Redox-responsive self-healing materials formed from host–guest polymers

PubMed Central

Nakahata, Masaki; Takashima, Yoshinori; Yamaguchi, Hiroyasu; Harada, Akira

2011-01-01

Expanding the useful lifespan of materials is becoming highly desirable, and self-healing and self-repairing materials may become valuable commodities. The formation of supramolecular materials through host–guest interactions is a powerful method to create non-conventional materials. Here we report the formation of supramolecular hydrogels and their redox-responsive and self-healing properties due to host–guest interactions. We employ cyclodextrin (CD) as a host molecule because it is environmentally benign and has diverse applications. A transparent supramolecular hydrogel quickly forms upon mixing poly(acrylic acid) (pAA) possessing β-CD as a host polymer with pAA possessing ferrocene as a guest polymer. Redox stimuli induce a sol−gel phase transition in the supramolecular hydrogel and can control self-healing properties such as re-adhesion between cut surfaces. PMID:22027591

Determination of dopamine hydrochloride by host-guest interaction based on water-soluble pillar[5]arene

NASA Astrophysics Data System (ADS)

Xiao, Xue-Dong; Shi, Lin; Guo, Li-Hui; Wang, Jun-Wen; Zhang, Xiang

2017-02-01

The supramolecular interaction between the water-soluble pillar[5]arene (WP[5]) as host and dopamine hydrochloride (DH) as guest was studied by spectrofluorometry. The fluorescence intensity of DH gradually decreased with increasing WP[5] concentration, and the possible interaction mechanism between WP[5] and DH was confirmed by 1H NMR, 2D NOESY, and molecular modelling. Based on significant DH fluorescence, a highly sensitive and selective method for DH determination was developed for the first time. The fluorescence intensity was measured at 312 nm, with excitation at 285 nm. The effects of pH, temperature, and reaction time on the fluorescence spectra of the WP[5]-DH complex were investigated. A linear relationship between fluorescence intensity and DH concentration in the range of 0.07-6.2 μg mL- 1 was obtained. The corresponding linear regression equation is ΔF = 25.76 C + 13.56 (where C denotes the concentration in μg mL- 1), with the limit of detection equal to 0.03 μg mL- 1 and the correlation coefficient equal to 0.9996. This method can be used for the determination of dopamine in injection and urine samples. In addition, the WP[5]-DH complex has potential applications in fluorescent sensing and pharmacokinetics studies of DH.

Recent Advances in Cyclodextrin-Based Light-Responsive Supramolecular Systems.

PubMed

Zhang, Xiaojin; Ma, Xin; Wang, Kang; Lin, Shijun; Zhu, Shitai; Dai, Yu; Xia, Fan

2018-06-01

Cyclodextrins (CDs), one of the host molecules in supramolecular chemistry, can host guest molecules to form inclusion complexes via non-covalent and reversible host-guest interactions. CD-based light-responsive supramolecular systems are typically constructed using CDs and guest molecules with light-responsive moieties, including azobenzene, arylazopyrazole, o-nitrobenzyl ester, pyrenylmethyl ester, coumarin, and anthracene. To date, numerous efforts have been reported on the topic of CD-based light-responsive supramolecular systems, but these have not yet been highlighted in a separated review. This review summarizes the efforts reported over the past ten years. The main text of this review is divided into five sections (vesicles, micelles, gels, capturers, and nanovalves) according to the formation of self-assemblies. This feature article aims to afford a comprehensive understanding of the light-responsive moieties used in the construction of CD-based light-responsive supramolecular systems and to provide a helpful guide for the further design of CD-based light-responsive supramolecular systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular interactions of nonsteroidal anti-inflammatory drug in nanochannels of molecular containers: a spectroscopic, thermogravimetric and microscopic investigation.

PubMed

Maity, Banibrata; Chatterjee, Aninda; Ahmed, Sayeed Ashique; Seth, Debabrata

2014-11-10

Supramolecular host-guest complexation between the nonsteroidal anti-inflammatory drug indomethacin (IMC) and molecular containers were investigated. The weakly fluorescent drug molecule becomes highly fluorescent on complexation with different molecular containers, and time-resolved fluorescence emission spectroscopy reveals that the lifetime components of IMC significantly increase in the presence of molecular containers, compared with the lifetimes in neat water. The respective solid host-guest complexes were synthesised and characterised by Fourier transform infrared and (1) H nuclear magnetic resonance spectroscopic analysis. Microscopy techniques were used to analyse modifications of the surface morphology, owing to the formation of supramolecular complexes. The effect of the molecular container on the optical properties of IMC has also been investigated to determine the effect of nanochannels of different size and structure. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular chemistry at interfaces: host-guest interactions for fabricating multifunctional biointerfaces.

PubMed

Yang, Hui; Yuan, Bin; Zhang, Xi; Scherman, Oren A

2014-07-15

CONSPECTUS: Host-guest chemistry can greatly improve the selectivity of biomolecule-ligand binding on account of recognition-directed interactions. In addition, functional structures and the actuation of supramolecular assemblies in molecular systems can be controlled efficiently through various host-guest chemistry. Together, these highly selective, strong yet dynamic interactions can be exploited as an alternative methodology for applications in the field of programmable and controllable engineering of supramolecular soft materials through the reversible binding between complementary components. Many processes in living systems such as biotransformation, transportation of matter, and energy transduction begin with interfacial molecular recognition, which is greatly influenced by various external stimuli at biointerfaces. Detailed investigations about the molecular recognition at interfaces can result in a better understanding of life science, and further guide us in developing new biomaterials and medicines. In order to mimic complicated molecular-recognition systems observed in nature that adapt to changes in their environment, combining host-guest chemistry and surface science is critical for fabricating the next generation of multifunctional biointerfaces with efficient stimuli-responsiveness and good biocompatibility. In this Account, we will summarize some recent progress on multifunctional stimuli-responsive biointerfaces and biosurfaces fabricated by cyclodextrin- or cucurbituril-based host-guest chemistry and highlight their potential applications including drug delivery, bioelectrocatalysis, and reversible adsorption and resistance of peptides, proteins, and cells. In addition, these biointerfaces and biosurfaces demonstrate efficient response toward various external stimuli, such as UV light, pH, redox chemistry, and competitive guests. All of these external stimuli can aid in mimicking the biological stimuli evident in complex biological environments. We begin by reviewing the current state of stimuli-responsive supramolecular assemblies formed by host-guest interactions, discussing how to transfer host-guest chemistry from solution onto surfaces required for fabricating multifunctional biosurfaces and biointerfaces. Then, we present different stimuli-responsive biosurfaces and biointerfaces, which have been prepared through a combination of cyclodextrin- or cucurbituril-based host-guest chemistry and various surface technologies such as self-assembled monolayers or layer-by-layer assembly. Moreover, we discuss the applications of these biointerfaces and biosurfaces in the fields of drug release, reversible adsorption and release of some organic molecules, peptides, proteins, and cells, and photoswitchable bioelectrocatalysis. In addition, we summarize the merits and current limitations of these methods for fabricating multifunctional stimuli-responsive biointerfaces in a dynamic noncovalent manner. Finally, we present possible strategies for future designs of stimuli-responsive multifunctional biointerfaces and biosurfaces by combining host-guest chemistry with surface science, which will lead to further critical development of supramolecular chemistry at interfaces.

Visible light-driven water oxidation promoted by host-guest interaction between photosensitizer and catalyst with a high quantum efficiency.

PubMed

Li, Hua; Li, Fei; Zhang, Biaobiao; Zhou, Xu; Yu, Fengshou; Sun, Licheng

2015-04-08

A highly active supramolecular system for visible light-driven water oxidation was developed with cyclodextrin-modified ruthenium complex as the photosensitizer, phenyl-modified ruthenium complexes as the catalysts, and sodium persulfate as the sacrificial electron acceptor. The catalysts were found to form 1:1 host-guest adducts with the photosensitizer. Stopped-flow measurement revealed the host-guest interaction is essential to facilitate the electron transfer from catalyst to sensitizer. As a result, a remarkable quantum efficiency of 84% was determined under visible light irradiation in neutral aqueous phosphate buffer. This value is nearly 1 order of magnitude higher than that of noninteraction system, indicating that the noncovalent incorporation of sensitizer and catalyst is an appealing approach for efficient conversion of solar energy into fuels.

Untangling the Diverse Interior and Multiple Exterior Guest Interactions of a Supramolecular Host by the Simultaneous Analysis of Complementary Observables.

PubMed

Sgarlata, Carmelo; Raymond, Kenneth N

2016-07-05

The entropic and enthalpic driving forces for encapsulation versus sequential exterior guest binding to the [Ga4L6](12-) supramolecular host in solution are very different, which significantly complicates the determination of these thermodynamic parameters. The simultaneous use of complementary techniques, such as NMR, UV-vis, and isothermal titration calorimetry, enables the disentanglement of such multiple host-guest interactions. Indeed, data collected by each technique measure different components of the host-guest equilibria and together provide a complete picture of the solution thermodynamics. Unfortunately, commercially available programs do not allow for global analysis of different physical observables. We thus resorted to a novel procedure for the simultaneous refinement of multiple parameters (ΔG°, ΔH°, and ΔS°) by treating different observables through a weighted nonlinear least-squares analysis of a constrained model. The refinement procedure is discussed for the multiple binding of the Et4N(+) guest, but it is broadly applicable to the deconvolution of other intricate host-guest equilibria.

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

PubMed

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.

Equilibrium isotope effects on noncovalent interactions in a supramolecular host-guest system.

PubMed

Mugridge, Jeffrey S; Bergman, Robert G; Raymond, Kenneth N

2012-02-01

The self-assembled supramolecular complex [Ga(4)L(6)](12-) (1; L = 1,5-bis[2,3-dihydroxybenzamido]naphthalene) can act as a molecular host in aqueous solution and bind cationic guest molecules to its highly charged exterior surface or within its hydrophobic interior cavity. The distinct internal cavity of host 1 modifies the physical properties and reactivity of bound guest molecules and can be used to catalyze a variety of chemical transformations. Noncovalent host-guest interactions in large part control guest binding, molecular recognition and the chemical reactivity of bound guests. Herein we examine equilibrium isotope effects (EIEs) on both exterior and interior guest binding to host 1 and use these effects to probe the details of noncovalent host-guest interactions. For both interior and exterior binding of a benzylphosphonium guest in aqueous solution, protiated guests are found to bind more strongly to host 1 (K(H)/K(D) > 1) and the preferred association of protiated guests is driven by enthalpy and opposed by entropy. Deuteration of guest methyl and benzyl C-H bonds results in a larger EIE than deuteration of guest aromatic C-H bonds. The observed EIEs can be well explained by considering changes in guest vibrational force constants and zero-point energies. DFT calculations further confirm the origins of these EIEs and suggest that changes in low-frequency guest C-H/D vibrational motions (bends, wags, etc.) are primarily responsible for the observed EIEs. © 2011 American Chemical Society

Three-dimensional periodic supramolecular organic framework ion sponge in water and microcrystals

DOE PAGES

Tian, Jia; Zhou, Tian-You; Zhang, Shao-Chen; ...

