in the human body and Chinese material medica (CMM) formed supramolecules by way of self-assembly, self-organization, self-recognition and self-replication, with themselves or with complexation, composition, chelation, inclusion, neutralization etc. Meridian and Zang-fu viscera in CMT might be a space channel structure continuously consisted of unique molecules cavity that was imprinted with the supramolecularly template inside and outside of cells, through which the molecules in CMM interacted with the meridian and Zang-fu viscera. When small molecules in human body imprinted with macromolecules in meridian and Zang-fu viscera, in other words, they migrated along within imprinting channels of meridian and Zang-fu viscera on behavior of "Qi chromatography" impulsed by the heart beat, finally showed up on macroscopic the anisotropy of tissue and organ, as described namely as visceral manifestation in Chinese medical science. When small molecules in CMM interacted with imprinting channel on meridian and Zang-fu viscera, the natural properties and efficacy regularities of CMM was reflected on macroscopic. Therefore, the special representation forms of basic CMT is based on the macroscopic expression of "Qi chromatography" abided by imprinting effect

Precision Synthesis of Functional Polysaccharide Materials by Phosphorylase-Catalyzed Enzymatic Reactions

Directory of Open Access Journals (Sweden)

Jun-ichi Kadokawa

2016-04-01

Full Text Available In this review article, the precise synthesis of functional polysaccharide materials using phosphorylase-catalyzed enzymatic reactions is presented. This particular enzymatic approach has been identified as a powerful tool in preparing well-defined polysaccharide materials. Phosphorylase is an enzyme that has been employed in the synthesis of pure amylose with a precisely controlled structure. Similarly, using a phosphorylase-catalyzed enzymatic polymerization, the chemoenzymatic synthesis of amylose-grafted heteropolysaccharides containing different main-chain polysaccharide structures (e.g., chitin/chitosan, cellulose, alginate, xanthan gum, and carboxymethyl cellulose was achieved. Amylose-based block, star, and branched polymeric materials have also been prepared using this enzymatic polymerization. Since phosphorylase shows a loose specificity for the recognition of substrates, different sugar residues have been introduced to the non-reducing ends of maltooligosaccharides by phosphorylase-catalyzed glycosylations using analog substrates such as α-d-glucuronic acid and α-d-glucosamine 1-phosphates. By means of such reactions, an amphoteric glycogen and its corresponding hydrogel were successfully prepared. Thermostable phosphorylase was able to tolerate a greater variance in the substrate structures with respect to recognition than potato phosphorylase, and as a result, the enzymatic polymerization of α-d-glucosamine 1-phosphate to produce a chitosan stereoisomer was carried out using this enzyme catalyst, which was then subsequently converted to the chitin stereoisomer by N-acetylation. Amylose supramolecular inclusion complexes with polymeric guests were obtained when the phosphorylase-catalyzed enzymatic polymerization was conducted in the presence of the guest polymers. Since the structure of this polymeric system is similar to the way that a plant vine twines around a rod, this polymerization system has been named �

High relative humidity in-package of fresh-cut fruits and vegetables: advantage or disadvantage considering microbiological problems and antimicrobial delivering systems?

Science.gov (United States)

Ayala-Zavala, J F; Del-Toro-Sánchez, L; Alvarez-Parrilla, E; González-Aguilar, G A

2008-05-01

This hypothesis article states that the high relative humidity (RH) of packaged fresh-cut fruits or vegetables that is associated with spoilage can be used as an advantageous way to deliver antimicrobial compounds using cyclodextrins (CDs) as carriers. CDs can function as antimicrobial delivery systems as they can release antioxidant and antimicrobial compounds (guest molecules) as the humidity levels increase in the headspace. Hydrophobic antimicrobial guests can be complexed with CDs due to the amphiphatic nature of the host. Then, at high RH values, due to the water-CDs interaction, host-guest interactions are weakened; consequently, the antimicrobial molecule is released and should protect the product against the microbial growth. Potential antimicrobial compounds capable of forming complexes with CDs are discussed, as well as possible applications to preserve fresh-cut produce and future research in this area.

Biomimetic catalysts responsive to specific chemical signals

Energy Technology Data Exchange (ETDEWEB)

Zhao, Yan [Iowa State Univ., Ames, IA (United States)

2015-03-04

Part 1. Design of Biomimetic Catalysts Based on Amphiphilic Systems The overall objective of our research is to create biomimetic catalysts from amphiphilic molecules. More specifically, we aim to create supramolecular systems that can be used to control the microenvironment around a catalytic center in a biomimetic fashion and apply the learning to construct supramolecular catalysts with novel functions found in enzymatic catalysts. We have prepared synthetic molecules (i.e., foldamers) that could fold into helical structures with nanometer-sized internal hydrophilic cavities. Cavities of this size are typically observed only in the tertiary and quaternary structures of proteins but were formed in our foldamer prepared in just a few steps from the monomer. Similar to many proteins, our foldamers displayed cooperativity in the folding/unfolding equilibrium and followed a two-state conformational transition. In addition, their conformational change could be triggered by solvent polarity, pH, or presence of metal ions and certain organic molecules. We studied their environmentally dependent conformational changes in solutions, surfactant micelles, and lipid bilayer membranes. Unlike conventional rigid supramolecular host, a foldamer undergoes conformational change during guest binding. Our study in the molecular recognition of an oligocholate host yielded some extremely exciting results. Cooperativity between host conformation and host–guest interactions was found to “magnify” weak binding interactions. In other words, since binding affinity is determined by the overall change of free energy during the binding, guest-induced conformational change of the host, whether near or far from the binding site, affects the binding. This study has strong implications in catalysis because enzymes have been hypothesized to harvest similar intramolecular forces to strengthen their binding with the transition state of an enzyme-catalyzed reaction. The supramolecular and

Diverse Supramolecular Nanofiber Networks Assembled by Functional Low-Complexity Domains.

Science.gov (United States)

An, Bolin; Wang, Xinyu; Cui, Mengkui; Gui, Xinrui; Mao, Xiuhai; Liu, Yan; Li, Ke; Chu, Cenfeng; Pu, Jiahua; Ren, Susu; Wang, Yanyi; Zhong, Guisheng; Lu, Timothy K; Liu, Cong; Zhong, Chao

2017-07-25

Self-assembling supramolecular nanofibers, common in the natural world, are of fundamental interest and technical importance to both nanotechnology and materials science. Despite important advances, synthetic nanofibers still lack the structural and functional diversity of biological molecules, and the controlled assembly of one type of molecule into a variety of fibrous structures with wide-ranging functional attributes remains challenging. Here, we harness the low-complexity (LC) sequence domain of fused in sarcoma (FUS) protein, an essential cellular nuclear protein with slow kinetics of amyloid fiber assembly, to construct random copolymer-like, multiblock, and self-sorted supramolecular fibrous networks with distinct structural features and fluorescent functionalities. We demonstrate the utilities of these networks in the templated, spatially controlled assembly of ligand-decorated gold nanoparticles, quantum dots, nanorods, DNA origami, and hybrid structures. Owing to the distinguishable nanoarchitectures of these nanofibers, this assembly is structure-dependent. By coupling a modular genetic strategy with kinetically controlled complex supramolecular self-assembly, we demonstrate that a single type of protein molecule can be used to engineer diverse one-dimensional supramolecular nanostructures with distinct functionalities.

Theoretical model estimation of guest diffusion in Metal-Organic Frameworks (MOFs)

KAUST Repository

Zheng, Bin

2015-08-11

Characterizing molecule diffusion in nanoporous matrices is critical to understanding the novel chemical and physical properties of metal-organic frameworks (MOFs). In this paper, we developed a theoretical model to fastly and accurately compute the diffusion rate of guest molecules in a zeolitic imidazolate framework-8 (ZIF-8). The ideal gas or equilibrium solution diffusion model was modified to contain the effect of periodical media via introducing the possibility of guests passing through the framework gate. The only input in our model is the energy barrier of guests passing through the MOF’s gate. Molecular dynamics (MD) methods were employed to gather the guest density profile, which then was used to deduce the energy barrier values. This produced reliable results that require a simulation time of 5 picoseconds, which is much shorter when using pure MD methods (in the billisecond scale) . Also, we used density functional theory (DFT) methods to obtain the energy profile of guests passing through gates, as this does not require specification of a force field for the MOF degrees of freedom. In the DFT calculation, we only considered one gate of MOFs each time; as this greatly reduced the computational cost. Based on the obtained energy barrier values we computed the diffusion rate of alkane and alcohol in ZIF-8 using our model, which was in good agreement with experimental test results and the calculation values from standard MD model. Our model shows the advantage of obtaining accurate diffusion rates for guests in MOFs for a lower computational cost and shorter calculation time. Thus, our analytic model calculation is especially attractive for high-throughput computational screening of the dynamic performance of guests in a framework.

Visualization of Stereoselective Supramolecular Polymers by Chirality-Controlled Energy Transfer.

Science.gov (United States)

Sarkar, Aritra; Dhiman, Shikha; Chalishazar, Aditya; George, Subi J

2017-10-23

Chirality-driven self-sorting is envisaged to efficiently control functional properties in supramolecular materials. However, the challenge arises because of a lack of analytical methods to directly monitor the enantioselectivity of the resulting supramolecular assemblies. Presented herein are two fluorescent core-substituted naphthalene-diimide-based donor and acceptor molecules with minimal structural mismatch and they comprise strong self-recognizing chiral motifs to determine the self-sorting process. As a consequence, stereoselective supramolecular polymerization with an unprecedented chirality control over energy transfer has been achieved. This chirality-controlled energy transfer has been further exploited as an efficient probe to visualize microscopically the chirality driven self-sorting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reversible networks in supramolecular polymers

NARCIS (Netherlands)

Havermans - van Beek, D.J.M.

2007-01-01

Non–covalent interactions between low molecular weight polymers form the basis of supramolecular polymers. The material properties of such polymers are determined by the strength and lifetime of the non–covalent reversible interactions. Due to the reversibility of the interactions between the low

Supramolecular Complexation of Carbohydrates for the Bioavailability Enhancement of Poorly Soluble Drugs.

Science.gov (United States)

Cho, Eunae; Jung, Seunho

2015-10-27

In this review, a comprehensive overview of advances in the supramolecular complexes of carbohydrates and poorly soluble drugs is presented. Through the complexation process, poorly soluble drugs could be efficiently delivered to their desired destinations. Carbohydrates, the most abundant biomolecules, have diverse physicochemical properties owing to their inherent three-dimensional structures, hydrogen bonding, and molecular recognition abilities. In this regard, oligosaccharides and their derivatives have been utilized for the bioavailability enhancement of hydrophobic drugs via increasing the solubility or stability. By extension, polysaccharides and their derivatives can form self-assembled architectures with poorly soluble drugs and have shown increased bioavailability in terms of the sustained or controlled drug release. These supramolecular systems using carbohydrate will be developed consistently in the field of pharmaceutical and medical application.

Synthesis and characterization of protocatechuic acid-loaded gadolinium-layered double hydroxide and gold nanocomposite for theranostic application

Science.gov (United States)

Usman, Muhammad Sani; Hussein, Mohd Zobir; Kura, Aminu Umar; Fakurazi, Sharida; Masarudin, Mas Jaffri; Saad, Fathinul Fikri Ahmad

2018-03-01

A theranostic nanocomposite was developed using anticancer agent, protocatechuic acid (PA) and magnetic resonance imaging (MRI) contrast agent gadolinium nitrate (Gd) for simultaneous delivery using layered double hydroxide (LDH) as the delivery agent. Gold nanoparticles (AuNPs) were adsorbed on the surface of the LDH, which served as a complementary contrast agent. Based on the concept of supramolecular chemistry (SPC) and multimodal delivery system (MDS), the PA and Gd guests were first intercalated into the LDH host and subsequently AuNPs were surface adsorbed as the third guest. The nanohybrid developed was named MAPGAu. The MAPGAu was exposed to various characterizations at different stages of synthesis, starting with XRD analysis, which was used to confirm the intercalation episode and surface adsorption of the guest molecules. Consequently, FESEM, Hi-TEM, XRD, ICP-OES, CHNS, FTIR and UV-Vis analyses were done on the nanohybrids. The result of XRD analysis indicated successful intercalation of the Gd and PA as well the adsorption of AuNPs. The UV-Vis release study showed 90% of the intercalated drug was released at pH 4.8, which is the pH of the cancer cells. The FESEM and TEM micrographs obtained equally confirmed the formation of MAGPAu nanocomposite, with AuNPs conspicuously deposited on the LDH surface. The cytotoxicity study of the nanohybrid also showed insignificant toxicity to normal cell lines and significant toxicity to cancer cell lines. The developed MAGPAu nanocomposite has shown prospects for future theranostic cancer treatment.

Artificial muscle-like function from hierarchical supramolecular assembly of photoresponsive molecular motors

NARCIS (Netherlands)

Chen, Jiawen; Leung, Franco King-Chi; Stuart, Marc C A; Kajitani, Takashi; Fukushima, Takanori; van der Giessen, Erik; Feringa, Ben L

A striking feature of living systems is their ability to produce motility by amplification of collective molecular motion from the nanoscale up to macroscopic dimensions. Some of nature's protein motors, such as myosin in muscle tissue, consist of a hierarchical supramolecular assembly of very large

Drastic symmetry breaking in supramolecular organization of enantiomerically unbalanced monolayers at surfaces

NARCIS (Netherlands)

Haq, S.; Liu, N.; Humblot, V.; Jansen, A.P.J.; Raval, R.

2009-01-01

There is considerable interest in skewing the transmission of chirality, or 'handedness', from the molecular to the supramolecular level so that single-handed superstructures are created from mixed enantiomer systems. One approach is to flip the chirality of all the molecular building blocks to the

Bio-inspired supramolecular materials by orthogonal self-assembly of hydrogelators and phospholipids

NARCIS (Netherlands)

Boekhoven, J.; Brizard, AMA; Stuart, M. C A; Florusse, L.J.; Raffy, G.; Del Guerzo, A.; van Esch, J.H.

2016-01-01

The orthogonal self-assembly of multiple components is a powerful strategy towards the formation of complex biomimetic architectures, but so far the rules for designing such systems are unclear. Here we show how to identify orthogonal self-assembly at the supramolecular level and describe

Monosaccharides as Versatile Units for Water-Soluble Supramolecular Polymers.