2014-12-02

Self-assembly has emerged as a powerful approach to generating complex supramolecular architectures. Despite there being many crystalline frameworks reported in the solid state, the construction of highly soluble periodic supramolecular networks in a three-dimensional space is still a challenge. In this paper we demonstrate that the encapsulation motif, which involves the dimerization of two aromatic units within cucurbit[8]uril, can be used to direct the co-assembly of a tetratopic molecular block and cucurbit[8]uril into a periodic three-dimensional supramolecular organic framework in water. The periodicity of the supramolecular organic framework is supported by solution-phase small-angle X-ray-scattering and diffraction experiments. Upon evaporating themore » solvent, the periodicity of the framework is maintained in porous microcrystals. Lastly, as a supramolecular 'ion sponge', the framework can absorb different kinds of anionic guests, including drugs, in both water and microcrystals, and drugs absorbed in microcrystals can be released to water with selectivity.« less

Fluorescent Phthalocyanine Assembly Distinguishes Chiral Isomers of Different Types of Amino Acids and Sugars.

PubMed

Jiang, Yuying; Liu, Chenxi; Wang, Xiqian; Wang, Tianyu; Jiang, Jianzhuang

2017-07-25

The functions of some natural supramolecular architectures, such as ribosomes, are dependent on the recognition of different types of chiral biomolecules. However, the recognition of different types of chiral molecules (multiobject chiral recognition), such as amino acids and sugars, by independent and identically artificial supramolecular assembly, was rarely achieved. In this article, simple amphiphilic achiral phthalocyanine was found to form supramolecular chiral assemblies with charged water-soluble polymers upon host-guest interactions at the air/water interface. Among these systems, one identical phthalocyanine/poly(l-lysine) assembly not only can distinguish enantiomers of different amino acids but also can recognize several epimers of monose. The chiral recognitions were achieved by comparing either the steady-state fluorescence intensity or fluorescence quenching rate of phthalocyanine/poly(l-lysine) assemblies, before and after interaction with different small chiral molecules. It was demonstrated that the interactions between poly(l-lysine) and different small chiral molecules could change the aggregation of phthalocyanines. And the sensitivity of fluorescence and the excellent multiobject chiral recognition properties of the phthalocyanine/poly(l-lysine) assembly are dependent on the subtle molecular packing mode and the cooperation of different noncovalent interactions.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 expandingmore » 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 of protonated guests was translated into chemical catalysis by taking advantage of the potential for accelerating reactions that take place via positively charged transition states, which could be potentially stabilized by encapsulation. Orthoformates, generally stable in neutral or basic solution, were found to be suitable substrates for catalytic hydrolysis by the assembly. Orthoformates small enough to undergo encapsulation were readily hydrolyzed by the assembly in basic solution, with rate acceleration factors up to 3900 compared with those of the corresponding uncatalyzed reactions. Furthering the analogy to enzymes that obey Michaelis-Menten kinetics, we observed competitive inhibition with the inhibitor NPr{sub 4}{sup +}, thereby confirming that the interior cavity of the assembly was the active site for catalysis. Mechanistic studies revealed that the assembly is required for catalysis and that the rate-limiting step of the reaction involves proton transfer from hydronium to the encapsulated substrate. Encapsulation in the assembly changes the orthoformate hydrolysis from an A-1 mechanism (in which decomposition of the protonated substrate is the rate-limiting step) to an A-S{sub E}2 mechanism (in which proton transfer is the rate-limiting step). The study of hydrolysis in the assembly was next extended to acetals, which were also catalytically hydrolyzed by the assembly in basic solution. Acetal hydrolysis changed from the A-1 mechanism in solution to an A-2 mechanism inside the assembly, where attack of water on the protonated substrate is rate limiting. This work provides rare examples of assembly-catalyzed reactions that proceed with substantial rate accelerations despite the absence of functional groups in the cavity and with mechanisms fully elucidated by quantitative kinetic studies.« less

Self-assembly behavior of a linear-star supramolecular amphiphile based on host-guest complexation.

PubMed

Wang, Juan; Wang, Xing; Yang, Fei; Shen, Hong; You, Yezi; Wu, Decheng

2014-11-04

A star polymer, β-cyclodextrin-poly(l-lactide) (β-CD-PLLA), and a linear polymer, azobenzene-poly(ethylene glycol) (Azo-PEG), could self-assemble into a supramolecular amphiphilic copolymer (β-CD-PLLA@Azo-PEG) based on the host-guest interaction between β-CD and azobenzene moieties. This linear-star supramolecular amphiphilic copolymer further self-assembled into a variety of morphologies, including sphere-like micelle, carambola-like micelle, naan-like micelle, shuttle-like lamellae, tube-like fiber, and random curled-up lamellae, by tuning the length of hydrophilic or hydrophobic chains. The variation of morphology was closely related to the topological structure and block ratio of the supramolecular amphiphiles. These self-assembly structures could disassemble upon an ultraviolet (UV) light irradiation.

Inclusion complex of benzocaine and β-cyclodextrin: 1H NMR and isothermal titration calorimetry studies

NASA Astrophysics Data System (ADS)

Mic, Mihaela; Pırnǎu, Adrian; Bogdan, Mircea; Turcu, Ioan

2013-11-01

The supramolecular structure of the inclusion complex of β-cyclodextrin with benzocaine in aqueous solution has been investigated by 1H NMR spectroscopy and isothermal titration nanocalorimetry (ITC). Analysis of 1H NMR data by continuous variation method indicates that the benzocaine: β-cyclodextrin inclusion complex occurs and has a 1:1 stoichiometry. Rotating frame NOE spectroscopy (ROESY) was used to ascertain the solution geometry of the host-guest complex which indicates that the benzocaine molecule was included with the aromatic ring into the cyclodextrin cavity. Although the affinity of benzocaine for cyclodextrin is relatively high, the association constant cannot be measured using ITC due to the low solubility of benzocaine in water.

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.

PubMed

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.

Self-healing pH-sensitive poly[(methyl vinyl ether)-alt-(maleic acid)]-based supramolecular hydrogels formed by inclusion complexation between cyclodextrin and adamantane.

PubMed

Ma, Xiaoe; Zhou, Naizhen; Zhang, Tianzhu; Hu, Wanjun; Gu, Ning

2017-04-01

Self-healing materials are of interest for drug delivery, cell and gene therapy, tissue engineering, and other biomedical applications. In this work, on the base of biocompatible polymer poly(methyl vinyl ether-alt-maleic acid) (P(MVE-alt-MA)), host polymer β-cyclodextrin-grafted P(MVE-alt-MA) (P(MVE-alt-MA)-g-β-CD) and guest polymer adamantane-grafted P(MVE-alt-MA) (P(MVE-alt-MA)-g-Ad) were first prepared. Then through taking advantage of the traditional host-guest interaction of β-cyclodextrin and adamantane, a novel self-healing pH-sensitive physical P(MVE-alt-MA)-g-β-CD/P(MVE-alt-MA)-g-Ad supramolecular hydrogels were obtained after simply mixing the aqueous solution of host polymer and guest polymer. This kind of supramolecular hydrogels not only possess pH-sensitivity, but also possess the ability to repair themselves after being damaged. Copyright © 2016 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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.

On some problems of inorganic supramolecular chemistry.

PubMed

Pervov, Vladislav S; Zotova, Anna E

2013-12-02

In this study, some features that distinguish inorganic supramolecular host-guest objects from traditional architectures are considered. Crystalline inorganic supramolecular structures are the basis for the development of new functional materials. Here, the possible changes in the mechanism of crystalline inorganic supramolecular structure self-organization at high interaction potentials are discussed. The cases of changes in the host structures and corresponding changes in the charge states under guest intercalation, as well as their impact on phase stability and stoichiometry are considered. It was demonstrated that the deviation from the geometrical and topological complementarity conditions may be due to the additional energy gain from forming inorganic supramolecular structures. It has been assumed that molecular recognition principles can be employed for the development of physicochemical analysis and interpretation of metastable states in inorganic crystalline alloys. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The synthesis and host-guest applications of synthetic receptor molecules

NASA Astrophysics Data System (ADS)

Osner, Zachary R.

2011-12-01

Host-guest chemistry involves the complimentary binding between two molecules. Host molecules have been synthesized to bind negative, positive, and neutral molecules such as proteins and enzymes, and have been used as optical sensors, electrochemical sensors, supramolecular catalysts, and in the pharmaceutical industry as anti-cancer agents.1 The field of nanoscience has exploited guest-host interactions to create optical sensors with colloidal gold and Dip-Pen nanolithography technologies. Gold nanoparticles, have been functionalized with DNA, and have been developed as a selective colorimetric detection system, that upon binding turns the solution from a red to blue in color.2 Cyclotriveratrylene (CTV) 1 is a common supramolecular scaffold that has been previously employed in guest-host chemistry, and the construction of CTV involves the cyclic trimerization of veratryl alcohol via the veratryl cation.3 Due to the rigid bowl shaped structure of CTV, CTV has been shown to act as a host molecule for fullerene-C60.4 Lectin binding receptor proteins are a specific class of proteins found in bacteria, viruses, plants, and animals that can bind to complimentary carbohydrates. It is these lectins that are believed to be responsible for cell-cell interactions and the formation of biofilms in pathenogenic bacteria.5 P. aeruginosa is a pathenogenic bacterium, shown to have a high resistance to many antibiotics, which can form biofilms in human lung tissue, causing respiratory tract infections in patients with compromised immune systems. 5 I will exploit guest-host interactions to create synthetic supramolecular and carbohydrate receptor molecules to that will be of use as biological sensing devices via self-assembled monolayers on solid surfaces and nanoparticle technologies. *Please refer to dissertation for references/footnotes.

Preparation, characterization and binding behaviors of host-guest inclusion complexes of metoclopramide hydrochloride with α- and β-cyclodextrin molecules

NASA Astrophysics Data System (ADS)

Barman, Siti; Barman, Biraj Kumar; Roy, Mahendra Nath

2018-03-01

The supramolecular interaction of metoclopramide hydrochloride (MP) with α-cyclodextrin (α-CD) and β-cyclodextrin (β-CD) has been inspected by ultraviolet-visible (UV-vis) light, infra-red (IR) light, fluorescence and 1H NMR spectroscopy. The formation of an inclusion complex greatly affects the physical-chemical properties of the guest molecules, such as solubility, chemical reactivity and the spectroscopic and electrochemical properties. Thus the changes in the spectral properties and physico-chemical properties confirm the inclusion complex formation. Surface tension, conductivity studies and Job's plot indicate a 1: 1 stoichiometry of the MP:CD host-guest inclusion complexes. The binding/association constants have been evaluated by both UV-Vis and fluorescence spectroscopic study indicating a higher degree of encapsulation for β-cyclodextrin (β-CD). Furthermore, the negative value of thermodynamic parameter (ΔG°) of the host-guest system suggests that the inclusion process proceeded spontaneously at 298.15 K. Based on the NMR data, the plausible mode of interaction of MP:α-CD and MP:β-CD complexes were proposed, which suggested that lipophilic aromatic ring of the MP entered into the cavity of CDs from the wider side, with the amide (sbnd CONH) and methoxy (-OMe) residues inside the CD cavity.

Elaboration of thermoresponsive supramolecular diblock copolymers in water from complementary CBPQT4+ and TTF end-functionalized polymers.

PubMed

Sambe, Léna; Stoffelbach, François; Poltorak, Katarzyna; Lyskawa, Joël; Malfait, Aurélie; Bria, Marc; Cooke, Graeme; Woisel, Patrice

2014-02-01

A well-defined poly(N-isopropyl acrylamide) 1 incorporating at one termini a cyclobis(paraquat-p-phenylene) (CBPQT(4+)) recognition unit is prepared via a RAFT polymerization followed by a copper-catalyzed azide-alkyne cycloaddition (CuAAC). (1)H NMR (1D, DOSY), UV-vis and ITC experiments reveal that polymer 1 is able of forming effective host-guest complexes with tetrathiafulvalene (TTF) end-functionalized polymers in water, thereby leading to the formation of non-covalently-linked double-hydrophilic block copolymers. The effect of the temperature on both the LCST phase transition of 1 and its complexes and on CBPQT(4+)/TTF host-guest interactions is investigated. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework

DOE PAGES

Yang, Sihai; Ramirez-Cuesta, Anibal J.; Newby, Ruth; ...

2014-12-01

Supramolecular interactions are fundamental to host–guest binding in many chemical and biological processes. Direct visualization of such supramolecular interactions within host–guest systems is extremely challenging, but crucial to understanding their function. Within this paper, we report a comprehensive study that combines neutron scattering, synchrotron X-ray and neutron diffraction, and computational modelling to define the detailed binding at a molecular level of acetylene, ethylene and ethane within the porous host NOTT-300. This study reveals simultaneous and cooperative hydrogen-bonding, π···π stacking interactions and intermolecular dipole interactions in the binding of acetylene and ethylene to give up to 12 individual weak supramolecular interactionsmore » aligned within the host to form an optimal geometry for the selective binding of hydrocarbons. In addition, we also report the cooperative binding of a mixture of acetylene and ethylene within the porous host, together with the corresponding breakthrough experiments and analysis of adsorption isotherms of gas mixtures.« less

Investigation of hydrophobic interactions mediating the self-assembly of supramolecular host/guest polymer complexes utilizing Simultaneous Multiple Sample Light Scattering (SMSLS)

NASA Astrophysics Data System (ADS)

Payne, Molly; Jarand, Curtis; Grayson, Scott; Reed, Wayne

While living systems spontaneously heal injuries, most man made materials cannot recover from damage. Incorporating self-healing properties into synthetic polymers could significantly extend product lifetime, safety, and applications. Most reported approaches to incorporate healing into synthetic materials, however, require external stimuli such as chemical additives, heat, and light exposure. Although dynamic bonds have been explored, particularly using a hydrogen bond motif, this has not been fully investigated in an aqueous environment. To address this, hosts and guests that dynamically associate in water have been investigated to build aqueous self-healing materials. These association values were probed for various host/guest complexes using Simultaneous Multiple Sample Light Scattering (SMSLS), a technique that measures the size of aggregates via light scattering while varying concentration and other environmental factors. NSF EPSCoR IIA1430280.

Obtaining control of cell surface functionalizations via Pre-targeting and Supramolecular host guest interactions

NASA Astrophysics Data System (ADS)

Rood, Mark T. M.; Spa, Silvia J.; Welling, Mick M.; Ten Hove, Jan Bart; van Willigen, Danny M.; Buckle, Tessa; Velders, Aldrik H.; van Leeuwen, Fijs W. B.

2017-01-01

The use of mammalian cells for therapeutic applications is finding its way into modern medicine. However, modification or “training” of cells to make them suitable for a specific application remains complex. By envisioning a chemical toolbox that enables specific, but straight-forward and generic cellular functionalization, we investigated how membrane-receptor (pre)targeting could be combined with supramolecular host-guest interactions based on β-cyclodextrin (CD) and adamantane (Ad). The feasibility of this approach was studied in cells with membranous overexpression of the chemokine receptor 4 (CXCR4). By combining specific targeting of CXCR4, using an adamantane (Ad)-functionalized Ac-TZ14011 peptide (guest; KD = 56 nM), with multivalent host molecules that entailed fluorescent β-CD-Poly(isobutylene-alt-maleic-anhydride)-polymers with different fluorescent colors and number of functionalities, host-guest cell-surface modifications could be studied in detail. A second set of Ad-functionalized entities enabled introduction of additional surface functionalities. In addition, the attraction between CD and Ad could be used to drive cell-cell interactions. Combined we have shown that supramolecular interactions, that are based on specific targeting of an overexpressed membrane-receptor, allow specific and stable, yet reversible, surface functionalization of viable cells and how this approach can be used to influence the interaction between cells and their surroundings.

Mastering fundamentals of supramolecular design with carboxylic acids. Common lessons from X-ray crystallography and scanning tunneling microscopy.

PubMed

Ivasenko, Oleksandr; Perepichka, Dmitrii F

2011-01-01

Hydrogen bonding is one of the most important non-covalent interactions in both biological (DNA, peptides, saccharides etc.) and artificial systems (various soft materials, host-guest architectures, molecular networks, etc.). Carboxylic acids are some of the most simple yet powerful hydrogen-bonding building blocks, that possess a particularly rich supramolecular chemistry. This tutorial review focuses on the structural diversity of supramolecular architectures accessible via hydrogen bonding of carboxylic acids, as observed both in single crystals using X-ray analysis and in monolayers on surfaces using scanning probe techniques. It provides a concise overview of the key concepts and principles of modern supramolecular design and is given in the form of case studies of finely selected literature examples, covering formation of macrocycles, chains, ladders, rotaxanes, catenanes, various 2D and 3D nets, host-guest systems and some applications thereof.

Indanedione based binary chromophore supramolecular systems as a NLO active polymer composites

NASA Astrophysics Data System (ADS)

Rutkis, M.; Tokmakovs, A.; Jecs, E.; Kreicberga, J.; Kampars, V.; Kokars, V.

2010-06-01

Novel route to obtain EO material is proposed by supramolecular assembly of neutral-ground-state (NGS) and zwitterionic (ZWI) NLO chromophores in binary chromophore organic glass (BCOG) host-guest system. On a basis of our Langeven Dynamics (LD) molecular modeling combined with quantum chemical calculations, we have shown that anticipated enhancement NLO efficiency of BCOG material is possible via electrostatic supramolecular assembly of NGS with ZWI chromophore in antiparallel manner. Binding energy of such complex could be more dependent on molecular compatibility of components and local (atomic) charge distribution, then overall molecular dipole moments. According to our LD simulations these supramolecular bind structures of NGS and ZWI chromophores can sustain thermally assisted electrical field poling. For the one of experimentally investigated systems, build from dimethylaminobenzylidene 1,3-indanedione containing host and zwitterionic indanedione-1,3 pyridinium betaine as a guest, almost twofold enhancement of NLO efficiency was observed.

A rapidly self-healing supramolecular polymer hydrogel with photostimulated room-temperature phosphorescence responsiveness.

PubMed

Chen, Hui; Ma, Xiang; Wu, Shuaifan; Tian, He

2014-12-15

Development of self-healing and photostimulated luminescent supramolecular polymeric materials is important for artificial soft materials. A supramolecular polymeric hydrogel is reported based on the host-guest recognition between a β-cyclodextrin (β-CD) host polymer (poly-β-CD) and an α-bromonaphthalene (α-BrNp) polymer (poly-BrNp) without any additional gelator, which can self-heal within only about one minute under ambient atmosphere without any additive. This supramolecular polymer system can be excited to engender room-temperature phosphorescence (RTP) signals based on the fact that the inclusion of β-CD macrocycle with α-BrNp moiety is able to induce RTP emission (CD-RTP). The RTP signal can be adjusted reversibly by competitive complexation of β-CD with azobenzene moiety under specific irradiation by introducing another azobenzene guest polymer (poly-Azo). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioorganometallic chemistry. 8. The molecular recognition of aromatic and aliphatic amino acids and substituted aromatic and aliphatic carboxylic acid guests with supramolecular ({eta}{sup 5}-pentamethylcyclopentadienyl)rhodium - nucleobase, nucleoside, and nucleotide cyclic trimer hosts via non-covalent {pi}-{pi} and hydrophobic interactions in water: Steric, electronic, and conformational parameters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, H.; Ogo, Seiji; Fish, R.H.

Molecular recognition, via non-covalent processes such as hydrogen bonding, {pi}-{pi}, and hydrophobic interactions, is an important biological phenomenon for guests, such as drugs, proteins, and other important biological molecules with, for example, host DNA/RNA. We have studied a novel molecular recognition process using guests that encompass aromatic and aliphatic amino acids [L-alanine, L-glutamine (L-Gln), L-histidine, L-isoleucine(L-Ile), L-leucine(L-Leu), L-phenylalanine(L-Phe), L-proline, L-tryptophan(L-Trp), L-valine(L-Val)], substituted aromatic carboxylic acids o-, m-, p-aminobenzoic acids (G1-3), benzoic acid (G4), phenylacetic acid (G5), p-methoxyphenylacetic acid (G6), o-methyoxybenozoic acid (G9), o-nitrobenzoic acid (G10), and aliphatic carboxylic acids [cyclohexylacetic acid (G7), 1-adamantanecarboxylic acid (G8)] with supramolecular, bioorganometallic hosts, ({eta}{supmore » 5}-pentamethylcyclopentadienyl)rhodium (Cp{sup *}Rh)-nucleobase, nucleoside, and nucleotide cyclic trimer complexes in aqueous solution at pH 7, utilizing {sup 1}H NMR, NOE, and molecular modeling techniques, and, as well, determining association constants (K{sub a}) and free energies of complexation ({Delta}{degree}G). The host-guest complexation occurs predominantly via non-covalent {pi}-{pi}, hydrophobic, and possible subtle H-bonding interactions, with steric, electronic, and molecular conformational parameters as important criteria. 8 refs., 6 figs., 3 tabs.« less

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

PubMed

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.