Science.gov (United States)

Leenders, Christianus M A; Jansen, Gijs; Frissen, Martijn M M; Lafleur, René P M; Voets, Ilja K; Palmans, Anja R A; Meijer, E W

2016-03-18

We introduce monosaccharides as versatile water-soluble units to compatibilise supramolecular polymers based on the benzene-1,3,5-tricarboxamide (BTA) moiety with water. A library of monosaccharide-based BTAs is evaluated, varying the length of the alkyl chain (hexyl, octyl, decyl and dodecyl) separating the BTA and saccharide units, as well as the saccharide units (α-glucose, β-glucose, α-mannose and α-galactose). In all cases, the monosaccharides impart excellent water compatibility. The length of the alkyl chain is the determining factor to obtain either long, one-dimensional supramolecular polymers (dodecyl spacer), small aggregates (decyl spacer) or molecularly dissolved (octyl and hexyl) BTAs in water. For the BTAs comprising a dodecyl spacer, our results suggest that a cooperative self-assembly process is operative and that the introduction of different monosaccharides does not significantly change the self- assembly behaviour. Finally, we investigate the potential of post-assembly functionalisation of the formed supramolecular polymers by taking advantage of dynamic covalent bond formation between the monosaccharides and benzoxaboroles. We observe that the supramolecular polymers readily react with a fluorescent benzoxaborole derivative permitting imaging of these dynamic complexes by confocal fluorescence microscopy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Get Your Hotel Operations Team Onboard The Tricycle of Guest Service

OpenAIRE

Kennedy, Doug

2018-01-01

As hospitality industry trainers know, using symbols and models can help trainees grasp abstract concepts and make seemingly-complex paradigms easy to understand. Seems like is a good time for the hotel industry to update its model, so let’s get your team onboard The Tricycle of Guest Service. When you think about it, a tricycle is a perfect model for a positive guest experience. For one, it has three wheels, just like the three components of a memorable guest stay. The back wheels repres...

Synchronous fluorescence based biosensor for albumin determination by cooperative binding of fluorescence probe in a supra-biomolecular host-protein assembly.

Science.gov (United States)

Patra, Digambara

2010-01-15

A synchronous fluorescence probe based biosensor for estimation of albumin with high sensitivity and selectivity was developed. Unlike conventional fluorescence emission or excitation spectral measurements, synchronous fluorescence measurement offered exclusively a new synchronous fluorescence peak in the shorter wavelength range upon binding of chrysene with protein making it an easy identification tool for albumin determination. The cooperative binding of a fluorescence probe, chrysene, in a supramolecular host-protein assembly during various albumin assessments was investigated. The presence of supramolecular host molecules such as beta-cyclodextrin, curucurbit[6]uril or curucurbit[7]uril have little influence on sensitivity or limit of detection during albumin determination but reduced dramatically interference from various coexisting metal ion quenchers/enhancers. Using the present method the limit of detection for BSA and gamma-Globulin was found to be 0.005 microM which is more sensitive than reported values. Copyright 2009 Elsevier B.V. All rights reserved.

Preparation of C.I. Pigment 52:1 anion-pillared layered double hydroxide and the thermo- and photostability of the resulting intercalated material

Science.gov (United States)

Guo, Shengchang; Evans, David G.; Li, Dianqing

2006-05-01

Intercalation of 2-naphthalenecarboxylic acid, 4-((4-chloro-5-methyl-2-sulfophenyl) azo)-3-hydroxy-, calcium salt (1:1) (C.I. Pigment Red 52:1, also known as New Rubine S6B) into a layered double hydroxide (LDHs) host was carried out using MgAl NO3 LDHs as a precursor in an effort to improve the thermal and photo stability of the pigment. After intercalation, the powder X-ray diffraction (XRD) pattern shows that the basal spacing of the LDHs increased from 0.86 to 1.92 nm. Infrared spectra and TG DTA curves demonstrate that there are supramolecular host guest interactions. It was found that the intercalated material is more stable than the pristine pigment at high temperatures. The pigment anion-pillared LDHs also exhibit much higher photostablity to UV-light than the pristine pigment.

Quality of customer service: perceptions from guests in all-inclusive resorts in Jamaica

Science.gov (United States)

Joel L. Frater

2007-01-01

With data collected from guests in all-inclusive resorts in Jamaica, West Indies, the purposes of this study were to: (1) delineate unique dimensions of customer service perceptions among guests and (2) report the finding of a study that measured guests' perceptions of the quality of customer service in all-inclusive resorts. The study asked the following research...

Nonintegrated Host Association of Myrmecophilus tetramorii, a Specialist Myrmecophilous Ant Cricket (Orthoptera: Myrmecophilidae

Directory of Open Access Journals (Sweden)

Takashi Komatsu

2013-01-01

Full Text Available Myrmecophilus ant crickets (Orthoptera: Myrmecophilidae are typical ant guests. In Japan, about 10 species are recognized on the basis of morphological and molecular phylogenetic frameworks. Some of these species have restricted host ranges and behave intimately toward their host ant species (i.e., they are host specialist. We focused on one species, M. tetramorii, which uses the myrmicine ant Tetramorium tsushimae as its main host. All but one M. tetramorii individuals were collected specifically from nests of T. tsushimae in the field. However, behavioral observation showed that all individuals used in the experiment received hostile reactions from the host ants. There were no signs of intimate behaviors such as grooming of hosts or receipt of mouth-to-mouth feeding from hosts, which are seen in some host-specialist Myrmecophilus species among obligate host-ant species. Therefore, it may be that M. tetramorii is the species that is specialized to exploit the host by means other than chemical integration.

Selecting non-classified hotels in Kenya: what really matters for business guests?

Directory of Open Access Journals (Sweden)

Alex K Kivuva

2014-01-01

Full Text Available Non-classified hotels, which comprise small hotels and guest houses, are important accommodation providers offering limited services and products as compared to the classified hotels. Through guest satisfaction, they can achieve repeat business and also get new business through word of mouth from previous guests. The main focus is for the hoteliers to know exactly the determinants of selection of hotels by their guests. In this case, the focus was on non-classified hotels in Mtwapa town at the Kenyan coast. The study adopted a cross-sectional descriptive survey design. Results from this study clearly indicate that all aspects of hotel operations are important to business guests’ selection of a non-classified hotel. However, it was revealed that this was not on equal basis. Results indicate that the core product (guestroom comfortability, hygiene and cleanliness were the most important factors in determining guests’ selection of where to stay. This research therefore suggests that any efforts towards quality improvement in a hotel should focus primarily on ensuring customer satisfaction with the guestroom. While acknowledging the importance of all aspects of hotel operations, managers should recognize the importance of the guestroom and its facilities towards hotel selection and overall customer satisfaction. Therefore, it is imperative that managers channel their resources towards improving guest services in the guestrooms in accordance with the requirements of the clientele. This includes such aspects as the look of the guest rooms, facilities provided in the guest rooms and comfortability of the bed and mattress.

The Vital Components of Restaurant Quality that Affect Guest Satisfaction

Directory of Open Access Journals (Sweden)

Snježana Gagić

2013-10-01

Full Text Available Nowadays, the trend of dining in restaurants has become quite prominent in Serbia. Frequent restaurant visits are not only the reflection of satisfying hedonistic needs, but also the result of increasing number of single-person households as well as adjustment to the European business hours.In an increasingly competitive environment, restaurants must be focused on guests using marketing concepts that identify their needs thus leading to their satisfaction and increased retention.Service quality is fundamental component which produce higher levels of guest satisfaction, which in turn lead to higher sales revenue.The main purpose of this study was to examine the quality dimensions that affect guest satisfaction in restaurant industry. Food and beverage quality, the quality of service delivery, physical environment and price fairness are analyzed as a key components of restaurant experience. The results could be helpful tool for restaurant managers to invest their resources more efficiently, making changes to crucial quality attributes that elicit the guests’ satisfaction level. A management approach focused on guest satisfaction can improve restaurant business performance.

Organização supramolecular da ftalocianina de cobalto(II e seu efeito na oxidação do aminoácido cisteína Supramolecular organization of cobalt (II phthalocyanine on the pathway of cysteine oxidation

Directory of Open Access Journals (Sweden)

Amanda Costa Santos

2010-01-01

Full Text Available The interest in the chemistry of cobalt (II tetrasulfonated phthalocyanine (PcTsCo comes mainly from its macrocycle-ligand structure combined with their special chemical characteristics, such as high solubility, well-defined redox reactions and remarkable optical absorption in the visible region. In this work, we use layer-by-layer technique in order to assemble CoTsPc and poly(allylaminehydrochloride (PAH in hybrid supramolecular system. The electronic spectroscopy and cyclic voltammetry techniques were utilized to study PAH/CoTsPc multilayers growth and the cysteine catalytic oxidation. PAH/CoTsPc showed high electrochemical stability and worthwhile to mention is the remarkable influence of supramolecular arrangement on the final redox properties of the system.

Determination of paraquat in water samples using a sensitive fluorescent probe titration method.

Science.gov (United States)

Yao, Feihu; Liu, Hailong; Wang, Guangquan; Du, Liming; Yin, Xiaofen; Fu, Yunlong

2013-06-01

Paraquat (PQ), a nonselective herbicide, is non-fluorescent in aqueous solutions. Thus, its determination through direct fluorescent methods is not feasible. The supramolecular inclusion interaction of PQ with cucurbit[7]uril was studied by a fluorescent probe titration method. Significant quenching of the fluorescence intensity of the cucurbit[7]uril-coptisine fluorescent probe was observed with the addition of PQ. A new fluorescent probe titration method with high selectivity and sensitivity at the ng/mL level was developed to determine PQ in aqueous solutions with good precision and accuracy based on the significant quenching of the supramolecular complex fluorescence intensity. The proposed method was successfully used in the determination of PQ in lake water, tap water, well water, and ditch water in an agricultural area, with recoveries of 96.73% to 105.77%. The fluorescence quenching values (deltaF) showed a good linear relationship with PQ concentrations from 1.0 x 10(-8) to 1.2 x 10(-5) mol/L with a detection limit of 3.35 x 10(-9) mol/L. In addition, the interaction models of the supramolecular complexes formed between the host and the guest were established using theoretical calculations. The interaction mechanism between the cucurbit[7]uril and PQ was confirmed by 1H NMR spectroscopy.

Coevolution in host-parasite systems: behavioural strategies of slave-making ants and their hosts.

OpenAIRE

Foitzik, S.; DeHeer, C. J.; Hunjan, D. N.; Herbers, J. M.

2001-01-01

Recently, avian brood parasites and their hosts have emerged as model systems for the study of host-parasite coevolution. However, empirical studies of the highly analogous social parasites, which use the workers of another eusocial species to raise their own young, have never explicitly examined the dynamics of these systems from a coevolutionary perspective. Here, we demonstrate interpopulational variation in behavioural interactions between a socially parasitic slave-maker ant and its host...

The benefit of guest loyalty programmes | La Rose | Research in ...

African Journals Online (AJOL)

In the literature review of this research, the following aspects are discussed: a loyalty programme and its use; the sort of loyalty programmes; the effects of a loyalty programme; and the wishes and needs of a leisure guest. Surveys were divided among 46 leisure guests of Apollo Hotels and Resorts in order to collect data on ...

Exploring Environmental Awareness and Behavior among Guests at Hotels That Apply Water-Saving Measures

Directory of Open Access Journals (Sweden)

Ariadna Gabarda-Mallorquí

2018-04-01

Full Text Available The aim of this study was to investigate guest profiles at a hotel that has created a best-practices water management model to determine how different types of guests contribute to saving water during their stay. To do this, we analyzed levels of environmental awareness and pro-environmental behavior among the guests. Information was gathered through 648 structured surveys with guests at Hotel Samba in the Spanish seaside resort of Lloret de Mar between September 2015 and August 2016. Cluster analysis revealed four profiles of guests with different sociodemographic characteristics and different levels of awareness and proactivity in relation to water conservation. We combined our findings to develop a framework that illustrates how the two dimensions of environmental awareness and pro-environmental behavior are related in this setting. This article provides new insights into how hotel guests’ environmental awareness and engagement can influence a hotel’s water-saving efforts. These insights should help hotel operators to devise new, guest-centered strategies for saving water.

Solvent Clathrate Driven Dynamic Stereomutation of a Supramolecular Polymer with Molecular Pockets.

Science.gov (United States)

Kulkarni, Chidambar; Korevaar, Peter A; Bejagam, Karteek K; Palmans, Anja R A; Meijer, E W; George, Subi J

2017-10-04

Control over the helical organization of synthetic supramolecular systems is intensively pursued to manifest chirality in a wide range of applications ranging from electron spin filters to artificial enzymes. Typically, switching the helicity of supramolecular assemblies involves external stimuli or kinetic traps. However, efforts to achieve helix reversal under thermodynamic control and to understand the phenomena at a molecular level are scarce. Here we present a unique example of helix reversal (stereomutation) under thermodynamic control in the self-assembly of a coronene bisimide that has a 3,5-dialkoxy substitution on the imide phenyl groups (CBI-35CH), leading to "molecular pockets" in the assembly. The stereomutation was observed only if the CBI monomer possesses molecular pockets. Detailed chiroptical studies performed in alkane solvents with different molecular structures reveal that solvent molecules intercalate or form clathrates within the molecular pockets of CBI-35CH at low temperature (263 K), thereby triggering the stereomutation. The interplay among the helical assembly, molecular pockets, and solvent molecules is further unraveled by explicit solvent molecular dynamics simulations. Our results demonstrate how the molecular design of self-assembling building blocks can orchestrate the organization of surrounding solvent molecules, which in turn dictates the helical organization of the resulting supramolecular assembly.

Supramolecular protein immobilization on lipid bilayers

NARCIS (Netherlands)

Bosmans, R.P.G.; Hendriksen, W.E.; Verheijden, Mark Lloyd; Eelkema, R.; Jonkheijm, Pascal; van Esch, J.H.; Brunsveld, Luc

2015-01-01

Protein immobilization on surfaces, and on lipid bilayers specifically, has great potential in biomolecular and biotechnological research. Of current special interest is the immobilization of proteins using supramolecular noncovalent interactions. This allows for a reversible immobilization and

Data from: Two different strategies of host manipulation allow parasites to persist in intermediate-definitive host systems

NARCIS (Netherlands)

Vries, de Lana; Langevelde, van F.

2017-01-01

Trophically-transmitted parasites start their development in an intermediate host, before they finish the development in their definitive host when the definitive host preys on the intermediate host. In intermediate-definitive host systems, two strategies of host manipulation have been evolved:

Importance of satisfaction and guests experience in hotel business organizations

Directory of Open Access Journals (Sweden)

Milošević Srđan

2012-01-01

Full Text Available Hotel companies which operate in today's competitive environment must constantly work on improving their products and services, at the request of their guests. Customer satisfaction is the key to retaining existing and attracting new guests. To achieve this goal, managers in the hotel organizations have become aware of the fact that the quality of staying in hotel represent unique experience for tourists. Lot of papers are dealing with the exploration of this topic, it only proves its importance nowadays. However, insufficient attention is paid to the simultaneous study of experience of guests and their satisfaction through the offered models (indexes that are created for this purpose. The purpose of this paper is to show the importance of these issues and identify their potential symbiosis.