Host-guest supramolecular nanosystems for cancer diagnostics and therapeutics.

PubMed

Wang, Lei; Li, Li-li; Fan, Yun-shan; Wang, Hao

2013-07-26

Extensive efforts have been devoted to the construction of functional supramolecular nanosystems for applications in catalysis, energy conversion, sensing and biomedicine. The applications of supramolecular nanosystems such as liposomes, micelles, inorganic nanoparticles, carbon materials for cancer diagnostics and therapeutics have been reviewed by other groups. Here, we will focus on the recent momentous advances in the implementation of typical supramolecular hosts (i.e., cyclodextrins, calixarenes, cucurbiturils and metallo-hosts) and their nanosystems in cancer diagnostics and therapeutics. We discuss the evolutive process of supramolecular nanosystems from the structural control and characterization to their diagnostic and therapeutic function exploitation and even the future potentials for clinical translation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Engineering responsive polymer building blocks with host-guest molecular recognition for functional applications.

PubMed

Hu, Jinming; Liu, Shiyong

2014-07-15

CONSPECTUS: All living organisms and soft matter are intrinsically responsive and adaptive to external stimuli. Inspired by this fact, tremendous effort aiming to emulate subtle responsive features exhibited by nature has spurred the invention of a diverse range of responsive polymeric materials. Conventional stimuli-responsive polymers are constructed via covalent bonds and can undergo reversible or irreversible changes in chemical structures, physicochemical properties, or both in response to a variety of external stimuli. They have been imparted with a variety of emerging applications including drug and gene delivery, optical sensing and imaging, diagnostics and therapies, smart coatings and textiles, and tissue engineering. On the other hand, in comparison with molecular chemistry held by covalent bonds, supramolecular chemistry built on weak and reversible noncovalent interactions has emerged as a powerful and versatile strategy for materials fabrication due to its facile accessibility, extraordinary reversibility and adaptivity, and potent applications in diverse fields. Typically involving more than one type of noncovalent interactions (e.g., hydrogen bonding, metal coordination, hydrophobic association, electrostatic interactions, van der Waals forces, and π-π stacking), host-guest recognition refers to the formation of supramolecular inclusion complexes between two or more entities connected together in a highly controlled and cooperative manner. The inherently reversible and adaptive nature of host-guest molecular recognition chemistry, stemming from multiple noncovalent interactions, has opened up a new platform to construct novel types of stimuli-responsive materials. The introduction of host-guest chemistry not only enriches the realm of responsive materials but also confers them with promising new applications. Most intriguingly, the integration of responsive polymer building blocks with host-guest recognition motifs will endow the former with further broadened responsiveness to external stimuli and accordingly more sophisticated functions. In this Account, we summarize recent progress in the field of responsive polymeric materials containing host-guest recognition motifs with selected examples and highlight their versatile functional applications, whereas small molecule-oriented host-guest supramolecular systems are excluded. We demonstrate how the introduction of host-guest chemistry into conventional polymer systems can modulate their responsive modes to external stimuli. Moreover, the responsive specificity and selectivity of polymeric systems can also be inherited from the host-guest recognition motifs, and these features provide extra advantages in terms of function integration. The following discussions are categorized in terms of design and functions, namely, host-guest chemistry toward the fabrication of responsive polymers and assemblies, optical sensing and imaging, drug and gene delivery, and self-healing materials. A concluding remark on future developments is also presented. We wish this prosperous field would incur more original and evolutionary ideas and benefit fundamental research and our daily life in a more convenient way.

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

PubMed

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.

Molecular recognition of curcumin (Indian Ayurvedic medicine) by the supramolecular probe, p-t-butyl calix(8)arene

NASA Astrophysics Data System (ADS)

Meenakshi, C.; Jayabal, P.; Ramakrishnan, V.

2014-06-01

The thermodynamic property of the host-guest complexes formed between the curcumin, component of Indian Ayurvedic medicine turmeric, a drug molecule, with the supra molecule, p-t-butyl calix(8)arene was studied. p-t-Butyl calix(8)arene has been used as a host molecule and curcumin as a guest molecule. Optical absorption spectral studies were carried out to investigate the molecular recognition properties of p-t-butyl calix(8)arene with curcumin. The stochiometry of the host-guest complexes formed and the binding constant were determined. An interesting 1:1 and 4:1 stochiometric host-guest complexes were formed. Job's continuous method of variation and Benesi-Hildebrand expression were used for the determination of binding constant and the stochiometry of the host-guest complex formed.

Metal Coordination Stoichiometry Controlled Formation of Linear and Hyperbranched Supramolecular Polymers.

PubMed

Lin, Cuiling; Xu, Luonan; Huang, Libo; Chen, Jia; Liu, Yuanyuan; Ma, Yifan; Ye, Feixiang; Qiu, Huayu; He, Tian; Yin, Shouchun

2016-09-01

Controlling the topologies of polymers is a hot topic in polymer chemistry because the physical and/or chemical properties of polymers are determined (at least partially) by their topologies. This study exploits the host-guest interactions between dibenzo-24-crown-8 and secondary ammonium salts and metal coordination interactions between 2,6-bis(benzimidazolyl)-pyridine units with metal ions (Zn(II) and/or Eu(III) ) as orthogonal non-covalent interactions to prepare supramolecular polymers. By changing the ratios of the metal ion additives (Zn(NO3 )2 and Eu(NO3 )3 ) linkers to join the host-guest dimeric complex, the linear supramolecular polymers (100 mol% Zn(NO3 )2 per ligand) and hyperbranched supramolecular polymers (97 mol% Zn(NO3 )2 and 3 mol% Eu(NO3 )3 per ligand) are separately and successfully constructed. This approach not only expands topological control over polymeric systems, but also paves the way for the functionalization of smart and adaptive materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

;Host-guest; interactions in Captisol®/Coumestrol inclusion complex: UV-vis, FTIR-ATR and Raman studies

NASA Astrophysics Data System (ADS)

Venuti, Valentina; Stancanelli, Rosanna; Acri, Giuseppe; Crupi, Vincenza; Paladini, Giuseppe; Testagrossa, Barbara; Tommasini, Silvana; Ventura, Cinzia Anna; Majolino, Domenico

2017-10-01

The ability of Captisol® (sulphobutylether-β-cyclodextrin, SBE-β-CD), to form inclusion complexes, both in solution and in the solid state, has been tested in order to improve some unfavorable chemical-physical characteristics, such as poor solubility in water, of a bioflavonoid, Coumestrol (Coum), well known for its anti-oxidant, anti-inflammatory, anti-fungal and anti-viral activity. In pure water, a phase-solubility study was carried out to evaluate the enhancement of the solubility of Coum and, therefore, the occurred complexation with the macrocycle. The stoichiometry and the stability constant of the SBE-β-CD/Coum complex were calculated with the phase solubility method and through the Job's plot. After that, the solid SBE-β-CD/Coum complex was prepared utilizing a kneading method. The spectral changes induced by complexation on characteristic vibrational band of Coum were complementary investigated by Fourier transform infrared spectroscopy in attenuated total reflectance geometry (FTIR-ATR) and Raman spectroscopy, putting into evidence the guest chemical groups involved in the "host-guest" interactions responsible of the formation and stabilization of the complex. Particular attention was paid to the Cdbnd O and Osbnd H stretching vibrations, whose temperature-evolution respectively furnished the enthalpy changes associated to the binding of host and guest in solid phase and to the reorganization of the hydrogen bond scheme upon complexation. From the whole set of results, an inclusion geometry is also proposed.

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

PubMed Central

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

2017-01-01

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. PMID:28205515

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

PubMed

Poorghorban, Masoomeh; Das, Umashankar; Alaidi, Osama; Chitanda, Jackson M; Michel, Deborah; Dimmock, Jonathan; Verrall, Ronald; Grochulski, Pawel; Badea, Ildiko

2015-01-01

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. 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. 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 structural features, supporting the formation of the host-guest complexes. Complexes of NC 2067 with CDgemini surfactants formed nanoparticles having sizes of 100-200 nm. NC 2067 retained its anticancer activity in the complex with CDgemini surfactant for different drug-to-carrier mole ratios, with an IC50 (half-maximal inhibitory concentration) value comparable to that for NC 2067 without the carrier. The formation of host-guest complexes of NC 2067 with CD or CDgemini surfactant has been confirmed and hence the CDgemini surfactant shows good potential to be used as a delivery system for anticancer agents.

Study of β-cyclodextrin inclusion complexes with volatile molecules geraniol and α-terpineol enantiomers in solid state and in solution

NASA Astrophysics Data System (ADS)

Ceborska, Magdalena; Szwed, Kamila; Asztemborska, Monika; Wszelaka-Rylik, Małgorzata; Kicińska, Ewa; Suwińska, Kinga

2015-11-01

Geraniol and α-terpineol are insoluble in water volatile compounds. α-Terpineol is a potentially important agent for medical applications. Formation of molecular complexes with β-cyclodextrin would lead to the increase of water solubility and bioavailability. β-Cyclodextrin forms 2:2 inclusion complexes with both enantiomers of α-terpineol and their precursor geraniol. Solid state complexes are thoroughly characterized by single X-ray crystallography and their stability over vast range of temperatures is proven by TG analysis. Intermolecular host-guest, host-host and guest-guest interactions give good insight into the nature of formed inclusion complexes. Stability constants of the complexes in solution are determined by HPLC.

Mechanical measurement of hydrogen bonded host-guest systems under non-equilibrium, near-physiological conditions.

PubMed

Naranjo, Teresa; Cerrón, Fernando; Nieto-Ortega, Belén; Latorre, Alfonso; Somoza, Álvaro; Ibarra, Borja; Pérez, Emilio M

2017-09-01

Decades after the birth of supramolecular chemistry, there are many techniques to measure noncovalent interactions, such as hydrogen bonding, under equilibrium conditions. As ensembles of molecules rapidly lose coherence, we cannot extrapolate bulk data to single-molecule events under non-equilibrium conditions, more relevant to the dynamics of biological systems. We present a new method that exploits the high force resolution of optical tweezers to measure at the single molecule level the mechanical strength of a hydrogen bonded host-guest pair out of equilibrium and under near-physiological conditions. We utilize a DNA reporter to unambiguously isolate single binding events. The Hamilton receptor-cyanuric acid host-guest system is used as a test bed. The force required to dissociate the host-guest system is ∼17 pN and increases with the pulling rate as expected for a system under non-equilibrium conditions. Blocking one of the hydrogen bonding sites results in a significant decrease of the force-to-break by 1-2 pN, pointing out the ability of the method to resolve subtle changes in the mechanical strength of the binding due to the individual H-bonding components. We believe the method will prove to be a versatile tool to address important questions in supramolecular chemistry.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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.