Polyoxometalates paneling through {Mo2O2S2} coordination: cation-directed conformations and chemistry of a supramolecular hexameric scaffold.

Science.gov (United States)

Marrot, Jérôme; Pilette, Marie Anne; Haouas, Mohamed; Floquet, Sébastien; Taulelle, Francis; López, Xavier; Poblet, Josep M; Cadot, Emmanuel

2012-01-25

The chemical system based on the [Mo(2)O(2)S(2)(OH(2))(6)](2+) aqua cation (noted L) and the trivacant [AsW(9)O(33)](9-) polyoxometalate (noted POM) has been investigated. Depending upon the ionic strength and the nature of the alkali cations, these complementary components assemble to yield three different architectures derived as hexamer (1), tetramer (2), and dimer (3). This series of clusters displays the same stoichiometry {POM(6)L(9)}(36-), {POM(4)L(6)}(24-), and {POM(2)L(3)}(12-) for 1, 2, and 3, respectively, and their conditions of formation differ mainly by the nature and the concentration of the alkali cation (from Li to Cs). Structural characterizations of 1 reveal a large hexameric supramolecular scaffold (about 25 Å in diameter), which encloses a large internal hole (about 200 Å(3)) filled by water molecules and alkali cations (Na(+) or K(+)). The hexameric scaffold 1 exhibits a rare flexibility property evidenced in the solid state by two distinct conformations, either eclipsed (1a) or staggered-off (1b). Both conformations appear clearly separated by a large twist angle (~40°) and depend mainly on the composition of the internal hole. Structure of anion 2 shows a tetrahedral arrangement where the four POM units and the six connecting {Mo(2)O(2)S(2)} linkers are located at the corners and at the edges, respectively. The structure of anion 3 corresponds to the simplest arrangement, described as a dimeric association of two POM units linked by three {Mo(2)S(2)O(2)} pillars. Stability of the hexameric scaffold has been investigated in solution by (183)W and (39)K NMR and by UV-vis, showing that stability of 1 depends strongly on the proportion of potassium ions, which interfere through host-guest exchange. Density functional methodology (DFT) has been applied to compute the geometries and energies of dimer (3), tetramer (2) and hexamer (1) based on {AsW(9)O(33)} (POM) and {Mo(2)O(2)S(2)} (L) units. Calculations tend to show that internal cations act

Pyrrole-Pyridine and Pyrrole-Naphthyridine Hosts for Anion Recognition

Directory of Open Access Journals (Sweden)

M. Angeles García

2015-05-01

Full Text Available The association constants of the complexes formed by two hosts containing pyrrole, amide and azine (pyridine and 1,8-naphthyridine groups and six guests, all monoanions (Cl−, CH3CO2−, NO3−, H2PO4−, BF4−, PF6−, have been determined using NMR titrations. The X-ray crystal structure of the host N2,N5-bis(6-methylpyridin-2-yl-3,4-diphenyl-1H-pyrrole- 2,5-dicarboxamide (1 has been solved (P21/c monoclinic space group. B3LYP/6-31G(d,p and calculations were carried out in an attempt to rationalize the trends observed in the experimental association constants.

Utilizing redox-chemistry to elucidate the nature of exciton transitions in supramolecular dye nanotubes

NARCIS (Netherlands)

Eisele, D. M.; Cone, C. W.; Bloemsma, E. A.; Vlaming, S. M.; van der Kwaak, C. G. F.; Silbey, R. J.; Bawendi, M. G.; Knoester, J.; Rabe, J. P.; Vanden Bout, D. A.

Supramolecular assemblies that interact with light have recently garnered much interest as well-defined nanoscale materials for electronic excitation energy collection and transport. However, to control such complex systems it is essential to understand how their various parts interact and whether

Understanding Periodic Dislocations in 2D Supramolecular Crystals: The PFP/Ag(111) Interface

DEFF Research Database (Denmark)

Goiri, E.; García Lastra, Juan Maria; Corso, M.

2012-01-01

In-plane dislocation networks arise in both inorganic and organic films as a way of relieving the elastic strain that builds up at the substrate interface. In molecule/surface systems, supramolecular interactions are weak and more complex (compared to the atomic bonds in inorganic films), and the...

Efficient luminescent materials based on the incorporation of a Eu(III)tris-(bipyridine-carboxylate) complex in mesoporous hybrid silicate hosts

International Nuclear Information System (INIS)

Botelho, M.B.S.; Queiroz, T.B. de; Eckert, H.; Camargo, A.S.S. de

2016-01-01

The study of the photoluminescent characteristics of host–guest systems based on highly emissive trivalent rare earth complexes such as Eu 3+ – tris-bipyridine-carboxylate, immobilized in solid state host matrices, is motivated by their potential applications in optoelectronic devices and bioanalytical systems. Besides offering the possibility of designing a favorable environment to improve the photophysical properties of the guest molecules, encapsulation in porous solids also serves to protect such molecules, prevents leakage (especially critical for bio-applications) and ultimately leads to more robust and versatile materials. Among the most interesting possible host matrices are mesoporous silica and hybrids (organo-silicates) in the form of powders (MCM-41 like) and transparent bulk or film xerogels. In this work we report the synthesis of highly efficient red emitting materials based on the wet impregnation of such host matrices with the new complex Eu[4-(4′-tert-butyl-biphenyl-4-yl)-2,2′-bipyridine-6-carboxyl] 3 (“[ t Bu–COO] 3 Eu”) whose synthesis and photophysical characterization was recently reported. Prior to the incorporation, the host matrices were thoroughly characterized by solid state 29 Si and 1 H NMR, N 2 adsorption/desorption isotherms, and scanning electron microscopy (SEM). Incorporation and retention of the complex molecules are found to be significantly higher in the phenyl-modified hybrid samples than in the regular mesoporous silica, suggesting efficient immobilization of the complex by π–π interactions. Long excited state lifetimes (up to 1.7 ms comparable to 1.8 ms for the complex in solution), and high quantum yields (up to 65%, versus 85% for the complex in solution) were measured for the bulk xerogel materials, suggesting the potential use of thin films for lighting and bioanalytical applications. - Highlights: • New Eu(III) complex in mesoporous hybrid matrices leads to highly emissive material • Matrix

Efficient luminescent materials based on the incorporation of a Eu(III)tris-(bipyridine-carboxylate) complex in mesoporous hybrid silicate hosts

Energy Technology Data Exchange (ETDEWEB)

Botelho, M.B.S. [Instituto de Física de São Carlos, Universidade de São Paulo, 13566-590 São Carlos, SP (Brazil); Universidade de Brasilia, 70910-900 Brasilia, DF (Brazil); Queiroz, T.B. de [Instituto de Física de São Carlos, Universidade de São Paulo, 13566-590 São Carlos, SP (Brazil); Eckert, H. [Instituto de Física de São Carlos, Universidade de São Paulo, 13566-590 São Carlos, SP (Brazil); Institut für Physikalische Chemie, Westfälische Wilhelms Universität Münster, D-48149 Münster (Germany); Camargo, A.S.S. de, E-mail: andreasc@ifsc.usp.br [Instituto de Física de São Carlos, Universidade de São Paulo, 13566-590 São Carlos, SP (Brazil)

2016-02-15

The study of the photoluminescent characteristics of host–guest systems based on highly emissive trivalent rare earth complexes such as Eu{sup 3+} – tris-bipyridine-carboxylate, immobilized in solid state host matrices, is motivated by their potential applications in optoelectronic devices and bioanalytical systems. Besides offering the possibility of designing a favorable environment to improve the photophysical properties of the guest molecules, encapsulation in porous solids also serves to protect such molecules, prevents leakage (especially critical for bio-applications) and ultimately leads to more robust and versatile materials. Among the most interesting possible host matrices are mesoporous silica and hybrids (organo-silicates) in the form of powders (MCM-41 like) and transparent bulk or film xerogels. In this work we report the synthesis of highly efficient red emitting materials based on the wet impregnation of such host matrices with the new complex Eu[4-(4′-tert-butyl-biphenyl-4-yl)-2,2′-bipyridine-6-carboxyl]{sub 3} (“[{sup t}Bu–COO]{sub 3}Eu”) whose synthesis and photophysical characterization was recently reported. Prior to the incorporation, the host matrices were thoroughly characterized by solid state {sup 29}Si and {sup 1}H NMR, N{sub 2} adsorption/desorption isotherms, and scanning electron microscopy (SEM). Incorporation and retention of the complex molecules are found to be significantly higher in the phenyl-modified hybrid samples than in the regular mesoporous silica, suggesting efficient immobilization of the complex by π–π interactions. Long excited state lifetimes (up to 1.7 ms comparable to 1.8 ms for the complex in solution), and high quantum yields (up to 65%, versus 85% for the complex in solution) were measured for the bulk xerogel materials, suggesting the potential use of thin films for lighting and bioanalytical applications. - Highlights: • New Eu(III) complex in mesoporous hybrid matrices leads to highly

Self-Assembly of Coordinative Supramolecular Polygons with Open Binding Sites.

Science.gov (United States)

Zheng, Yao-Rong; Wang, Ming; Kobayashi, Shiho; Stang, Peter J

2011-04-27

The design and synthesis of coordinative supramolecular polygons with open binding sites is described. Coordination-driven self-assembly of 2,6-bis(pyridin-4-ylethynyl)pyridine with 60° and 120° organoplatinum acceptors results in quantitative formation of a supramolecular rhomboid and hexagon, respectively, both bearing open pyridyl binding sites. The structures were determined by multinuclear ((31)P and (1)H) NMR spectroscopy and electrospray ionization (ESI) mass spectrometry, along with a computational study.

Supramolecular fluorene based materials

OpenAIRE

Abbel, R.J.

2008-01-01

This thesis describes the use of noncovalent interactions in order to manipulate and control the self-assembly and morphology of electroactive fluorene-based materials. The supramolecular arrangement of p-conjugated polymers and oligomers can strongly influence their electronic and photophysical properties. Therefore, a detailed understanding of such organisation processes is essential for the optimisation of the performance of these materials as applied in optoelectronic devices. In order to...

Solid structures of the stepwise self-assembled copillar[5]arene-based supramolecular polymers

International Nuclear Information System (INIS)

Park, Yeon Sil; Hwang, Seong Min; Shin, Jae Yeon; Paek, Kyung Soo

2016-01-01

Development of supramolecular polymer has attracted much interest because of their interesting properties such as stimuli-responsiveness, recycling, self-healing and degradability, and their consequential applications. The essential feature of this class of polymers is the self-assembly of discrete monomeric subunits via non-covalent interactions or dynamic covalent bonds. Among the many monomeric subunits, pillar[n]arenes have been ideal building blocks for the fabrication of polymeric supramolecules because of their intrinsic characteristics. The ring-shaped morphologies in supramolecular polymer P are probably due to the tendency of the end-to-end connection in the solid state of long flexible supramolecular chains. The size increase of nano-rings as the stepwise addition increases might be due to the fact that the linear supramolecular polymer P in solution seems to be maintained until the nano-ring formation by solidification

Solid structures of the stepwise self-assembled copillar[5]arene-based supramolecular polymers

Energy Technology Data Exchange (ETDEWEB)

Park, Yeon Sil; Hwang, Seong Min; Shin, Jae Yeon; Paek, Kyung Soo [Dept. of Chemistry, Soongsil University, Seoul (Korea, Republic of)

2016-10-15

Development of supramolecular polymer has attracted much interest because of their interesting properties such as stimuli-responsiveness, recycling, self-healing and degradability, and their consequential applications. The essential feature of this class of polymers is the self-assembly of discrete monomeric subunits via non-covalent interactions or dynamic covalent bonds. Among the many monomeric subunits, pillar[n]arenes have been ideal building blocks for the fabrication of polymeric supramolecules because of their intrinsic characteristics. The ring-shaped morphologies in supramolecular polymer P are probably due to the tendency of the end-to-end connection in the solid state of long flexible supramolecular chains. The size increase of nano-rings as the stepwise addition increases might be due to the fact that the linear supramolecular polymer P in solution seems to be maintained until the nano-ring formation by solidification.

Side-Chain Supramolecular Polymers Employing Conformer Independent Triple Hydrogen Bonding Arrays

OpenAIRE

Gooch, Adam; Murphy, Natasha S.; Thomson, Neil H.; Wilson, Andrew J.

2013-01-01

Derivatives of thymine have been extensively used to promote supramolecular materials assembly. Such derivatives can be synthetically challenging to access and may be susceptible to degradation. The current article uses a conformer-independent acceptor-donor-acceptor array (ureidopyrimidine) which forms moderate affinity interactions with diamidopyridine derivatives to effect supramolecular blend formation between polystyrene and poly(methyl methacrylate) polymers obtained by RAFT which have ...

Supramolecular photocatalyst of RGO-cyclodextrin-TiO2

International Nuclear Information System (INIS)

Shen, Jianfeng; Li, Na; Ye, Mingxin

2013-01-01

Graphical abstract: Supramolecular photocatalyst of RGO-cyclodextrin-TiO 2 was achieved, which showed high photocatalytic activity and adsorption capacity. Highlights: •Supramolecular photocatalyst of RGO-cyclodextrin-TiO 2 was achieved. •β-CD molecules acted as linkers between RGO and monodisperse TiO 2 nanoparticles. •Reduction of GO and preparation of RGO-cyclodextrin-TiO 2 was simultaneous. •The prepared RGO-cyclodextrin-TiO 2 shows high photocatalytic activity and adsorption capacity. -- Abstract: Reduced graphene oxide (RGO)/β-cyclodextrin (β-CD)/titanium oxide (TiO 2 ) supramolecular photocatalyst was synthesized with a one-pot hydrothermal method. The reducing process was accomplished with the attaching of β-CD and generation of TiO 2 . β-CD acted as a linker between RGO and monodisperse TiO 2 nanoparticles. The structure and composition of the hybrid had been characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, thermal gravimetric analysis, X-ray diffraction and Transmission electron microscopy. The as-prepared RGO-CD-TiO 2 showed significant enhanced performance for phenol and Cr (VI) removal, due to the effective transfer of photo-generated electron from TiO2 to RGO and improved absorbance performance of the hybrid

Laser Spectroscopic and Theoretical Studies of Encapsulation Complexes of Calix[4]arene

Energy Technology Data Exchange (ETDEWEB)

Kaneko, Shohei; Inokuchi, Yoshiya; Ebata, Takayuki; Apra, Edoardo; Xantheas, Sotiris S.

2011-10-13

The complexes between the host calix[4]arene (C4A) and various guest molecules such as NH3, N2, CH4, and C2H2 have been investigated via experimental and theoretical methods. The S1-S0 electronic spectra of these guest-host complexes are observed by mass-selected resonant two-photon ionization (R2PI) and laser induced fluorescence (LIF) spectroscopy. The infrared (IR) spectra of the complexes formed in molecular beams are obtained by IR-UV double resonance (IR-UV DR) and IR photodissociation (IRPD) spectroscopy. The supramolecular structures of the complexes are investigated by electronic structure methods (density functional and second order perturbation theory). The current results for the various molecular guests are put in perspective with the previously reported ones for the C4A-Rare Gas (Rg) (Phys. Chem. Chem. Phys. 2007, 126, 141101) and C4A-H2O complexes (J. Phys. Chem. A, 2010, 114, 2967). The electronic spectra of the complexes of C4A with N2, CH4 and C2H2 exhibit red-shifts of similar magnitudes with the ones observed for the C4A-Rg complexes, whereas the complexes of C4A with H2O and NH3 show much larger red-shifts. Most of the IR-UV DR spectra of the complexes, except for C4A-C2H2, show a broad hydrogen bonded OH stretching band with a peak at ~3160 cm-1. The analysis of the experimental results, in agreement with the ones resulted from the electronic structure calculations, suggest that C4A preferentially forms endo-complexes with all the guest species reported in this study. We discuss the similarities and differences of the structures, binding energies and the nature of the interaction between the C4A host and the various guest species. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy

Supramolecular interactions in the solid state

Directory of Open Access Journals (Sweden)

Giuseppe Resnati

2015-11-01

Full Text Available In the last few decades, supramolecular chemistry has been at the forefront of chemical research, with the aim of understanding chemistry beyond the covalent bond. Since the long-range periodicity in crystals is a product of the directionally specific short-range intermolecular interactions that are responsible for molecular assembly, analysis of crystalline solids provides a primary means to investigate intermolecular interactions and recognition phenomena. This article discusses some areas of contemporary research involving supramolecular interactions in the solid state. The topics covered are: (1 an overview and historical review of halogen bonding; (2 exploring non-ambient conditions to investigate intermolecular interactions in crystals; (3 the role of intermolecular interactions in morphotropy, being the link between isostructurality and polymorphism; (4 strategic realisation of kinetic coordination polymers by exploiting multi-interactive linker molecules. The discussion touches upon many of the prerequisites for controlled preparation and characterization of crystalline materials.

Self-Healing Natural Rubber with Tailorable Mechanical Properties Based on Ionic Supramolecular Hybrid Network.

Science.gov (United States)

Xu, Chuanhui; Cao, Liming; Huang, Xunhui; Chen, Yukun; Lin, Baofeng; Fu, Lihua

2017-08-30

In most cases, the strength of self-healing supramolecular rubber based on noncovalent bonds is in the order of KPa, which is a challenge for their further applications. Incorporation of conventional fillers can effectively enhance the strength of rubbers, but usually accompanied by a sacrifice of self-healing capability due to that the filler system is independent of the reversible supramolecular network. In the present work, in situ reaction of methacrylic acid (MAA) and excess zinc oxide (ZnO) was realized in natural rubber (NR). Ionic cross-links in NR matrix were obtained by limiting the covalent cross-linking of NR molecules and allowing the in situ polymerization of MAA/ZnO. Because of the natural affinity between Zn 2+ ion-rich domains and ZnO, the residual nano ZnO participated in formation of a reversible ionic supramolecular hybrid network, thus having little obstructions on the reconstruction of ionic cross-links. Meanwhile, the well dispersed residual ZnO could tailor the mechanical properties of NR by changing the MAA/ZnO molar ratios. The present study thus provides a simple method to fabricate a new self-healing NR with tailorable mechanical properties that may have more potential applications.

Hologenomics: Systems-Level Host Biology.

Science.gov (United States)

Theis, Kevin R

2018-01-01

The hologenome concept of evolution is a hypothesis explaining host evolution in the context of the host microbiomes. As a hypothesis, it needs to be evaluated, especially with respect to the extent of fidelity of transgenerational coassociation of host and microbial lineages and the relative fitness consequences of repeated associations within natural holobiont populations. Behavioral ecologists are in a prime position to test these predictions because they typically focus on animal phenotypes that are quantifiable, conduct studies over multiple generations within natural animal populations, and collect metadata on genetic relatedness and relative reproductive success within these populations. Regardless of the conclusion on the hologenome concept as an evolutionary hypothesis, a hologenomic perspective has applied value as a systems-level framework for host biology, including in medicine. Specifically, it emphasizes investigating the multivarious and dynamic interactions between patient genomes and the genomes of their diverse microbiota when attempting to elucidate etiologies of complex, noninfectious diseases.

Preparation of supramolecular hydrogel-enzyme hybrids exhibiting biomolecule-responsive gel degradation.

Science.gov (United States)

Shigemitsu, Hajime; Fujisaku, Takahiro; Onogi, Shoji; Yoshii, Tatsuyuki; Ikeda, Masato; Hamachi, Itaru

2016-09-01

Hydrogelators are small, self-assembling molecules that form supramolecular nanofiber networks that exhibit unique dynamic properties. Development of supramolecular hydrogels that degrade in response to various biomolecules could potentially be used for applications in areas such as drug delivery and diagnostics. Here we provide a synthetic procedure for preparing redox-responsive supramolecular hydrogelators that are used to create hydrogels that degrade in response to oxidizing or reducing conditions. The synthesis takes ∼2-4 d, and it can potentially be carried out in parallel to prepare multiple hydrogelator candidates. This described solid-phase peptide synthesis protocol can be used to produce previously described hydrogelators or to construct a focused molecular library to efficiently discover and optimize new hydrogelators. In addition, we describe the preparation of redox-responsive supramolecular hydrogel-enzyme hybrids that are created by mixing aqueous solutions of hydrogelators and enzymes, which requires 2 h for completion. The resultant supramolecular hydrogel-enzyme hybrids exhibit gel degradation in response to various biomolecules, and can be rationally designed by connecting the chemical reactions of the hydrogelators with enzymatic reactions. Gel degradation in response to biomolecules as triggers occurs within a few hours. We also describe the preparation of hydrogel-enzyme hybrids arrayed on flat glass slides, enabling high-throughput analysis of biomolecules such as glucose, uric acid, lactate and so on by gel degradation, which is detectable by the naked eye. The protocol requires ∼6 h to prepare the hydrogel-enzyme hybrid array and to complete the biomolecule assay.

Hydrogen bonding in tight environments

DEFF Research Database (Denmark)

Pirrotta, Alessandro; Solomon, Gemma C.; Franco, Ignacio

2016-01-01

The single-molecule force spectroscopy of a prototypical class of hydrogen-bonded complexes is computationally investigated. The complexes consist of derivatives of a barbituric acid and a Hamilton receptor that can form up to six simultaneous hydrogen bonds. The force-extension (F-L) isotherms...... of the host-guest complexes are simulated using classical molecular dynamics and the MM3 force field, for which a refined set of hydrogen bond parameters was developed from MP2 ab initio computations. The F-L curves exhibit peaks that signal conformational changes during elongation, the most prominent...... of which is in the 60-180 pN range and corresponds to the force required to break the hydrogen bonds. These peaks in the F-L curves are shown to be sensitive to relatively small changes in the chemical structure of the host molecule. Thermodynamic insights into the supramolecular assembly were obtained...

Relationship between the cohesion of guest particles on the flow behaviour of interactive mixtures.

Science.gov (United States)

Mangal, Sharad; Gengenbach, Thomas; Millington-Smith, Doug; Armstrong, Brian; Morton, David A V; Larson, Ian

2016-05-01

In this study, we aimed to investigate the effects cohesion of small surface-engineered guest binder particles on the flow behaviour of interactive mixtures. Polyvinylpyrrolidone (PVP) - a model pharmaceutical binder - was spray-dried with varying l-leucine feed concentrations to create small surface-engineered binder particles with varying cohesion. These spray-dried formulations were characterised by their particle size distribution, morphology and cohesion. Interactive mixtures were produced by blending these spray-dried formulations with paracetamol. The resultant blends were visualised under scanning electron microscope to confirm formation of interactive mixtures. Surface coverage of paracetamol by guest particles as well as the flow behaviour of these mixtures were examined. The flow performance of interactive mixtures was evaluated using measurements of conditioned bulk density, basic flowability energy, aeration energy and compressibility. With higher feed l-leucine concentrations, the surface roughness of small binder particles increased, while their cohesion decreased. Visual inspection of the SEM images of the blends indicated that the guest particles adhered to the surface of paracetamol resulting in effective formation of interactive mixtures. These images also showed that the low-cohesion guest particles were better de-agglomerated that consequently formed a more homogeneous interactive mixture with paracetamol compared with high-cohesion formulations. The flow performance of interactive mixtures changed as a function of the cohesion of the guest particles. Interactive mixtures with low-cohesion guest binder particles showed notably improved bulk flow performance compared with those containing high-cohesion guest binder particles. Thus, our study suggests that the cohesion of guest particles dictates the flow performance of interactive mixtures. Crown Copyright © 2016. Published by Elsevier B.V. All rights reserved.

Applications of supramolecular chemistry

CERN Document Server

Schneider, Hans-Jörg

2012-01-01

""The time is ripe for the present volume, which gathers thorough presentations of the numerous actually realized or potentially accessible applications of supramolecular chemistry by a number of the leading figures in the field. The variety of topics covered is witness to the diversity of the approaches and the areas of implementation…a broad and timely panorama of the field assembling an eminent roster of contributors.""-Jean-Marie Lehn, 1987 Noble Prize Winner in Chemistry

A rapid pathway toward a superb gene delivery system: programming structural and functional diversity into a supramolecular nanoparticle library.

Science.gov (United States)

Wang, Hao; Liu, Kan; Chen, Kuan-Ju; Lu, Yujie; Wang, Shutao; Lin, Wei-Yu; Guo, Feng; Kamei, Ken-ichiro; Chen, Yi-Chun; Ohashi, Minori; Wang, Mingwei; Garcia, Mitch André; Zhao, Xing-Zhong; Shen, Clifton K-F; Tseng, Hsian-Rong

2010-10-26

Nanoparticles are regarded as promising transfection reagents for effective and safe delivery of nucleic acids into a specific type of cells or tissues providing an alternative manipulation/therapy strategy to viral gene delivery. However, the current process of searching novel delivery materials is limited due to conventional low-throughput and time-consuming multistep synthetic approaches. Additionally, conventional approaches are frequently accompanied with unpredictability and continual optimization refinements, impeding flexible generation of material diversity creating a major obstacle to achieving high transfection performance. Here we have demonstrated a rapid developmental pathway toward highly efficient gene delivery systems by leveraging the powers of a supramolecular synthetic approach and a custom-designed digital microreactor. Using the digital microreactor, broad structural/functional diversity can be programmed into a library of DNA-encapsulated supramolecular nanoparticles (DNA⊂SNPs) by systematically altering the mixing ratios of molecular building blocks and a DNA plasmid. In vitro transfection studies with DNA⊂SNPs library identified the DNA⊂SNPs with the highest gene transfection efficiency, which can be attributed to cooperative effects of structures and surface chemistry of DNA⊂SNPs. We envision such a rapid developmental pathway can be adopted for generating nanoparticle-based vectors for delivery of a variety of loads.

Light Responsive Two-Component Supramolecular Hydrogel: A Sensitive Platform for Humidity Sensors

KAUST Repository

Samai, Suman

2016-02-15

The supramolecular assembly of anionic azobenzene dicarboxylate and cationic cetyltrimethylammonium bromide (CTAB) formed a stimuli responsive hydrogel with a critical gelation concentration (CGC) of 0.33 wt%. This self-sustainable two-component system was able to repair damage upon light irradiation. Moreover, it was successfully employed in the fabrication of highly sensitive humidity sensors for the first time.

Light Responsive Two-Component Supramolecular Hydrogel: A Sensitive Platform for Humidity Sensors

KAUST Repository

Samai, Suman; Sapsanis, Christos; Patil, Sachin; Ezzeddine, Alaa; Moosa, Basem; Omran, Hesham; Emwas, Abdul-Hamid M.; Salama, Khaled N.; Khashab, Niveen M.

2016-01-01

The supramolecular assembly of anionic azobenzene dicarboxylate and cationic cetyltrimethylammonium bromide (CTAB) formed a stimuli responsive hydrogel with a critical gelation concentration (CGC) of 0.33 wt%. This self-sustainable two-component system was able to repair damage upon light irradiation. Moreover, it was successfully employed in the fabrication of highly sensitive humidity sensors for the first time.

 α-Cyclodextrin dimer complexes of dopamine and levodopa derivatives to assess drug delivery to the central nervous system: ADME and molecular docking studies

Directory of Open Access Journals (Sweden)

Shityakov S

2012-06-01

Full Text Available Sergey Shityakov, Jens Broscheit, Carola FörsterDepartment of Anesthesiology and Critical Care, University of Würzburg, Würzburg, GermanyAbstract: This paper attempts to predict and emphasize molecular interactions of dopamine, levodopa, and their derivatives (Dopimid compounds containing 2-phenyl-imidazopyridine moiety with the α-cyclodextrin dimer in order to assess and improve drug delivery to the central nervous system. The molecular docking method is used to determine the energetic profiles, hydrogen bond formation, and hydrophobic effect of 14 host–guest complexes. The results show that the “chemical branching” represented by additional ethyl-acetate residue is energetically unfavorable and promotes a conformational shift due to the high root mean square deviation levels. This phenomenon is characterized by a low number of H-bonds and a significant decrease of the host–guest hydrophobic potential surface. Finally, the overall docking procedure presents a powerful rationale for screening and analyzing various sets of promising drug-like chemical compounds in the fields of supramolecular chemistry, molecular sensing, synthetic receptors, and nanobiotechnology.Keywords: dopamine, levodopa, Dopimid compounds, α-CD dimer, molecular docking, complexation

A room with a viewpoint revisited: descriptive norms and hotel guests' towel reuse behavior.