Synthesis and characterization of water-soluble hydroxybutenyl cyclomaltooligosaccharides (cyclodextrins).

PubMed

Buchanan, Charles M; Alderson, Susan R; Cleven, Curtis D; Dixon, Daniel W; Ivanyi, Robert; Lambert, Juanelle L; Lowman, Douglas W; Offerman, Rick J; Szejtli, Jozsef; Szente, Lajos

2002-03-15

We have examined the synthesis of hydroxybutenyl cyclomaltooligosaccharides (cyclodextrins) and the ability of these cyclodextrin ethers to form guest-host complexes with guest molecules. The hydroxybutenyl cyclodextrin ethers were prepared by a base-catalyzed reaction of 3,4-epoxy-1-butene with the parent cyclodextrins in an aqueous medium. Reaction byproducts were removed by nanofiltration before the hydroxybutenyl cyclodextrins were isolated by co-evaporation of water-EtOH. Hydroxybutenyl cyclodextrins containing no unsubstituted parent cyclodextrin typically have a degree of substitution of 2-4 and a molar substitution of 4-7. These hydroxybutenyl cyclodextrins are randomly substituted, amorphous solids. The hydroxybutenyl cyclodextrin ethers were found to be highly water soluble. Complexes of HBen-beta-CD with glibenclamide and ibuprofen were prepared and isolated. In both cases, the guest content of the complexes was large, and a significant increase in the solubility of the free drug was observed. Dissolution of the complexes in pH 1.4 water was very rapid, and significant increases in the solubility of the free drugs were observed. Significantly, after reaching equilibrium concentration, a decrease in the drug concentration over time was not observed.

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

PubMed

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.

A synthetic mimic of protein inner space: buried polar interactions in a deep water-soluble host.

PubMed

Butterfield, Sara M; Rebek, Julius

2006-12-06

A deep water-soluble cavitand was functionalized with a carboxylic acid directed toward the hydrophobic interior of the host. The buried salt-bridge interaction formed with a quinuclidium cationic guest was determined to be worth -3 kcal/mol using a free energy cycle. The strength of the interaction correlates well with buried salt bridges in proteins, indicating that the cavitand interior mimics the hydrophobic inner space of proteins.

Supramolecular guests in solvent driven block copolymer assembly: From internally structured nanoparticles to micelles

PubMed Central

Klinger, Daniel; Robb, Maxwell J.; Spruell, Jason M.; Lynd, Nathaniel A.; Hawker, Craig J.

2014-01-01

Supramolecular interactions between different hydrogen-bonding guests and poly(2-vinyl pyridine)-block-poly (styrene) can be exploited to prepare remarkably diverse self-assembled nanostructures in dispersion from a single block copolymer (BCP). The characteristics of the BCP can be efficiently controlled by tailoring the properties of a guest which preferentially binds to the P2VP block. For example, the incorporation of a hydrophobic guest creates a hydrophobic BCP complex that forms phase separated nanoparticles upon self-assembly. Conversely, the incorporation of a hydrophilic guest results in an amphiphilic BCP complex that forms spherical micelles in water. The ability to tune the self-assembly behavior and access dramatically different nanostructures from a single BCP substrate demonstrates the exceptional versatility of the self-assembly of BCPs driven by supramolecular interactions. This approach represents a new methodology that will enable the further design of complex, responsive self-assembled nanostructures. PMID:25525473

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

PubMed

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.

Sequential energy and charge transfer processes in mixed host-guest complexes of subphthalocyanine, porphyrin and phthalocyanine chromophores.

PubMed

Menting, Roel; Ng, Dennis K P; Röder, Beate; Ermilov, Eugeny A

2012-11-14

Porphyrins, phthalocyanines and subphthalocyanines are three attractive classes of chromophores with intriguing properties making them suitable for the design of artificial photosynthetic systems. The assembly of these components by a supramolecular approach is of particular interest as it provides a facile means to build multi-chromophoric arrays with various architectures and tuneable photophysical properties. In this paper, we show the formation of mixed host-guest supramolecular complexes that consist of a β-cyclodextrin-conjugated subphthalocyanine, a tetrasulfonated porphyrin and a series of silicon(IV) phthalocyanines substituted axially with two β-cyclodextrins via different spacers. We found that the three components form supramolecular complexes held by host-guest interactions in aqueous solution. Upon excitation of the subphthalocyanine part of the complex, the excitation energy is delivered to the phthalocyanine unit via excitation energy transfer and the porphyrin chromophore acts as an energy transfer bridge enabling this process. It was shown that photo-induced charge transfer also takes place. A sequential electron transfer process from the porphyrin unit to the phthalocyanine moiety and subsequently from the subphthalocyanine moiety to the porphyrin unit takes place, and the probability of this process is controlled by the linker between β-cyclodextrin and phthalocyanine. The lifetime of the charge-separated state was found to be 1.7 ns by transient absorption spectroscopy.

Vesicular perylene dye nanocapsules as supramolecular fluorescent pH sensor systems.

PubMed

Zhang, Xin; Rehm, Stefanie; Safont-Sempere, Marina M; Würthner, Frank

2009-11-01

Water-soluble, self-assembled nanocapsules composed of a functional bilayer membrane and enclosed guest molecules can provide smart (that is, condition responsive) sensors for a variety of purposes. Owing to their outstanding optical and redox properties, perylene bisimide chromophores are interesting building blocks for a functional bilayer membrane in a water environment. Here, we report water-soluble perylene bisimide vesicles loaded with bispyrene-based energy donors in their aqueous interior. These loaded vesicles are stabilized by in situ photopolymerization to give nanocapsules that are stable over the entire aqueous pH range. On the basis of pH-tunable spectral overlap of donors and acceptors, the donor-loaded polymerized vesicles display pH-dependent fluorescence resonance energy transfer from the encapsulated donors to the bilayer dye membrane, providing ultrasensitive pH information on their aqueous environment with fluorescence colour changes covering the whole visible light range. At pH 9.0, quite exceptional white fluorescence could be observed for such water-soluble donor-loaded perylene vesicles.

Versatile types of polysaccharide-based supramolecular polycation/pDNA nanoplexes for gene delivery

NASA Astrophysics Data System (ADS)

Hu, Yang; Zhao, Nana; Yu, Bingran; Liu, Fusheng; Xu, Fu-Jian

2014-06-01

Different polysaccharide-based supramolecular polycations were readily synthesized by assembling multiple β-cyclodextrin-cored star polycations with an adamantane-functionalized dextran via host-guest interaction in the absence or presence of bioreducible linkages. Compared with nanoplexes of the starting star polycation and pDNA, the supramolecular polycation/pDNA nanoplexes exhibited similarly low cytotoxicity, improved cellular internalization and significantly higher gene transfection efficiencies. The incorporation of disulfide linkages imparted the supramolecular polycation/pDNA nanoplexes with the advantage of intracellular bioreducibility, resulting in better gene delivery properties. In addition, the antitumor properties of supramolecular polycation/pDNA nanoplexes were also investigated using a suicide gene therapy system. The present study demonstrates that the proper assembly of cyclodextrin-cored polycations with adamantane-functionalized polysaccharides is an effective strategy for the production of new nanoplex delivery systems.Different polysaccharide-based supramolecular polycations were readily synthesized by assembling multiple β-cyclodextrin-cored star polycations with an adamantane-functionalized dextran via host-guest interaction in the absence or presence of bioreducible linkages. Compared with nanoplexes of the starting star polycation and pDNA, the supramolecular polycation/pDNA nanoplexes exhibited similarly low cytotoxicity, improved cellular internalization and significantly higher gene transfection efficiencies. The incorporation of disulfide linkages imparted the supramolecular polycation/pDNA nanoplexes with the advantage of intracellular bioreducibility, resulting in better gene delivery properties. In addition, the antitumor properties of supramolecular polycation/pDNA nanoplexes were also investigated using a suicide gene therapy system. The present study demonstrates that the proper assembly of cyclodextrin-cored polycations with adamantane-functionalized polysaccharides is an effective strategy for the production of new nanoplex delivery systems. Electronic supplementary information (ESI) available: 1H NMR assay and synthetic route of Dex-Ad and Dex-SS-Ad. See DOI: 10.1039/c4nr01590h

Bioadhesive Polymersome for Localized and Sustained Drug Delivery at Pathological Sites with Harsh Enzymatic and Fluidic Environment via Supramolecular Host-Guest Complexation.

PubMed

Zhu, Meiling; Wei, Kongchang; Lin, Sien; Chen, Xiaoyu; Wu, Chia-Ching; Li, Gang; Bian, Liming

2018-02-01

Targeted and sustained delivery of drugs to diseased tissues/organs, where body fluid exchange and catabolic activity are substantial, is challenging due to the fast cleansing and degradation of the drugs by these harsh environmental factors. Herein, a multifunctional and bioadhesive polycaprolactone-β-cyclodextrin (PCL-CD) polymersome is developed for localized and sustained co-delivery of hydrophilic and hydrophobic drug molecules. This PCL-CD polymersome affords multivalent crosslinking action via surface CD-mediated host-guest interactions to generate a supramolecular hydrogel that exhibits evident shear thinning and efficient self-healing behavior. The co-delivery of small molecule and proteinaceous agents by the encapsulated PCL-CD polymersomes enhances the differentiation of stem cells seeded in the hydrogel. Furthermore, the PCL-CD polymersomes are capable of in situ grafting to biological tissues via host-guest complexation between surface CD and native guest groups in the tissue matrix both in vitro and in vivo, thereby effectively extending the retention of loaded cargo in the grafted tissue. It is further demonstrated that the co-delivery of small molecule and proteinaceous drugs via PCL-CD polymersomes averts cartilage degeneration in animal osteoarthritic (OA) knee joints, which are known for their biochemically harsh and fluidically dynamic environment. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

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

PubMed

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.

Host-Guest Complexes of Carboxylated Pillar[n]arenes With Drugs.

PubMed

Wheate, Nial J; Dickson, Kristie-Ann; Kim, Ryung Rae; Nematollahi, Alireza; Macquart, René B; Kayser, Veysel; Yu, Guocan; Church, W Bret; Marsh, Deborah J

2016-12-01

Pillar[n]arenes are a new family of nanocapsules that have shown application in a number of areas, but because of their poor water solubility their biomedical applications are limited. Recently, a method of synthesizing water-soluble pillar[n]arenes was developed. In this study, carboxylated pillar[n]arenes (WP[n], n = 6 or 7) have been examined for their ability to form host-guest complexes with compounds relevant to drug delivery and biodiagnostic applications. Both pillar[n]arenes form host-guest complexes with memantine, chlorhexidine hydrochloride, and proflavine by 1 H nuclear magnetic resonance and modeling. Binding is stabilized by hydrophobic effects within the cavities, and hydrogen bonding and electrostatic interactions at the portals. Encapsulation within WP[6] results in the complete and efficient quenching of proflavine fluorescence, giving rise to "on" and "off" states that have potential in biodiagnostics. The toxicity of the pillar[n]arenes was examined using in vitro growth assays with the OVCAR-3 and HEK293 cell lines. The pillar[n]arenes are relatively nontoxic to cells except at high doses and after prolonged continuous exposure. Overall, the results show that there could be a potentially large range of medical applications for carboxylated pillar[n]arene nanocapsules. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Rotaxane and catenane host structures for sensing charged guest species.

PubMed

Langton, Matthew J; Beer, Paul D

2014-07-15

CONSPECTUS: The promise of mechanically interlocked architectures, such as rotaxanes and catenanes, as prototypical molecular switches and shuttles for nanotechnological applications, has stimulated an ever increasing interest in their synthesis and function. The elaborate host cavities of interlocked structures, however, can also offer a novel approach toward molecular recognition: this Account describes the use of rotaxane and catenane host systems for binding charged guest species, and for providing sensing capability through an integrated optical or electrochemical reporter group. Particular attention is drawn to the exploitation of the unusual dynamic properties of interlocked molecules, such as guest-induced shuttling or conformational switching, as a sophisticated means of achieving a selective and functional sensor response. We initially survey interlocked host systems capable of sensing cationic guests, before focusing on our accomplishments in synthesizing rotaxanes and catenanes designed for the more challenging task of selective anion sensing. In our group, we have developed the use of discrete anionic templation to prepare mechanically interlocked structures for anion recognition applications. Removal of the anion template reveals an interlocked host system, possessing a unique three-dimensional geometrically restrained binding cavity formed between the interlocked components, which exhibits impressive selectivity toward complementary anionic guest species. By incorporating reporter groups within such systems, we have developed both electrochemical and optical anion sensors which can achieve highly selective sensing of anionic guests. Transition metals, lanthanides, and organic fluorophores integrated within the mechanically bonded structural framework of the receptor are perturbed by the binding of the guest, with a concomitant change in the emission profile. We have also exploited the unique dynamics of interlocked hosts by demonstrating that an 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.

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

PubMed

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

NASA Astrophysics Data System (ADS)

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.

Carbohydrates in Supramolecular Chemistry.

PubMed

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.

Formation of Cucurbit[8]uril-Based Supramolecular Hydrogel Beads Using Droplet-Based Microfluidics.

PubMed

Xu, Xuejiao; Appel, Eric A; Liu, Xin; Parker, Richard M; Scherman, Oren A; Abell, Chris

2015-09-14

Herein we describe the use of microdroplets as templates for the fabrication of uniform-sized supramolecular hydrogel beads, assembled by supramolecular cross-linking of functional biopolymers with the macrocyclic host molecule, cucurbit[8]uril (CB[8]). The microdroplets were formed containing diluted hydrogel precursors in solution, including the functional polymers and CB[8], in a microfluidic device. Subsequent evaporation of water from collected microdroplets concentrated the contents, driving the formation of the CB[8]-mediated host-guest ternary complex interactions and leading to the assembly of condensed three-dimensional polymeric scaffolds. Rehydration of the dried particles gave monodisperse hydrogel beads. Their equilibrium size was shown to be dependent on both the quantity of material loaded and the dimensions of the microfluidic flow focus. Fluorescein-labeled dextran was used to evaluate the efficacy of the hydrogel beads as a vector for controlled cargo release. Both passive, sustained release (hours) and triggered, fast release (minutes) of the FITC-dextran was observed, with the rate of sustained release dependent on the formulation. The kinetics of release was fitted to the Ritger-Peppas controlled release equation and shown to follow an anomalous (non-Fickian) transport mechanism.

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

PubMed Central

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

Efficient active-template synthesis of calix[6]arene-based oriented pseudorotaxanes and rotaxanes.

PubMed

Zanichelli, Valeria; Ragazzon, Giulio; Orlandini, Guido; Venturi, Margherita; Credi, Alberto; Silvi, Serena; Arduini, Arturo; Secchi, Andrea

2017-08-16

A substrate can modify its chemical features, including a change of its reactivity, as a consequence of non-covalent interactions upon inclusion within a molecular host. Since the rise of supramolecular chemistry, this phenomenon has stimulated the ingenuity of scientists to emulate the function of enzymes by designing supramolecular systems in which the energetics and selectivity of reactions can be manipulated through programmed host-guest interactions and/or steric confinement. In this paper we investigate how the engulfment of a positively charged pyridinium-based guest inside the π-rich cavity of a tris-(N-phenylureido)calix[6]arene host affects its reactivity towards a S N 2 reaction. We found that the alkylation of complexed substrates leads to the formation of pseudorotaxanes and rotaxanes with faster kinetics and higher yields with respect to the standard procedures exploited so far. More importantly, the strategy described here expands the range of efficient synthetic routes for the formation of mechanically interlocked species with a strict control of the mutual orientation of their non-symmetric molecular components.

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

PubMed

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.

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

PubMed

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 release from the doxorubicin (DOX)-loaded supramolecular star-shaped micelles due to the oxidation-induced dissociation of β-CD/Fc pair and the consequent loss of the colloidal stability of the star-shaped micelles. Studies of the delivery efficacy by an in vitro cytotoxicity study further indicated that higher DBs and longer hydrophilic arm compromised the therapeutic efficacy of the DOX-loaded supramolecular star-shaped micelles, resulting in significantly reduced cytotoxicity, as measured by increased IC 50 value. Overall, our results revealed that the screening of hydrophilic block by DB and MW for an optimized star-shaped copolymer should balance the stability versus therapeutic efficacy tradeoff for a comprehensive consideration. Therefore, the 12-arm star-shaped copolymer with POEGMA 30 is the best formulation tested. Copyright © 2017 Elsevier Inc. All rights reserved.

3D nitrogen-doped graphene/β-cyclodextrin: host-guest interactions for electrochemical sensing

NASA Astrophysics Data System (ADS)

Liu, Jilun; Leng, Xuanye; Xiao, Yao; Hu, Chengguo; Fu, Lei

2015-07-01

Host-guest interactions, especially those between cyclodextrins (CDs, including α-, β- and γ-CD) and various guest molecules, exhibit a very high supramolecular recognition ability. Thus, they have received considerable attention in different fields. These specific interactions between host and guest molecules are promising for biosensing and clinical detection. However, there is a lack of an ideal electrode substrate for CDs to increase their performance in electrochemical sensing. Herein, we propose a new 3D nitrogen-doped graphene (3D-NG) based electrochemical sensor, taking advantage of the superior sensitivity of host-guest interactions. Our 3D-NG was fabricated by a template-directed chemical vapour deposition (CVD) method, and it showed a large specific surface area, a high capacity for biomolecules and a high electron transfer efficiency. Thus, for the first time, we took 3D-NG as an electrode substrate for β-CD to establish a new type of biosensor. Using dopamine (DA) and acetaminophen (APAP) as representative guest molecules, our 3D-NG/β-CD biosensor shows extremely high sensitivities (5468.6 μA mM-1 cm-2 and 2419.2 μA mM-1 cm-2, respectively), which are significantly higher than those reported in most previous studies. The stable adsorption of β-CD on 3D-NG indicates potential applications in clinical detection and medical testing.Host-guest interactions, especially those between cyclodextrins (CDs, including α-, β- and γ-CD) and various guest molecules, exhibit a very high supramolecular recognition ability. Thus, they have received considerable attention in different fields. These specific interactions between host and guest molecules are promising for biosensing and clinical detection. However, there is a lack of an ideal electrode substrate for CDs to increase their performance in electrochemical sensing. Herein, we propose a new 3D nitrogen-doped graphene (3D-NG) based electrochemical sensor, taking advantage of the superior sensitivity of host-guest interactions. Our 3D-NG was fabricated by a template-directed chemical vapour deposition (CVD) method, and it showed a large specific surface area, a high capacity for biomolecules and a high electron transfer efficiency. Thus, for the first time, we took 3D-NG as an electrode substrate for β-CD to establish a new type of biosensor. Using dopamine (DA) and acetaminophen (APAP) as representative guest molecules, our 3D-NG/β-CD biosensor shows extremely high sensitivities (5468.6 μA mM-1 cm-2 and 2419.2 μA mM-1 cm-2, respectively), which are significantly higher than those reported in most previous studies. The stable adsorption of β-CD on 3D-NG indicates potential applications in clinical detection and medical testing. Electronic supplementary information (ESI) available: The procedure for preparing the sensor, wide survey XPS, XRD patterns, the effect of scan rate, more CV data on the stability and selectivity, and a comparison with previous studies. See DOI: 10.1039/c5nr03109e

Thermodynamics of hydrogen bond patterns in supramolecular assemblies of water molecules.

PubMed

Henry, Marc

2002-07-02

The PACHA (Partial Atomic Charges and Hardnesses Analysis) formalism is applied to various supramolecular assemblies of water molecules. After a detailed study of all available crystal structures for ice polymorphs, we shown that the hydrogen bond strength is roughly constant below 1 GPa and considerably weakened above that value. New hydrogen bond patterns are proposed for ice IV, V, and VI after (EB) (electrostatic balance) minimization. For other polymorphs, there is an almost perfect coincidence between experimental and predicted hydrogen bond patterns. The evolution of hydrogen bond energy as a function of molecular geometry in water clusters with up to 280 water molecules and in large supramolecular compounds is quantitatively described. Intermolecular hydrogen bonds are found to lie between -9 and -32 kJ mol-1, the stronger interaction occurs within the spherical fully disordered water droplet buried at the heart of Müller's superfullerene keplerate. The weakest one occurs in a chiral molecular snub cube built from six calix[4]resorcinarene and eight water molecules. Intramolecular hydrogen bonds are found in the range -10-100 kJ mol-1 and can thus be considerably stronger than intermolecular bonds. Finally, through the investigation of a clathrate type I compound, it was possible to obtain a deep insight of the host-guest interactions and self-assembly rules of water cages in these materials.