Science.gov (United States)

Bohner, Gerd; Schlüter, Lena E

2014-01-01

Field experiments on descriptive norms as a means to increase hotel guests' towel reuse [1] were replicated and extended. In two hotels in Germany (Study 1: N = 724; Study 2: N = 204), descriptive norm messages suggesting that 75% of guests had reused their towels, or a standard message appealing to environmental concerns, were placed in guests' bathrooms. Descriptive norm messages varied in terms of proximity of the reference group ("hotel guests" vs. "guests in this room") and temporal proximity (currently vs. two years previous). Reuse of towels was unobtrusively recorded. Results showed that reuse rates were high overall and that both standard and descriptive norm messages increased reuse rates compared to a no-message baseline. However, descriptive norm messages were not more effective than the standard message, and effects of proximity were inconsistent across studies. Discussion addresses cultural and conceptual issues in comparing the present findings with previous ones.

A supramolecular strategy for self-mobile adsorption sites in affinity membrane.

Science.gov (United States)

Lin, Ligang; Dong, Meimei; Liu, Chunyu; Wei, Chenjie; Wang, Yuanyuan; Sun, Hui; Ye, Hui

2014-09-01

Disclosed here is the design of a novel supramolecular membrane with self-mobile adsorption sites for biomolecules purification. In the 3D micropore channels of membrane matrix, the ligands are conjugated onto the cyclic compounds in polyrotaxanes for protein adsorption. During membrane filtration, the adsorption sites can rotate and/or slide along the axial chain, which results in the enhanced adsorption capacity. The excellent performance of supra-molecular membrane is related with the dynamic working manner of adsorption sites, which plays a crucial role on avoiding spatial mismatching and short-circuit effect. The supra-molecular strategy described here has general suggestions for the "sites" involved technologies such as catalysis, adsorption, and sensors, which is of broad interest. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrothermal crystal growth and Vernier structures of the metal benzenedicarboxylates MIL-47 and MIL-53 containing guest molecules of benzenecarboxylic acid

International Nuclear Information System (INIS)

Wang, Xiqu; Jacobson, Allan J.

2016-01-01

The nanoporous frameworks VO(bdc), MIL-47, and M(OH)(bdc), MIL-53; bdc=1,4-benzenedicarboxylate, can absorb various guest species in their channels. As synthesized, the channels are filled with H 2 bdc molecules that have been reported to be disordered, except for [In(OH)bdc](H 2 bdc) 3/4 , 1, which has a inorganic-organic hybrid Vernier structure with the H 2 bdc molecules forming an ordered sublattice. Based on X-ray data from large single crystals grown by hydrothermal techniques, similar Vernier structures have been found for MIL-47, [VO(bdc)](H 2 bdc) 5/7 , 2, MIL-53Al, [Al(OH)(bdc)](H 2 bdc) 11/16 , 3, and MIL-53Ga, [Ga(OH)(bdc)](H 2 bdc) 12/17 , 4. The Vernier structures of 2–4 at room temperature were determined based on superstructure unit cells that index both host and guest sublattices: 2, space group P2 1 , a=23.903(2), b=17.191(2), c=25.722(2) Å, β=105.914(8)°; 3, P2 1 /n, a=105.224(4), b=12.2441(5), c=17.0143(6) Å, β=89.99(1)°; 4, P2 1 , a=114.562(5), b=12.1503(5), c=17.4275(7) Å, β=89.99(1)°. The number of guest H 2 bdc molecules per framework metal ion is determined by the ratio of the repeat distances of the two sublattices which depends on the size of the metal ion in the octahedral chain. The octahedral chains are parallel to [201] in 2, and to [100] in 3 and 4. Remarkably, all atoms in 3 and 4 show significant sinusoidal modulations transverse to the chain axis. - Graphical abstract: The sinusoidal modulation along the channel axis direction involving all atoms in the structure of [Al(OH)(bdc)](H 2 bdc) 11/16 . - Highlights: • Crystal growth of MIL-47, MIL-53Al, and MIL-53Ga. • The Vernier structures have corner-sharing MO6 octrahedral chains and chains of H2BDC molecules. • The stoichiometry is determined by the ratio of the host framework to the guest H2BDC column lengths. • A correlation is established between the stoichiometry and the radius of the metal ion. • All atoms in the Al and Ga compounds show sinusoidal

An outstanding guest

CERN Multimedia

2004-01-01

The person celebrating CERN's 25th anniversary whose photograph we published last week was not just any guest. Readers have pointed out that it was Wim Klein, whose remarkable abilities are part of CERN's history. Well known as one of the best "human calculators", Wim was recruited by CERN in 1957 to verify computer programs, which at the time were still stumbling. Moreover, he regularly beat their speed in calculating and gave breath-taking demonstrations. During one such demonstration in September 1973, he calculated the 19th root of a 133-digit number in less than 2 minutes !

Co-assembly of Peptide Amphiphiles and Lipids into Supramolecular Nanostructures Driven by Anion-π Interactions

Energy Technology Data Exchange (ETDEWEB)

Yu, Zhilin; Erbas, Aykut; Tantakitti, Faifan; Palmer, Liam C.; Jackman, Joshua A.; Olvera de la Cruz, Monica; Cho, Nam-Joon; Stupp, Samuel I. (Nanyang); (NWU)

2017-06-01

Co-assembly of binary systems driven by specific non-covalent interactions can greatly expand the structural and functional space of supramolecular nanostructures. We report here on the self-assembly of peptide amphiphiles and fatty acids driven primarily by anion-π interactions. The peptide sequences investigated were functionalized with a perfluorinated phenylalanine residue to promote anion-π interactions with carboxylate headgroups in fatty acids. These interactions were verified here by NMR and circular dichroism experiments as well as investigated using atomistic simulations. Positioning the aromatic units close to the N-terminus of the peptide backbone near the hydrophobic core of cylindrical nanofibers leads to strong anion-π interactions between both components. With a low content of dodecanoic acid in this position, the cylindrical morphology is preserved. However, as the aromatic units are moved along the peptide backbone away from the hydrophobic core, the interactions with dodecanoic acid transform the cylindrical supramolecular morphology into ribbon-like structures. Increasing the ratio of dodecanoic acid to PA leads to either the formation of large vesicles in the binary systems where the anion-π interactions are strong, or a heterogeneous mixture of assemblies when the peptide amphiphiles associate weakly with dodecanoic acid. Our findings reveal how co-assembly involving designed specific interactions can drastically change supramolecular morphology and even cross from nano to micro scales.

Recruiting Future Engineers Through Effective Guest Speaking In Elementary School Classrooms

Energy Technology Data Exchange (ETDEWEB)

Kevin Young

2007-11-01

In this paper, the author describes how engineers can increase the number of future engineers by volunteering as guest speakers in the elementary school classroom. The paper is divided into three main subjects. First, the importance of engineers speaking directly with young students is discussed. Next, several best practice techniques for speaking with young students are described. Finally, information on getting started as a guest speaker is presented, and a list of resources available to guest speakers is provided. The guest engineer speaking to an elementary school audience (ages 6-11) performs a critical role in encouraging young students to pursue a career in engineering. Often, he or she is the first engineer these students meet in person, providing a crucial first impression of the engineering career field and a positive visual image of what an engineer really looks like. A dynamic speaker presenting a well-delivered talk creates a lasting, positive impression on students, influencing their future decisions to pursue careers in engineering. By reaching these students early in life, the guest speaker will help dispel the many prevailing stereotypes about engineers which discourage so many students, especially young women, from considering this career. The guest speaker can ensure young students gain a positive first impression of engineers and the engineering career field by following some best practice techniques in preparing for and delivering their presentation. The author, an electrical engineer, developed these best practice techniques over the past 10 years while presenting over 350 talks on engineering subjects to elementary school students as a volunteer speaker with the U.S. Department of Energy, Idaho National Laboratory’s Speakers Bureau. Every engineer can make a meaningful contribution toward reversing the predicted shortfall of future engineers by volunteering to speak with young students at the elementary school level. Elementary school

Surface-Assisted Self-Assembly Strategies Leading to Supramolecular Hydrogels.

Science.gov (United States)

Vigier-Carrière, Cécile; Boulmedais, Fouzia; Schaaf, Pierre; Jierry, Loïc

2018-02-05

Localized molecular self-assembly processes leading to the growth of nanostructures exclusively from the surface of a material is one of the great challenges in surface chemistry. In the last decade, several works have been reported on the ability of modified or unmodified surfaces to manage the self-assembly of low-molecular-weight hydrogelators (LMWH) resulting in localized supramolecular hydrogel coatings mainly based on nanofiber architectures. This Minireview highlights all strategies that have emerged recently to initiate and localize LMWH supramolecular hydrogel formation, their related fundamental issues and applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phthalocyanine-nanocarbon ensembles: from discrete molecular and supramolecular systems to hybrid nanomaterials.

Science.gov (United States)

Bottari, Giovanni; de la Torre, Gema; Torres, Tomas

2015-04-21

Phthalocyanines (Pcs) are macrocyclic and aromatic compounds that present unique electronic features such as high molar absorption coefficients, rich redox chemistry, and photoinduced energy/electron transfer abilities that can be modulated as a function of the electronic character of their counterparts in donor-acceptor (D-A) ensembles. In this context, carbon nanostructures such as fullerenes, carbon nanotubes (CNTs), and, more recently, graphene are among the most suitable Pc "companions". Pc-C60 ensembles have been for a long time the main actors in this field, due to the commercial availability of C60 and the well-established synthetic methods for its functionalization. As a result, many Pc-C60 architectures have been prepared, featuring different connectivities (covalent or supramolecular), intermolecular interactions (self-organized or molecularly dispersed species), and Pc HOMO/LUMO levels. All these elements provide a versatile toolbox for tuning the photophysical properties in terms of the type of process (photoinduced energy/electron transfer), the nature of the interactions between the electroactive units (through bond or space), and the kinetics of the formation/decay of the photogenerated species. Some recent trends in this field include the preparation of stimuli-responsive multicomponent systems with tunable photophysical properties and highly ordered nanoarchitectures and surface-supported systems showing high charge mobilities. A breakthrough in the Pc-nanocarbon field was the appearance of CNTs and graphene, which opened a new avenue for the preparation of intriguing photoresponsive hybrid ensembles showing light-stimulated charge separation. The scarce solubility of these 1-D and 2-D nanocarbons, together with their lower reactivity with respect to C60 stemming from their less strained sp(2) carbon networks, has not meant an unsurmountable limitation for the preparation of variety of Pc-based hybrids. These systems, which show improved

A room with a viewpoint revisited: descriptive norms and hotel guests' towel reuse behavior.

Directory of Open Access Journals (Sweden)

Gerd Bohner

Full Text Available Field experiments on descriptive norms as a means to increase hotel guests' towel reuse [1] were replicated and extended. In two hotels in Germany (Study 1: N = 724; Study 2: N = 204, descriptive norm messages suggesting that 75% of guests had reused their towels, or a standard message appealing to environmental concerns, were placed in guests' bathrooms. Descriptive norm messages varied in terms of proximity of the reference group ("hotel guests" vs. "guests in this room" and temporal proximity (currently vs. two years previous. Reuse of towels was unobtrusively recorded. Results showed that reuse rates were high overall and that both standard and descriptive norm messages increased reuse rates compared to a no-message baseline. However, descriptive norm messages were not more effective than the standard message, and effects of proximity were inconsistent across studies. Discussion addresses cultural and conceptual issues in comparing the present findings with previous ones.

Facile preparation of luminescent and intelligent gold nanodots based on supramolecular self-assembly

International Nuclear Information System (INIS)

Shi Yunfeng; Li Sujuan; Zhou Yahui; Zhai Qingpan; Hu Mengyue; Cai Fensha; Du Jimin; Liang Jiamiao; Zhu Xinyuan

2012-01-01

A new strategy for preparing luminescent and intelligent gold nanodots based on supramolecular self-assembly is described in this paper. The supramolecular self-assembly was initiated through electrostatic interactions and ion pairing between palmitic acid and hyperbranched poly(ethylenimine). The resulting structures not only have the dynamic reversible properties of supramolecules but also possess torispherical and highly branched architectures. Thus they can be regarded as a new kind of ideal nanoreactor for preparing intelligent Au nanodots. By preparing Au nanodots within this kind of supramolecular self-assembly, the environmental sensitivity of intelligent polymers and the optical, electrical properties of Au nanodots can be combined, endowing the Au nanodots with intelligence. In this paper, a supramolecular self-assembly process based on dendritic poly(ethylenimine) and palmitic acid was designed and then applied to prepare fluorescent and size-controlled Au nanodots. The pH response of Au nanodots embodied by phase transfer from oil phase to water phase was also investigated. (paper)

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry.

Science.gov (United States)

Cremer, Paul S; Flood, Amar H; Gibb, Bruce C; Mobley, David L

2017-12-19

On planet Earth, water is everywhere: the majority of the surface is covered with it; it is a key component of all life; its vapour and droplets fill the lower atmosphere; and even rocks contain it and undergo geomorphological changes because of it. A community of physical scientists largely drives studies of the chemistry of water and aqueous solutions, with expertise in biochemistry, spectroscopy and computer modelling. More recently, however, supramolecular chemists - with their expertise in macrocyclic synthesis and measuring supramolecular interactions - have renewed their interest in water-mediated non-covalent interactions. These two groups offer complementary expertise that, if harnessed, offer to accelerate our understanding of aqueous supramolecular chemistry and water writ large. This Review summarizes the state-of-the-art of the two fields, and highlights where there is latent chemical space for collaborative exploration by the two groups.

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

Science.gov (United States)

Cremer, Paul S.; Flood, Amar H.; Gibb, Bruce C.; Mobley, David L.

2018-01-01

On planet Earth, water is everywhere: the majority of the surface is covered with it; it is a key component of all life; its vapour and droplets fill the lower atmosphere; and even rocks contain it and undergo geomorphological changes because of it. A community of physical scientists largely drives studies of the chemistry of water and aqueous solutions, with expertise in biochemistry, spectroscopy and computer modelling. More recently, however, supramolecular chemists -- with their expertise in macrocyclic synthesis and measuring supramolecular interactions -- have renewed their interest in water-mediated non-covalent interactions. These two groups offer complementary expertise that, if harnessed, offer to accelerate our understanding of aqueous supramolecular chemistry and water writ large. This Review summarizes the state-of-the-art of the two fields, and highlights where there is latent chemical space for collaborative exploration by the two groups.