Ball and socket nanostructures: New supramolecular chemistry based on cyclotriveratrylene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steed, J.W.; Junk, P.C.; Atwood, J.L.

1994-11-02

This paper outlines new vistas for the inclusion chemistry of hosts based upon the cyclotriveratrylene motif. A simple method of retrieving pure fullerenes from fullerite without the use of chromatographic techniques has been outlined, and a new class of ball and socket-type inclusion species has been realized by simple modification of either host or guest electronic and steric properties. 14 refs., 2 figs.

Stimuli-responsive supramolecular micellar assemblies of cetylpyridinium chloride with cucurbit[5/7]urils.

PubMed

Choudhury, Sharmistha Dutta; Barooah, Nilotpal; Aswal, Vinod Kumar; Pal, Haridas; Bhasikuttan, Achikanath C; Mohanty, Jyotirmayee

2014-05-21

This article demonstrates, for the first time, construction of novel cucurbituril (CB)-adorned supramolecular micellar assemblies of a cationic surfactant, cetylpyridinium chloride (CPC), through noncovalent host-guest interactions. The distinct cation receptor features and cavity dimensions of the CB5 and CB7 homologues assert that the macrocyclic hosts remain complexed with the CPC monomers and take part in the micelle formation, a unique observation in contrast to that of the classical host, β-cyclodextrin. The cooperative contributions of the CB macrocycles in the micelle formation have been documented by the photochemical, surface tension, conductivity, DOSY NMR, and SANS measurements. The contrasting downward and upward shifts in the cmc of the CPC surfactant, respectively, with CB5 and CB7 hosts provide a unique opportunity for the controlled tuning of the micellization region for CPC from 0.57 to 1.6 mM, by using a combination of the macrocyclic hosts. The article also establishes the reversible response of these soft supramolecular micellar structures to thermal-stimuli, which projects their utility for on-demand smart drug-delivery vehicles.

Complexation induced aggregation and deaggregation of acridine orange with sulfobutylether-β-cyclodextrin.

PubMed

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.

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

PubMed

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.

ESI-MS of Cucurbituril Complexes Under Negative Polarity.

PubMed

Rodrigues, Maria A A; Mendes, Débora C; Ramamurthy, Vaidhyanathan; Da Silva, José P

2017-11-01

Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool to study host-guest supramolecular interactions. ESI-MS can be used for detailed gas-phase reactivity studies, to clarify the structure, or simply to verify the formation of complexes. Depending on the structure of the host and of the guest, negative and/or positive ESI are used. Here we report the unexpected formation of host-guest complexes between cucurbit[n]urils (n = 7, 8, CB[n]) and amine, styryl pyridine, and styryl pyridine dimer cations, under negative ESI. Non-complexed CB[n] form double charged halide (Br - , Cl - , F - ) adducts. Under negative ESI, halide ions interact with CB[n] outer surface hydrogen atoms. One to one host-guest complexes (1:1) of CB[n] with positive charged guests were also observed as single and double charged ions under negative ESI. The positive charge of guests is neutralized by ion-pairing with halide anions. Depending on the number of positive charges guests retain in the gas phase, one or two additional halide ions are required for neutralization. Complexes 1:2 of CB[8] with styryl pyridines retain two halide ions in the gas phase, one per guest. Styryl pyridine dimers form 1:1 complexes possessing a single extra halide ion and therefore a single positive charge. Negative ESI is sensitive to small structural differences between complexes, distinguishing between 1:2 complexes of styryl pyridine-CB[8] and corresponding 1:1 complexes with the dimer. Negative ESI gives simpler spectra than positive ESI and allows the determination of guest charge state of CB[n] complexes in the gas phase. Graphical Abstract ᅟ.

The SAMPL4 host-guest blind prediction challenge: an overview.

PubMed

Muddana, Hari S; Fenley, Andrew T; Mobley, David L; Gilson, Michael K

2014-04-01

Prospective validation of methods for computing binding affinities can help assess their predictive power and thus set reasonable expectations for their performance in drug design applications. Supramolecular host-guest systems are excellent model systems for testing such affinity prediction methods, because their small size and limited conformational flexibility, relative to proteins, allows higher throughput and better numerical convergence. The SAMPL4 prediction challenge therefore included a series of host-guest systems, based on two hosts, cucurbit[7]uril and octa-acid. Binding affinities in aqueous solution were measured experimentally for a total of 23 guest molecules. Participants submitted 35 sets of computational predictions for these host-guest systems, based on methods ranging from simple docking, to extensive free energy simulations, to quantum mechanical calculations. Over half of the predictions provided better correlations with experiment than two simple null models, but most methods underperformed the null models in terms of root mean squared error and linear regression slope. Interestingly, the overall performance across all SAMPL4 submissions was similar to that for the prior SAMPL3 host-guest challenge, although the experimentalists took steps to simplify the current challenge. While some methods performed fairly consistently across both hosts, no single approach emerged as consistent top performer, and the nonsystematic nature of the various submissions made it impossible to draw definitive conclusions regarding the best choices of energy models or sampling algorithms. Salt effects emerged as an issue in the calculation of absolute binding affinities of cucurbit[7]uril-guest systems, but were not expected to affect the relative affinities significantly. Useful directions for future rounds of the challenge might involve encouraging participants to carry out some calculations that replicate each others' studies, and to systematically explore parameter options.

Size-controlled and redox-responsive supramolecular nanoparticles

PubMed Central

2015-01-01

Summary 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 moiety. The SNPs are composed of a core of positively charged poly(ethylene imine) grafted with β-cyclodextrin (CD) and a positively charged ferrocene (Fc)-terminated poly(amidoamine) dendrimer, with a monovalent stabilizer at the surface. Fc was chosen for its loss of CD-binding properties when oxidizing it to the ferrocenium cation. The ionic strength was shown to play an important role in controlling the aggregate growth. The attractive supramolecular and repulsive electrostatic interactions constitute a balance of forces in this system at low ionic strengths. At higher ionic strengths, the increased charge screening led to a loss of electrostatic repulsion and therefore to faster aggregate growth. A Job plot showed that a 1:1 stoichiometry of host and guest moieties gave the most efficient aggregate growth. Different stabilizers were used to find the optimal stopper to limit the growth. A weaker guest moiety was shown to be less efficient in stabilizing the SNPs. Also steric repulsion is important for achieving SNP stability. SNPs of controlled particle size and good stability (up to seven days) were prepared by fine-tuning the ratio of multivalent and monovalent interactions. Finally, reversibility of the SNPs was confirmed by oxidizing the Fc guest moieties in the core of the SNPs. PMID:26733345

Host-guest chemistry of cyclodextrin carbamates and cellulose derivatives in aqueous solution.

PubMed

Guo, Xin; Jia, Xiangxiang; Du, Jiaojiao; Xiao, Longqiang; Li, Feifei; Liao, Liqiong; Liu, Lijian

2013-10-15

Supramolecular polymer micelles were prepared on basis of the inclusion complexation between cyclodextrin carbamates and cellulose derivatives in aqueous media. Cyclodextrin carbamates were synthesized by microwave-assisted method from cyclodextrin and urea. The urea modified cyclodextrin shows the higher yield than the physical mixture of urea/cyclodextrin in the micellization with cellulose derivatives. The supramolecular structure of the core-shell micelles was demonstrated by (1)H NMR spectra, TEM images, and fluorescence spectra. The drug release behavior of the supramolecular polymer micelles was evaluated using prednisone acetate as a model drug. The drug loaded micelles showed steady and long time drug release behavior. With these properties, the supramolecular polymer micelles are attractive as drug carriers for pharmaceutical applications. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

PubMed

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.

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

PubMed

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.

Energetics of small molecule and water complexation in hydrophobic calixarene cavities.

PubMed

Notestein, Justin M; Katz, Alexander; Iglesia, Enrique

2006-04-25

Calixarenes grafted on silica are energetically uniform hosts that bind aromatic guests with 1:1 stoichiometry, as shown by binding energies that depend upon the calixarene upper rim composition but not on their grafted surface density (0.02-0.23 nm(-2)). These materials are unique in maintaining a hydrophilic silica surface, as probed by H2O physisorption measurements, while possessing a high density of hydrophobic binding sites that are orthogonal to the silica surface below them. The covalently enforced cone-shaped cavities and complete accessibility of these rigidly grafted calixarenes allow the first unambiguous measurements of the thermodynamics of guest interaction with the same calixarene cavities in aqueous solution and vapor phase. Similar to adsorption into nonpolar protein cavities, adsorption into these hydrophobic cavities from aqueous solution is enthalpy-driven, which is in contrast to entropy-driven adsorption into water-soluble hydrophobic hosts such as beta cyclodextrin. The adsorption thermodynamics of several substituted aromatics from vapor and liquid are compared by (i) describing guest chemical potentials relative to pure guest, which removes differences among guests because of aqueous solvation and van der Waals contacts in the pure condensed phase, and (ii) passivating residual guest binding sites on exposed silica, titrated by water during adsorption from aqueous solution, using inorganic salts before vapor adsorption. Adsorption isotherms depend only upon the saturation vapor pressure of each guest, indicating that guest binding from aqueous or vapor media is controlled by van der Waals contacts with hydrophobic calixarene cavities acting as covalently assembled condensation nuclei, without apparent contributions from CH-pi or other directional interactions. These data also provide the first direct quantification of free energies for interactions of water with the calixarene cavity interior. The calixarene-water interface is stabilized by approximately 20 kJ/mol relative to the water-vapor interface, indicating that water significantly competes with the aromatic guests for adsorption at these ostensibly hydrophobic cavities. This result is useful for understanding models of water interactions with other concave hydrophobic surfaces, including those commonly observed within proteins.

Design of a photoswitchable hollow microcapsular drug delivery system by using a supramolecular drug-loading approach.