Dihydrogen phosphate-water tape and layers vs dihydrogen phosphate layers tuned by hydrophobic isomeric pyridine-diamine functionalized molecules

Science.gov (United States)

Huang, Jing; Liu, Tong-Peng; Huo, Li-Hua; Deng, Zhao-Peng; Gao, Shan

2017-01-01

Assembly of six isomeric pyridine-diamine-based molecules, N,N‧-bis(pyridin-4-ylmethyl)ethane-1,2-diamine (M1), N,N‧-bis(pyridin-3-ylmethyl)ethane-1,2-diamine (M2), N,N‧-bis(pyridin-2-ylmethyl)ethane-1,2-diamine (M3), N,N‧-bis(pyridin-4-ylmethyl)propane-1,3-diamine (M4), N,N‧-bis(pyridin-3-ylmethyl)propane-1,2-diamine (M5), and N,N‧-bis(pyridin-2-ylmethyl)propane-1,3-diamine (M6), with phosphoric acid (H3PO4) in different ratio (1:2 and 1:4), leads to the formation of nine salts, H2M12+·2H2PO4-·4H2O (1), H2M22+·2H2PO4-·2H2O (2), H2M32+·2H2PO4-·2H2O (3), H4M14+·4H2PO4- (4), H4M24+·4H2PO4- (5), H4M34+·4H2PO4- (6), H2M42+·2H2PO4-·3H2O (7), 2H2M52+·4H2PO4-·2H3PO4 (8), and H2M62+·2H2PO4- (9), which have been characterized by elemental analysis, IR, TG, PL, powder and single-crystal X-ray diffraction. Structural analyses indicate that hydrogen-bonding patterns of H2PO4- anions, conformation of protonated cations can effectively influence the supramolecular architectures through diverse non-covalent interactions. Hydrous salts 1-3 and 7 present 2D and 3D host-guest supramolecular networks, in which the connection of H2PO4- anions and water molecules generates diverse tape and layer motifs. H2PO4- anions in anhydrous salts 4-6 interconnect with each other through hydrogen bonds to form two types of layers, which are joined by discrete H4M4+ cations into 3D inorganic-organic hybrid supramolecular networks. Salts 8-9 also present 2D and 3D host-guest supramolecular networks where the interconnection of H2PO4- anions and its combination with H3PO4 molecules leads to diverse layers. Luminescent analyses indicate that salts 1-9 exhibit violet and blue emission maximum in the range of 390-467 nm at room temperature.

Supramolecular Encapsulation of Vitamin B6 by Macrocyclic Nanocontainer Cucurbit[7]uril

Directory of Open Access Journals (Sweden)

Wanying Li

2015-01-01

Full Text Available A pharmaceutically and biologically relevant molecule, pyridoxine hydrochloride (vitamin B6, was encapsulated inside the cavity of a molecular container, cucurbit[7]uril (CB[7], in aqueous solution. The CB[7] based “nanocapsule” of vitamin B6 has been investigated for the first time, via 1H NMR and UV-visible spectroscopic titrations (including Job’s plot and ab initio molecular modeling. The results have demonstrated that vitamin B6 forms stable host-guest complexes within CB[7] in 1 : 1 stoichiometry, with a binding affinity of (4.0±0.5×103 M−1. Such a nanocapsule could potentially find application in vitamin B6 formulation for the purpose of enhancing the stability, absorption, and delivery of this important vitamin.

The role of supramolecular chemistry in stimuli responsive and hierarchically structured functional organic materials

NARCIS (Netherlands)

Schenning, A.P.H.J.; Bastiaansen, C.W.M.; Broer, D.J.; Debije, M.G.

2014-01-01

ABSTRACT: In this review, we show the important role of supramolecular chemistry in the fabrication of stimuli responsive and hierarchically structured liquid crystalline polymer networks. Supramolecular interactions can be used to create three dimensional order or as molecular triggers in materials

Spectrofluorimetric study of the β-cyclodextrin-dapsone-linear alcohol supramolecular system and determination of dapsone

International Nuclear Information System (INIS)

Ma Li; Tang Bo; Chu Chun

2002-01-01

Dapsone (DDS) forms a 1:1 supramolecular complex with β-cyclodextrin (β-CD) both in the absence and presence of linear alcohols. The apparent association constants (K app ) were measured using a steady-state fluorescence method. K app decreases linearly with an increasing number of carbon atoms in the chain of the alcohol. We attribute this to a competition between dapsone and linear alcohol for the β-CD hydrophobic cavity as detailed analysis of K app as a function of the concentration of alcohol suggests that the interactions in the β-CD-dapsone-linear alcohol system do not result in the formation of ternary supramolecular complex. Quenching the fluorescence of dapsone with NaI shows that the β-CD cavity acts as a shield against contact between dapsone and this aqueous phase quencher, while addition of alcohols inhibits this protective effect. This again suggests that alcohols occupy the space within the β-CD cavity with the result that dapsone molecules are forced to reside in the aqueous environment. Based on the significant enhancement of the fluorescence intensity of dapsone produced through complex formation, a spectrofluorimetric method for the determination of dapsone in bulk aqueous solution in the presence of β-CD is developed. The linear relationship between the fluorescence intensity and dapsone concentration was obtained in the range of 3.39 to 1.50x10 3 ng ml -1 , with a correlation coefficient (r) of 0.9998. The detection limit was 1.02 ng ml -1 . There was no interference from the excipients normally used in tablet formulations. The application of the present method to the determination of dapsone in tablets and human plasma gave satisfactory results and was compared with the pharmacopoeia method

The Reciprocal Principle of Selectand-Selector-Systems in Supramolecular Chromatography †.

Science.gov (United States)

Schurig, Volker

2016-11-15

In selective chromatography and electromigration methods, supramolecular recognition of selectands and selectors is due to the fast and reversible formation of association complexes governed by thermodynamics. Whereas the selectand molecules to be separated are always present in the mobile phase, the selector employed for the separation of the selectands is either part of the stationary phase or is added to the mobile phase. By the reciprocal principle, the roles of selector and selectand can be reversed. In this contribution in honor of Professor Stig Allenmark, the evolution of the reciprocal principle in chromatography is reviewed and its advantages and limitations are outlined. Various reciprocal scenarios, including library approaches, are discussed in efforts to optimize selectivity in separation science.

Low driving voltage simplified tandem organic light-emitting devices by using exciplex-forming hosts

Science.gov (United States)

Zhou, Dong-Ying; Cui, Lin-Song; Zhang, Ying-Jie; Liao, Liang-Sheng; Aziz, Hany

2014-10-01

Tandem organic light-emitting devices (OLEDs), i.e., OLEDs containing multiple electroluminescence (EL) units that are vertically stacked, are attracting significant interest because of their ability to realize high current efficiency and long operational lifetime. However, stacking multiple EL units in tandem OLEDs increases driving voltage and complicates fabrication process relative to their standard single unit counterparts. In this paper, we demonstrate low driving voltage tandem OLEDs via utilizing exciplex-forming hosts in the EL units instead of conventional host materials. The use of exciplex-forming hosts reduces the charge injection barriers and the trapping of charges on guest molecules, resulting in the lower driving voltage. The use of exciplex-forming hosts also allows using fewer layers, hence simpler EL configuration which is beneficial for reducing the fabrication complexity of tandem OLEDs.

A Student-Centered Guest Lecturing: A Constructivism Approach to Promote Student Engagement

Science.gov (United States)

Li, Lei; Guo, Rong

2015-01-01

Student engagement has become a big challenge in higher education, especially when distance learning is getting more and more popular. Guest lecturing is a popular method to bring relevance to the classroom and engage in students. Ground on the theory of constructivism, this paper introduces a student-centered guest lecturing that allows students…

Design of supramolecular ordered systems for mesoscopic colloids and molecular composites. Progress report, November 10, 1993--June 10, 1994

Energy Technology Data Exchange (ETDEWEB)

1995-01-01

During this reporting period, the authors group has been active in five areas of research: (1) improvements on their x-ray instrumentation at the SUNY Beamline, National Synchrotron Light Source (NSLS) so that they can perform new experiments which are not accessible otherwise; (2) characterization of functionalized hairy rod polymers designed for studying the macromolecular structures in molecular composites; (3) investigation of supramolecular ordered systems composed mainly of block copolymers from dilute to concentrated solutions, including the gel state; (4) evolution of crystalline structures in polymer blends and melts; and (5) multiphase structure of segment polyurethanes.

Strong and Reversible Monovalent Supramolecular Protein Immobilization

NARCIS (Netherlands)

Young, Jacqui F.; Nguyen, Hoang D.; Yang, Lanti; Huskens, Jurriaan; Jonkheijm, Pascal; Brunsveld, Luc

2010-01-01

Proteins with an iron clasp: Site-selective incorporation of a ferrocene molecule into a protein allows for easy, strong, and reversible supramolecular protein immobilization through a selective monovalent interaction of the ferrocene with a cucurbit[7]uril immobilized on a gold surface. The

Stoichiometry-Controlled Inversion of Supramolecular Chirality in Nanostructures Co-assembled with Bipyridines.

Science.gov (United States)

Wang, Fang; Feng, Chuan-Liang

2018-02-01

To control supramolecular chirality of the co-assembled nanostructures, one of the remaining issues is how stoichiometry of the different molecules involved in co-assembly influence chiral transformation. Through co-assembly of achiral 1,4-bis(pyrid-4-yl)benzene and chiral phenylalanine-glycine derivative hydrogelators, stoichiometry is found to be an effective tool for controlling supramolecular chirality inversion processes. This inversion is mainly mediated by a delicate balance between intermolecular hydrogen bonding interactions and π-π stacking of the two components, which may subtly change the stacking of the molecules, in turn, the self-assembled nanostructures. This study exemplifies a simplistic way to invert the handedness of chiral nanostructures and provide fundamental understanding of the inherent principles of supramolecular chirality. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular Rotor and Translator at Work: On-Surface Movement of Single Atoms.

Science.gov (United States)

Ohmann, Robin; Meyer, Jörg; Nickel, Anja; Echeverria, Jorge; Grisolia, Maricarmen; Joachim, Christian; Moresco, Francesca; Cuniberti, Gianaurelio

2015-08-25

A supramolecular nanostructure composed of four 4-acetylbiphenyl molecules and self-assembled on Au (111) was loaded with single Au adatoms and studied by scanning tunneling microscopy at low temperature. By applying voltage pulses to the supramolecular structure, the loaded Au atoms can be rotated and translated in a controlled manner. The manipulation of the gold adatoms is driven neither by mechanical interaction nor by direct electronic excitation. At the electronic resonance and driven by the tunneling current intensity, the supramolecular nanostructure performs a small amount of work of about 8 × 10(-21) J, while transporting the single Au atom from one adsorption site to the next. Using the measured average excitation time necessary to induce the movement, we determine the mechanical motive power of the device, yielding about 3 × 10(-21) W.

Combining Host-based and network-based intrusion detection system

African Journals Online (AJOL)

These attacks were simulated using hping. The proposed system is implemented in Java. The results show that the proposed system is able to detect attacks both from within (host-based) and outside sources (network-based). Key Words: Intrusion Detection System (IDS), Host-based, Network-based, Signature, Security log.

Reversible Self-Assembly of Supramolecular Vesicles and Nanofibers Driven by Chalcogen-Bonding Interactions.

Science.gov (United States)

Chen, Liang; Xiang, Jun; Zhao, Yue; Yan, Qiang

2018-05-29

Chalcogen-bonding interactions have been viewed as new noncovalent forces in supramolecular chemistry. However, harnessing chalcogen bonds to drive molecular self-assembly processes is still unexplored. Here we report for the first time a novel class of supra-amphiphiles formed by Te···O or Se···O chalcogen-bonding interactions, and their self-assembly into supramolecular vesicles and nanofibers. A quasi-calix[4]chalcogenadiazole (C4Ch) as macrocyclic donor and a tailed pyridine N-oxide surfactant as molecular acceptor are designed to construct the donor-acceptor complex via chalcogen-chalcogen connection between the chalcogenadiazole moieties and oxide anion. The affinity of such chalcogen-bonding can dictate the geometry of supra-amphiphiles, driving diverse self-assembled morphologies. Furthermore, the reversible disassembly of these nanostructures can be promoted by introducing competing anions, such as halide ions, or by decreasing the systemic pH value.

Interactions of Native Cyclodextrins with Metal Ions and Inorganic Nanoparticles: Fertile Landscape for Chemistry and Materials Science.

Science.gov (United States)

Prochowicz, Daniel; Kornowicz, Arkadiusz; Lewiński, Janusz

2017-11-22

Readily available cyclodextrins (CDs) with an inherent hydrophobic internal cavity and hydrophilic external surface are macrocyclic entities that display a combination of molecular recognition and complexation properties with vital implications for host-guest supramolecular chemistry. While the host-guest chemistry of CDs has been widely recognized and led to their exploitation in a variety of important functions over the last five decades, these naturally occurring macrocyclic systems have emerged only recently as promising macrocyclic molecules to fabricate environmentally benign functional nanomaterials. This review surveys the development in the field paying special attention to the synthesis and emerging uses of various unmodified CD-metal complexes and CD-inorganic nanoparticle systems and identifies possible future directions. The association of a hydrophobic cavity of CDs with metal ions or various inorganic nanoparticles is a very appealing strategy for controlling the inorganic subunits properties in the very competitive water environment. In this review we provide the most prominent examples of unmodified CDs' inclusion complexes with organometallic guests and update the research in this field from the past decade. We discuss also the coordination flexibility of native CDs to metal ions in CD-based metal complexes and summarize the progress in the synthesis and characterization of CD-metal complexes and their use in catalysis and sensing as well as construction of molecular magnets. Then we provide a comprehensive overview of emerging applications of native CDs in materials science and nanotechnology. Remarkably, in the past few years CDs have appeared as attractive building units for the synthesis of carbohydrate metal-organic frameworks (CD-MOFs) in a combination of alkali-metal cations. The preparation of this new class of highly porous materials and their applications in the separation of small molecules, the loading of drug molecules, as well as

Structure and dynamics in low-dimensional guest-host systems

Energy Technology Data Exchange (ETDEWEB)

John E. Fischer

2000-05-01

This is the final report of the fourth of four three year grants of the same title. The program evolved from an earlier DOE grant on graphite intercalation compounds. Since its inception eight years ago, the focus evolved continuously from conjugated polymers to fullerenes, disordered carbons for Li-ion battery applications, and most recently carbon nanotubes, with side excursion back to GIC's to exploit a recent advance in synthesis of a potentially exciting new phase. The unifying themes are the versatility of carbon in forming novel solids, and the flexibility of intercalation chemistry to provide new materials with potentially useful properties.

Supramolecular architectures in layer-by-layer films of single-walled carbon nanotubes, chitosan and cobalt (II) phthalocyanine

International Nuclear Information System (INIS)

Sousa Luz, Roberto A. de; Martins, Marccus Victor A.; Magalhaes, Janildo L.; Siqueira, Jose R.; Zucolotto, Valtencir; Oliveira, Osvaldo N.; Crespilho, Frank N.; Cantanhede da Silva, Welter

2011-01-01

Highlights: → Platforms were assembled from cobalt phthalocyanine, chitosan and carbon nanotubes. → Supramolecular organization of multilayer films was investigated. → Increase of the supramolecular charge transfer after carbon nanotube incorporation. → Functional modulation based on constitutional dynamic chemistry was achieved. - Abstract: The building of supramolecular structures in nanostructured films has been exploited for a number of applications, with the film properties being controlled at the molecular level. In this study, we report on the layer-by-layer (LbL) films combining cobalt (II) tetrasulfonated phthalocyanine (CoTsPc), chitosan (Chit) and single-walled carbon nanotubes (SWCNTs) in two architectures, {Chit/CoTsPc} n and {Chit-SWCNTs/CoTsPc} n (n = 1-10). The physicochemical properties of the films were evaluated and the multilayer formation was monitored with microgravimetry measurements using a quartz microbalance crystal and an electrochemical technique. According to atomic force microscopy (AFM) results, the incorporation of SWCNTs caused the films to be thicker, with a thickness ca. 3 fold that of a 2-bilayer LbL film with no SWCNTs. Cyclic voltammetry revealed a quasi-reversible, one electron process with E 1/2 at -0.65 V (vs SCE) and an irreversible oxidation process at 0.80 V in a physiological medium for both systems, which can be attributed to [CoTsPc(I)] 5- /[CoTsPc(II)] 4- and CoTsPc(II) to CoTsPc(III), respectively. The {Chit-SWCNTs/CoTsPc} 5 multilayer film exhibited an increased faradaic current, probably associated with the supramolecular charge transfer interaction between cobalt phthalocyanine and SWCNTs. The results demonstrate that an intimate contact at the supramolecular level between functional SWCNTs immobilized into biocompatible chitosan polymer and CoTsPc improves the electron flow from CoTsPc redox sites to the electrode surface.

Correlation as a Determinant of Configurational Entropy in Supramolecular and Protein Systems

Science.gov (United States)

2015-01-01

For biomolecules in solution, changes in configurational entropy are thought to contribute substantially to the free energies of processes like binding and conformational change. In principle, the configurational entropy can be strongly affected by pairwise and higher-order correlations among conformational degrees of freedom. However, the literature offers mixed perspectives regarding the contributions that changes in correlations make to changes in configurational entropy for such processes. Here we take advantage of powerful techniques for simulation and entropy analysis to carry out rigorous in silico studies of correlation in binding and conformational changes. In particular, we apply information-theoretic expansions of the configurational entropy to well-sampled molecular dynamics simulations of a model host–guest system and the protein bovine pancreatic trypsin inhibitor. The results bear on the interpretation of NMR data, as they indicate that changes in correlation are important determinants of entropy changes for biologically relevant processes and that changes in correlation may either balance or reinforce changes in first-order entropy. The results also highlight the importance of main-chain torsions as contributors to changes in protein configurational entropy. As simulation techniques grow in power, the mathematical techniques used here will offer new opportunities to answer challenging questions about complex molecular systems. PMID:24702693

Chemical Sensors Based on Cyclodextrin Derivatives.

Science.gov (United States)

Ogoshi, Tomoki; Harada, Akira

2008-08-25

This review focuses on chemical sensors based on cyclodextrin (CD) derivatives. This has been a field of classical interest, and is now of current interest for numerous scientists. First, typical chemical sensors using chromophore appended CDs are mentioned. Various "turn-off" and "turn-on" fluorescent chemical sensors, in which fluorescence intensity was decreased or increased by complexation with guest molecules, respectively, were synthesized. Dye modified CDs and photoactive metal ion-ligand complex appended CDs, metallocyclodextrins, were also applied for chemical sensors. Furthermore, recent novel approaches to chemical sensing systems using supramolecular structures such as CD dimers, trimers and cooperative binding systems of CDs with the other macrocycle [2]rotaxane and supramolecular polymers consisting of CD units are mentioned. New chemical sensors using hybrids of CDs with p-conjugated polymers, peptides, DNA, nanocarbons and nanoparticles are also described in this review.

Magnetic ordering in TCNQ-based metal–organic frameworks with host–guest interactions

Energy Technology Data Exchange (ETDEWEB)

Zhang, Xuan; Saber, Mohamed R.; Prosvirin, Andrey P.; Reibenspies, Joseph H.; Sun, Lei; Ballesteros-Rivas, Maria; Zhao, Hanhua; Dunbar, Kim R. (MIT); (TAM)

2015-09-03

Host–guest interactions between the aromatic molecules benzene, toluene, aniline and nitrobenzene and the redox-active TCNQ-based metal–organic framework (MOF), Fe(TCNQ)(4,4'-bpy) (1) (TCNQ = 7,7,8,8-tetracyanoquinodimethane), have been found to modulate spontaneous magnetization behaviours at low temperatures. An analogous MOF, Mn(TCNQ)(4,4'-bpy) (2) with isotropic Mn(II) ions as well as the two-dimensional compound Fe(TCNQ)(DMF)2·2DMF (3·2DMF), were also prepared as models for studying the effects of single-ion magnetic anisotropy and structural distortion on spin canting. The results indicate guest-dependent long range magnetic ordering occurs at low temperatures, which correlates with the electrostatic and steric effects of the incorporated aromatic guests.

A polyamidoamine dendrimer-streptavidin supramolecular architecture for biosensor development.

Science.gov (United States)

Soda, N; Arotiba, O A

2017-12-01

A novel polyamidoamine dendrimer-streptavidin supramolecular architecture suitable as a versatile platform for biosensor development is reported. The dendrimer was electrodeposited on a glassy carbon electrode via cyclic voltammetry. The dendrimer electrode was further modified with streptavidin by electrostatic attraction upon drop coating. The platform i.e. the dendrimer-streptavidin modified electrode was electrochemically interrogated in phosphate buffer, ferrocyanide and H 2 O 2 . The dendrimer-streptavidin platform was used in the preparation of a simple DNA biosensor as a proof of concept. The supramolecular architecture of dendrimer-streptavidin was stable, electroactive and thus lends itself as a versatile immobilisation layer for any biotinylated bioreceptors in biosensor development. Copyright © 2017 Elsevier B.V. All rights reserved.

Electroluminescence Properties of IrQ(ppy)2 Dual-Emitter Organometallic Compound in Organic Light-Emitting Devices

Science.gov (United States)

Ciobotaru, Constantin Claudiu; Polosan, Silviu; Ciobotaru, Iulia Corina

2018-02-01

This paper reports the influence of the charge carrier mobility on the electroluminescent properties of a dual-emitter organometallic compound dispersed in two conjugated organic small-molecule host materials and embedded in organic light-emitting devices (OLEDs). The electroluminescent processes in OLEDs are strongly influenced by the host-guest interaction. The charge carrier mobility in the host material plays an important role in the electroluminescent processes but also depends on the triplet-triplet interaction with the organometallic compound. The low charge carrier mobility in 4,4'-bis( N-carbazolyl)-1,1'-biphenyl (CBP) host material reduces the electroluminescent processes, but they are slightly enhanced by the triplet-triplet exothermic charge transfer. The higher charge carrier mobility in the case of N, N'-bis(3-methylphenyl)- N, N'-diphenylbenzidine (TPD) host material influences the electroluminescent processes by the endothermic energy transfer at room temperature, which facilitates the triplet-triplet harvesting in the host-guest system. The excitation is transferred to the guest molecules by triplet-triplet interaction as a Dexter transfer, which occurs by endothermic transfer from the triplet exciton in the host to the triplet exciton in the guest.

Enzymatic Dissolution of Biocomposite Solids Consisting of Phosphopeptides to Form Supramolecular Hydrogels

KAUST Repository

Shi, Junfeng; Yuan, Dan; Haburcak, Richard; Zhang, Qiang; Zhao, Chao; Zhang, Xixiang; Xu, Bing

2015-01-01

Enzyme-catalyzed dephosphorylation is essential for biomineralization and bone metabolism. Here we report the exploration of using enzymatic reaction to transform biocomposites of phosphopeptides and calcium (or strontium) ions to supramolecular hydrogels as a mimic of enzymatic dissolution of biominerals. 31P NMR shows that strong affinity between the phosphopeptides and alkaline metal ions (e.g., Ca2+ or Sr2+) induces the formation of biocomposites as precipitates. Electron microscopy reveals that the enzymatic reaction regulates the morphological transition from particles to nanofibers. Rheology confirms the formation of a rigid hydrogel. As the first example of enzyme-instructed dissolution of a solid to form supramolecular nanofibers/hydrogels, this work provides an approach to generate soft materials with desired properties, expands the application of supramolecular hydrogelators, and offers insights to control the demineralization of calcified soft tissues.

Enzymatic Dissolution of Biocomposite Solids Consisting of Phosphopeptides to Form Supramolecular Hydrogels

KAUST Repository

Shi, Junfeng

2015-10-14

Enzyme-catalyzed dephosphorylation is essential for biomineralization and bone metabolism. Here we report the exploration of using enzymatic reaction to transform biocomposites of phosphopeptides and calcium (or strontium) ions to supramolecular hydrogels as a mimic of enzymatic dissolution of biominerals. 31P NMR shows that strong affinity between the phosphopeptides and alkaline metal ions (e.g., Ca2+ or Sr2+) induces the formation of biocomposites as precipitates. Electron microscopy reveals that the enzymatic reaction regulates the morphological transition from particles to nanofibers. Rheology confirms the formation of a rigid hydrogel. As the first example of enzyme-instructed dissolution of a solid to form supramolecular nanofibers/hydrogels, this work provides an approach to generate soft materials with desired properties, expands the application of supramolecular hydrogelators, and offers insights to control the demineralization of calcified soft tissues.

Hydrothermal crystal growth and Vernier structures of the metal benzenedicarboxylates MIL-47 and MIL-53 containing guest molecules of benzenecarboxylic acid

Energy Technology Data Exchange (ETDEWEB)

Wang, Xiqu; Jacobson, Allan J., E-mail: ajjacob@uh.edu

2016-04-15

The nanoporous frameworks VO(bdc), MIL-47, and M(OH)(bdc), MIL-53; bdc=1,4-benzenedicarboxylate, can absorb various guest species in their channels. As synthesized, the channels are filled with H{sub 2}bdc molecules that have been reported to be disordered, except for [In(OH)bdc](H{sub 2}bdc){sub 3/4}, 1, which has a inorganic-organic hybrid Vernier structure with the H{sub 2}bdc molecules forming an ordered sublattice. Based on X-ray data from large single crystals grown by hydrothermal techniques, similar Vernier structures have been found for MIL-47, [VO(bdc)](H{sub 2}bdc){sub 5/7}, 2, MIL-53Al, [Al(OH)(bdc)](H{sub 2}bdc){sub 11/16}, 3, and MIL-53Ga, [Ga(OH)(bdc)](H{sub 2}bdc){sub 12/17}, 4. The Vernier structures of 2–4 at room temperature were determined based on superstructure unit cells that index both host and guest sublattices: 2, space group P2{sub 1}, a=23.903(2), b=17.191(2), c=25.722(2) Å, β=105.914(8)°; 3, P2{sub 1}/n, a=105.224(4), b=12.2441(5), c=17.0143(6) Å, β=89.99(1)°; 4, P2{sub 1}, a=114.562(5), b=12.1503(5), c=17.4275(7) Å, β=89.99(1)°. The number of guest H{sub 2}bdc molecules per framework metal ion is determined by the ratio of the repeat distances of the two sublattices which depends on the size of the metal ion in the octahedral chain. The octahedral chains are parallel to [201] in 2, and to [100] in 3 and 4. Remarkably, all atoms in 3 and 4 show significant sinusoidal modulations transverse to the chain axis. - Graphical abstract: The sinusoidal modulation along the channel axis direction involving all atoms in the structure of [Al(OH)(bdc)](H{sub 2}bdc){sub 11/16}. - Highlights: • Crystal growth of MIL-47, MIL-53Al, and MIL-53Ga. • The Vernier structures have corner-sharing MO6 octrahedral chains and chains of H2BDC molecules. • The stoichiometry is determined by the ratio of the host framework to the guest H2BDC column lengths. • A correlation is established between the stoichiometry and the radius of the metal ion

Cellular uptake: lessons from supramolecular organic chemistry.

Science.gov (United States)

Gasparini, Giulio; Bang, Eun-Kyoung; Montenegro, Javier; Matile, Stefan

2015-07-04

The objective of this Feature Article is to reflect on the importance of established and emerging principles of supramolecular organic chemistry to address one of the most persistent problems in life sciences. The main topic is dynamic covalent chemistry on cell surfaces, particularly disulfide exchange for thiol-mediated uptake. Examples of boronate and hydrazone exchange are added for contrast, comparison and completion. Of equal importance are the discussions of proximity effects in polyions and counterion hopping, and more recent highlights on ring tension and ion pair-π interactions. These lessons from supramolecular organic chemistry apply to cell-penetrating peptides, particularly the origin of "arginine magic" and the "pyrenebutyrate trick," and the currently emerging complementary "disulfide magic" with cell-penetrating poly(disulfide)s. They further extend to the voltage gating of neuronal potassium channels, gene transfection, and the delivery of siRNA. The collected examples illustrate that the input from conceptually innovative chemistry is essential to address the true challenges in biology beyond incremental progress and random screening.

Hydrodynamic and Thermophoretic Effects on the Supramolecular Chirality of Pyrene-Derived Nanosheets.

Science.gov (United States)

Micali, Norberto; Vybornyi, Mykhailo; Mineo, Placido; Khorev, Oleg; Häner, Robert; Villari, Valentina

2015-06-22

Chiroptical properties of two-dimensional (2D) supramolecular assemblies (nanosheets) of achiral, charged pyrene trimers (Py3 ) are rendered chiral by asymmetric physical perturbations. Chiral stimuli in a cuvette can originate either from controlled temperature gradients or by very gentle stirring. The chiroptical activity strongly depends on the degree of supramolecular order of the nanosheets, which is easily controlled by the method of preparation. The high degree of structural order ensures strong cooperative effects within the aggregates, rendering them more susceptible to external stimuli. The samples prepared by using slow thermal annealing protocols are both CD and LD active (in stagnant and stirred solutions), whereas for isothermally aged samples chiroptical activity was in all cases undetectable. In the case of temperature gradients, the optical activity of 2D assemblies could be recorded for a stagnant solution due to migration of the aggregates from the hottest to the coldest regions of the system. However, a considerably stronger exciton coupling, coinciding with the J-band of the interacting pyrenes, is developed upon subtle vortexing (0.5 Hz, 30 rpm) of the aqueous solution of the nanosheets. The sign of the exciton coupling is inverted upon switching between clockwise and counter-clockwise rotation. The supramolecular chirality is evidenced by the appearance of CD activity. To exclude artefacts from proper CD spectra, the contribution from LD to the observed CD was determined. The data suggest that the aggregates experience asymmetrical deformation and alignment effects because of the presence of chiral flows. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic Stability of Structure H Hydrates Based on the Molecular Properties of Large Guest Molecules

OpenAIRE

Tezuka, Kyoichi; Taguchi, Tatsuhiko; Alavi, Saman; Sum, Amadeu K.; Ohmura, Ryo

2012-01-01

This paper report analyses of thermodynamic stability of structure-H clathrate hydrates formed with methane and large guest molecules in terms of their gas phase molecular sizes and molar masses for the selection of a large guest molecule providing better hydrate stability. We investigated the correlation among the gas phase molecular sizes, the molar masses of large molecule guest substances, and the equilibrium pressures. The results suggest that there exists a molecular-size value for the ...

Business Guests Satisfaction in the Hotel Industry: A Case Study of North American Hotel Chains

OpenAIRE

Milan Bradić; Ljiljana Kosar; Bojana Kalenjuk

2013-01-01

This paper considers the problem of satisfaction of business guests with hotel brands in North America. In analysis we used the guests responses (scores) given for 12 different elements of hotel product. In order to arrive at more accurate results, monitored hotel chains are grouped into price tiers. The aim of this paper is to indicate what facilities and services the North American business guests appreciate most. Industry trends and results may be beneficial to all hoteliers, especially in...

Fabrication of Supramolecular Chirality from Achiral Molecules at the Liquid/Liquid Interface Studied by Second Harmonic Generation.

Science.gov (United States)

Lin, Lu; Zhang, Zhen; Guo, Yuan; Liu, Minghua

2018-01-09

We present the investigation into the supramolecular chirality of 5-octadecyloxy-2-(2-pyridylazo)phenol (PARC18) at water/1,2-dichloroethane interface by second harmonic generation (SHG). We observe that PARC18 molecules form supramolecular chirality through self-assembly at the liquid/liquid interface although they are achiral molecules. The bulk concentration of PARC18 in the organic phase has profound effects on the supramolecular chirality. By increasing bulk concentration, the enantiomeric excess at the interface first grows and then decreases until it eventually vanishes. Further analysis reveals that the enantiomeric excess is determined by the twist angle of PARC18 molecules at the interface rather than their orientational angle. At lower and higher bulk concentrations, the average twist angle of PARC18 molecules approaches zero, and the assemblies are achiral; whereas at medium bulk concentrations, the average twist angle is nonzero, so that the assemblies show supramolecular chirality. We also estimate the coverage of PARC18 molecules at the interface versus the bulk concentration and fit it to Langmuir adsorption model. The result indicates that PARC18 assemblies show strongest supramolecular chirality in a half-full monolayer. These findings highlight the opportunities for precise control of supramolecular chirality at liquid/liquid interfaces by manipulating the bulk concentration.

Minimalistic peptide supramolecular co-assembly: expanding the conformational space for nanotechnology.

Science.gov (United States)

Makam, Pandeeswar; Gazit, Ehud

2018-05-21

Molecular self-assembly is a ubiquitous process in nature and central to bottom-up nanotechnology. In particular, the organization of peptide building blocks into ordered supramolecular structures has gained much interest due to the unique properties of the products, including biocompatibility, chemical and structural diversity, robustness and ease of large-scale synthesis. In addition, peptides, as short as dipeptides, contain all the molecular information needed to spontaneously form well-ordered structures at both the nano- and the micro-scale. Therefore, peptide supramolecular assembly has been effectively utilized to produce novel materials with tailored properties for various applications in the fields of material science, engineering, medicine, and biology. To further expand the conformational space of peptide assemblies in terms of structural and functional complexity, multicomponent (two or more) peptide supramolecular co-assembly has recently evolved as a promising extended approach, similar to the structural diversity of natural sequence-defined biopolymers (proteins) as well as of synthetic covalent co-polymers. The use of this methodology was recently demonstrated in various applications, such as nanostructure physical dimension control, the creation of non-canonical complex topologies, mechanical strength modulation, the design of light harvesting soft materials, fabrication of electrically conducting devices, induced fluorescence, enzymatic catalysis and tissue engineering. In light of these significant advancements in the field of peptide supramolecular co-assembly in the last few years, in this tutorial review, we provide an updated overview and future prospects of this emerging subject.

Hyper capacity of MCM-41 supramoleculer structure in the radio- frequency range

OpenAIRE

I.I. Grygorchak; S.A. Vojtovych; Z.A. Stotsko; B.A. Seredyuk; N.K. Tovstyuk

2011-01-01

Purpose: of this paper was: 1) to synthesize supramolecular МСМ-41 structure (p-cyanogen phenyl ether of n-heptyl benzoic acid - 40%)>> with inserted guested nematic and 2) to study its dielectric properties.Design/methodology/approach: Supramolecular МСМ-41 structure has been synthesized by vacuum encapsulated method at room temperature. Dielectric properties have been studied by impedance spectroscopy method in the frequency range 10-3-106 Hz by “AUTOLAB” complex of “ECO CHEMIE” (Holland),...

The hotel comment card: a motivator of guest satisfaction

Directory of Open Access Journals (Sweden)

Alfred W. Ogle

2013-12-01

Full Text Available This   paper   explores   the   traditional   pen   and   paper   hotel   comment   card   (HCC   from   the  guests’  perspective  to  gain  an  insight  and  to  improve  its  effectiveness.  The  HCC  has  long  been   the  predominant  method  of  soliciting  guest  feedback.  Although  electronic  methods  of  collection  are  now  available  the  HCC  has  a  sense  of  familiarity,  has  general  acceptance,  and   is   widely   employed.   Initially,   a   literature   review   of   the   hotel   comment   card   is  provided.  Then,  the  study  explores  how  frequent  guests  categorize  HCC  attributes.  These  attributes  are  then  extended  to  include  evaluation  criteria  identified  in  the  literature  and  desired  by  hotel  managers.    The  extended  evaluation  criterion  is  then  used  to  explore  how  frequent  hotel  guests  believe  that  future  HCCs  may  motivate  guests  to  provide  feedback   and   assist   in   the   co-­creation   of   value.   The   overall   finding   is   that   the   HCCs   design   and  execution  can  be  improved.

Zwitterionic supramolecular nanoparticles: self-assembly and responsive properties

NARCIS (Netherlands)

Stoffelen, C.; Huskens, Jurriaan

2015-01-01

Supramolecular nanoparticles (SNPs) are of high interest in both nanoscience and molecular diagnostics and therapeutics, because of their reversible and designable properties. To ensure colloidal stabilization and biocompatibility, most reported strategies require the use of hydrophilic long-chain

Cluster analysis as a tool of guests segmentation by the degree of their demand

Directory of Open Access Journals (Sweden)

Damijan Mumel

2002-01-01

Full Text Available Authors demonstrate the use of cluster analysis in finding out (ascertaining the homogenity/heterogenity of guests as to the degree of their demand. The degree of guests’ demand is defined according to the importance of perceived service quality components measured by SERVQUAL, which was adopted and adapted, according to the specifics of health spa industry in Slovenia. Goals of the article are: (a the identification of the profile of importance of general health spa service quality components, and (b the identification of groups of guests (segments according to the degree of their demand in the research in 1991 compared with 1999. Cluster analysis serves as useful tool for guest segmentation since it reveals the existence of important differences in the structure of guests in the year 1991 compared with the year 1999. The results serve as a useful database for management in health spas.

Complexation induced aggregation and deaggregation of acridine orange with sulfobutylether-β-cyclodextrin.

Science.gov (United States)

Sayed, Mhejabeen; Jha, Shruti; Pal, Haridas

2017-09-13

The present study reports a contrasting interaction behaviour of a biologically important dye, acridine orange (AOH + ), with a highly water soluble anionic host, based on a β-cyclodextrin (βCD) scaffold, i.e. sulfobutylether-β-cyclodextrin (SBEβCD), in comparison to native βCD. AOH + shows striking modulation in its photophysical properties, representing sequential changes in the modes of interaction with increasing SBEβCD concentration. At lower SBEβCD concentrations, AOH + preferentially binds in dimeric forms at the negatively charged SBEβCD portals, leading to strong fluorescence quenching. At higher SBEβCD concentrations, the dimeric dyes convert to monomeric forms and subsequently undergo both inclusion and exo complex formation with 1 : 1 stoichiometry, resulting in a large fluorescence enhancement. The intriguing observation of sequential fluorescence switch off and switch on for an AOH + -SBEβCD system is clearly facilitated by the presence of butylether chains with SO 3 - end groups at the portals of SBEβCD, providing an additional ion-ion interaction and much enhanced hydrophobic interaction for cationic AOH + compared to the native βCD host. To the best of our knowledge, such fluorescence off/on switching through multistep host-guest binding has not been reported so far in the literature. The present study not only provides a detailed insight into the unique binding interactions of AOH + with the SBEβCD host, but the findings of this study are also expected to be useful in designing supramolecular based drug formulations, drug delivery systems, sensors, and so on.

Highly Efficient Solution-Processed Deep-Red Organic Light-Emitting Diodes Based on an Exciplex Host Composed of a Hole Transporter and a Bipolar Host.

Science.gov (United States)

Huang, Manli; Jiang, Bei; Xie, Guohua; Yang, Chuluo

2017-10-19

With the aim to achieve highly efficient deep-red emission, we introduced an exciplex forming cohost, 4,4',4″-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA): 2,5-bis(2-(9H-carbazol-9-yl)phenyl)-1,3,4-oxadiazole (o-CzOXD) (1:1). Due to the efficient triplet up-conversion processes upon the exciplex forming cohost, excellent performances of the devices were achieved with deep-red emission. Using the heteroleptic iridium complexes as the guest dopants, the solution-processed deep-red phosphorescent organic light-emitting diodes (PhOLEDs) with the iridium(III) bis(6-(4-(tert-butyl)phenyl)phenanthridine)acetylacetonate [(TP-BQ) 2 Ir(acac)]-based phosphorescent emitter exhibited an electroluminescent peak at 656 nm and a maximum external quantum efficiency (EQE) of 11.9%, which is 6.6 times that of the device based on the guest emitter doped in the polymer-based cohost. The unique exciplex with a typical hole transporter and a bipolar material is ideal and universal for hosting the red PhOLEDs and tremendously improves the device performances.

Self-assemblage and post-radiation recovery of cell supramolecular structures

International Nuclear Information System (INIS)

Grodzinskij, D.M.; Kolomiets, K.D.

1979-01-01

The role of the molecular equation and self-assemblage in post-radiation chromatin recovery of meristematic cells of pea rootlets is shown. Found are the two repair types at the chromatin level by fractionating of the radiation dose. The first type comprises transient processes including DNA repair, the second type comprises processes including biosynthesis of the chromatin components and proteins, in the first place. The role of protein biosynthesis in the process of recovery of the chromatin supramolecular structure is shown. The improved radiostability of chromatin self-assemblage is characteristic for the level of its subunits. The supramolecular chromatin structure of the other levels has less radiostability

Self-assembly of a supramolecular square between [Ni(dppe(TOF2] and 4,4'-Bipyridine

Directory of Open Access Journals (Sweden)

Paulo Torres

2013-08-01

Full Text Available The main interest of this research is to contribute to the development and understanding of supramolecular chemistry and molecular architectures, which are constructed by the self-assembly of supramolecular entities. Therefore, the synthesis and characterization (IR, UV, 1H NMR, 31P, 19F, 1H-1H COSY of a nickel (II supramolecular square [7] was performed through the synthesis between nickel chloride [1] and diphenylphosphinoethane (dppe [2] to form the precursor complex [Ni(dppeCl2] [3]. This was followed by the synthesis of the complex of interest, [Ni(dppe(TOF2] [5], using the precursor and silver trifluoromethanesulfonate (Ag-TOF. Finally, the self-assembly was performed between the complex [1,2-bis(diphenylphosphinoethanebistriflatonickel(II] [Ni(dppe(OSO2CF32] [5] and the organic ligand 4,4'-bipyridine [6], which act as vertex and edge, respectively.According to various analyses, it was found that the self-assembly generated only one supramolecular species; a square is the most probable thermodynamic structure.

Injectable self-healing carboxymethyl chitosan-zinc supramolecular hydrogels and their antibacterial activity.

Science.gov (United States)

Wahid, Fazli; Zhou, Ya-Ning; Wang, Hai-Song; Wan, Tong; Zhong, Cheng; Chu, Li-Qiang

2018-04-07

Injectable and self-healing hydrogels have found numerous applications in drug delivery, tissue engineering and 3D cell culture. Herein, we report an injectable self-healing carboxymethyl chitosan (CMCh) supramolecular hydrogels cross-linked by zinc ions (Zn 2+ ). Supramolecular hydrogels were obtained by simple addition of metal ions solution to CMCh solution at an appropriate pH value. The mechanical properties of these hydrogels were adjustable by the concentration of Zn 2+ . For example, the hydrogel with the highest concentration of Zn 2+ (CMCh-Zn4) showed strongest mechanical properties (storage modulus~11,000Pa) while hydrogel with the lowest concentration of Zn 2+ (CMCh-Zn1) showed weakest mechanical properties (storage modulus~220Pa). As observed visually and confirmed rheologically, the CMCh-Zn1 hydrogel with the lowest Zn 2+ concentration showed thixotropic property. CMCh-Zn1 hydrogel also presented injectable property. Moreover, the antibacterial properties of the prepared supramolecular hydrogels were studied against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) by agar well diffusion method. The results revealed Zn 2+ dependent antibacterial properties against both kinds of strains. The inhibition zones were ranging from ~11-24mm and ~10-22mm against S. aureus and E. coli, respectively. We believe that the prepared supramolecular hydrogels could be used as a potential candidate in biomedical fields. Copyright © 2018 Elsevier B.V. All rights reserved.

Guest Editorial: Functional neurosurgery | Enslin | South African ...

African Journals Online (AJOL)

South African Medical Journal. Journal Home · ABOUT · Advanced Search · Current Issue · Archives · Journal Home > Vol 106, No 8 (2016) >. Log in or Register to get access to full text downloads. Username, Password, Remember me, or Register. Guest Editorial: Functional neurosurgery. JMN Enslin. Abstract. No Abstract.

Business Guests Satisfaction in the Hotel Industry: A Case Study of North American Hotel Chains

Directory of Open Access Journals (Sweden)