PubMed

Xiao, Wang; Chen, Wei-Hai; Zhang, Jing; Li, Cao; Zhuo, Ren-Xi; Zhang, Xian-Zheng

2011-11-24

In this study, photoswitchable microcapsules were fabricated based on host-guest interactions between α-cyclodextrin (α-CD) and azobenzene (Azo). Carboxymethyl dextran-graft-α-CD (CMD-g-α-CD) and poly(acrylic acid) N-aminododecane p-azobenzeneaminosuccinic acid (PAA-C(12)-Azo) were assembled layer by layer on CaCO(3) particles. α-CD-rhodamine B (α-CD-RhB), used as a model drug, was loaded on PAA-C(12)-Azo layers by host-guest interaction. After removal of CaCO(3) particles by ethylenediaminetetraacetic acid (EDTA), hollow microcapsules loaded with α-CD-RhB were obtained. Since the interactions between α-CD and Azo were photosensitive, the capsules could be dissociated with the irradiation of UV light, followed by the release of the model drug, α-CD-RhB. Compared with traditional drug-loading approaches such as chemical bonding and physical adsorption, our supramolecular drug-loading system has a facile loading process, ideal bonding strength, and photoswitchable behavior. These photosensitive microcapsules exhibit great potential in biomedical applications. © 2011 American Chemical Society

Host-guest interaction induced supramolecular amphiphilic star architecture and uniform nanovesicle formation for anticancer drug delivery

NASA Astrophysics Data System (ADS)

Zhu, Jing-Ling; Liu, Kerh Li; Wen, Yuting; Song, Xia; Li, Jun

2016-01-01

A star polymer of poly[(R,S)-3-hydroxybutyrate] (PHB) with adamantyl end-terminals extended from an α-cyclodextrin (α-CD) core is designed. It subsequently self-assembles to form controllable and uniform nanovesicles induced by host-guest interactions between heptakis(2,6-di-O-methyl)-β-CD and the adamantyl ends. The nanovesicles are suitable for loading and intracellular delivery of the anticancer drug doxorubicin.A star polymer of poly[(R,S)-3-hydroxybutyrate] (PHB) with adamantyl end-terminals extended from an α-cyclodextrin (α-CD) core is designed. It subsequently self-assembles to form controllable and uniform nanovesicles induced by host-guest interactions between heptakis(2,6-di-O-methyl)-β-CD and the adamantyl ends. The nanovesicles are suitable for loading and intracellular delivery of the anticancer drug doxorubicin. Electronic supplementary information (ESI) available: Polymer synthesis, characterization, preparation of drug-loaded nanovesicles, intracellular drug release and cytotoxicity assays, TEM and DLS measurements. See DOI: 10.1039/c5nr06744h

Host-guest interaction between pinocembrin and cyclodextrins: Characterization, solubilization and stability

NASA Astrophysics Data System (ADS)

Zhou, Shu-Ya; Ma, Shui-Xian; Cheng, Hui-Lin; Yang, Li-Juan; Chen, Wen; Yin, Yan-Qing; Shi, Yi-Min; Yang, Xiao-Dong

2014-01-01

The inclusion complexation behavior, characterization and binding ability of pinocembrin with β-cyclodextrin (β-CD) and its derivative 2-hydroxypropyl-β-cyclodextrin (HPβCD) were investigated in both solution and the solid state by means of XRD, DSC, 1H and 2D NMR and UV-vis spectroscopy. The results showed that the water solubility and thermal stability of pinocembrin were obviously increased in the inclusion complex with cyclodextrins. This satisfactory water solubility and high stability of the pinocembrin/CD complexes will be potentially useful for their application as herbal medicines or healthcare products.

Intracellular guest exchange between dynamic supramolecular hosts.

PubMed

Swaminathan, Subramani; Fowley, Colin; McCaughan, Bridgeen; Cusido, Janet; Callan, John F; Raymo, Françisco M

2014-06-04

Decyl and oligo(ethylene glycol) chains were appended to the same poly(methacrylate) backbone to generate an amphiphilic polymer with a ratio between hydrophobic and hydrophilic segments of 2.5. At concentrations greater than 10 μg mL(-1) in neutral buffer, multiple copies of this particular macromolecule assemble into nanoparticles with a hydrodynamic diameter of 15 nm. In the process of assembling, these nanoparticles can capture anthracene donors and borondipyrromethene acceptors within their hydrophobic interior and permit the transfer of excitation energy with an efficiency of 95%. Energy transfer is observed also if nanocarriers containing exclusively the donors are mixed with nanoparticles preloaded separately with the acceptors in aqueous media. The two sets of supramolecular assemblies exchange their guests with fast kinetics upon mixing to co-localize complementary chromophores within the same nanostructured container and enable energy transfer. After guest exchange, the nanoparticles can cross the membrane of cervical cancer cells and bring the co-entrapped donors and acceptors within the intracellular environment. Alternatively, intracellular energy transfer is also established after sequential cell incubation with nanoparticles containing the donors first and then with nanocarriers preloaded with the acceptors or vice versa. Under these conditions, the nanoparticles exchange their cargo only after internalization and allow energy transfer exclusively within the cell interior. Thus, the dynamic character of such supramolecular containers offers the opportunity to transport independently complementary species inside cells and permit their interaction only within the intracellular space.

Cyclic Bis-porphyrin-Based Flexible Molecular Containers: Controlling Guest Arrangements and Supramolecular Catalysis by Tuning Cavity Size.

PubMed

Mondal, Pritam; Sarkar, Sabyasachi; Rath, Sankar Prasad

2017-05-23

Three cyclic zinc(II) bis-porphyrins (CB) with highly flexible linkers are employed as artificial molecular containers that efficiently encapsulate/coordinate various aromatic aldehydes within their cavities. Interestingly, the arrangements of guests and their reactivity inside the molecular clefts are significantly influenced by the cavity size of the cyclic containers. In the presence of polycyclic aromatic aldehydes, such as 3-formylperylene, as a guest, the cyclic bis-porphyrin host with a smaller cavity (CB1) forms a 1:1 sandwich complex. Upon slightly increasing the spacer length and thereby the cavity size, the cyclic host (CB2) encapsulates two molecules of 3-formylperylene that are also stacked together due to strong π-π interactions between them and CH-π interactions with the porphyrin rings. However, in the cyclic host (CB3) with an even larger cavity, two metal centers of the bis-porphyrin axially coordinate two molecules of 3-formylperylene within its cavity. Different arrangements of guest inside the cyclic bis-porphyrin hosts are investigated by using UV/Vis, ESI-MS, and 1 H NMR spectroscopy, along with X-ray structure determination of the host-guest complexes. Moreover, strong binding of guests within the cyclic bis-porphyrin hosts support the robust nature of the host-guest assemblies in solution. Such preferential binding of the bis-porphyrinic cavity towards aromatic aldehydes through encapsulation/coordination has been employed successfully to catalyze the Knoevenagel condensation of a series of polycyclic aldehydes with active methylene compounds (such as Meldrum's acid and 1, 3-dimethylbarbituric acid) under ambient conditions. Interestingly, the yields of the condensed products significantly increase upon increasing spacer lengths of the cyclic bis-porphyrins because more substrates can then be encapsulated within the cavity. Such controllable cavity size of the cyclic containers has profound implications for constructing highly functional and modular enzyme mimics. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

Injectable supramolecular hydrogel formed from α-cyclodextrin and PEGylated arginine-functionalized poly(l-lysine) dendron for sustained MMP-9 shRNA plasmid delivery.

PubMed

Lin, Qianming; Yang, Yumeng; Hu, Qian; Guo, Zhong; Liu, Tao; Xu, Jiake; Wu, Jianping; Kirk, Thomas Brett; Ma, Dong; Xue, Wei

2017-02-01

Hydrogels have attracted much attention in cancer therapy and tissue engineering due to their sustained gene delivery ability. To obtain an injectable and high-efficiency gene delivery hydrogel, methoxypolyethylene glycol (MPEG) was used to conjugate with the arginine-functionalized poly(l-lysine) dendron (PLLD-Arg) by click reaction, and then the synthesized MPEG-PLLD-Arg interacted with α-cyclodextrin (α-CD) to form the supramolecular hydrogel by the host-guest interaction. The gelation dynamics, hydrogel strength and shear viscosity could be modulated by α-CD content in the hydrogel. MPEG-PLLD-Arg was confirmed to bind and deliver gene effectively, and its gene transfection efficiency was significantly higher than PEI-25k under its optimized condition. After gelation, MMP-9 shRNA plasmid (pMMP-9) could be encapsulated into the hydrogel matrix in situ and be released from the hydrogels sustainedly, as the release rate was dependent on α-CD content. The released MPEG-PLLD-Arg/pMMP-9 complex still showed better transfection efficiency than PEI-25k and induced sustained tumor cell apoptosis. Also, in vivo assays indicated that this pMMP-9-loaded supramolecular hydrogel could result in the sustained tumor growth inhibition meanwhile showed good biocompatibility. As an injectable, sustained and high-efficiency gene delivery system, this supramolecular hydrogel is a promising candidate for long-term gene therapy. To realize the sustained gene delivery for gene therapy, a supramolecular hydrogel with high-efficiency gene delivery ability was prepared through the host-guest interaction between α-cyclodextrin and PEGylated arginine-functionalized poly(l-lysine) dendron. The obtained hydrogel was injectable and biocompatible with adjustable physicochemical property. More importantly, the hydrogel showed the high-efficiency and sustained gene transfection to our used cells, better than PEI-25k. The supramolecular hydrogel resulted in the sustained tumor growth inhibition meanwhile keep good biocompatibility. As an injectable, sustained and high-efficiency gene delivery system, this supramolecular hydrogel is a promising candidate in long-term gene therapy and tissue engineering. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Aggregation of p-Sulfonatocalixarene-Based Amphiphiles and Supra-Amphiphiles

PubMed Central

Basilio, Nuno; Francisco, Vitor; Garcia-Rio, Luis

2013-01-01

p-Sulfonatocalixarenes are a special class of water soluble macrocyclic molecules made of 4-hydroxybenzenesulfonate units linked by methylene bridges. One of the main features of these compounds relies on their ability to form inclusion complexes with cationic and neutral species. This feature, together with their water solubility and apparent biological compatibility, had enabled them to emerge as one the most important host receptors in supramolecular chemistry. Attachment of hydrophobic alkyl chains to these compounds leads to the formation of macrocyclic host molecules with amphiphilic properties. Like other oligomeric surfactants, these compounds present improved performance with respect to their monomeric counterparts. In addition, they hold their recognition abilities and present several structural features that depend on the size of the macrocycle and on the length of the alkyl chain, such as preorganization, flexibility and adopted conformations, which make these molecules very interesting to study structure-aggregation relationships. Moreover, the recognition abilities of p-sulfonatocalixarenes enable them to be applied in the design of amphiphiles constructed from non-covalent, rather than covalent, bonds (supramolecular amphiphiles). In this review, we summarize the developments made on the design and synthesis of p-sulfonatocalixarenes-based surfactants, the characterization of their self-assembly properties and on how their structure affects these properties. PMID:23380960

High degree of polymerization in a fullerene-containing supramolecular polymer.

PubMed

Isla, Helena; Pérez, Emilio M; Martín, Nazario

2014-05-26

Supramolecular polymers based on dispersion forces typically show lower molecular weights (MW) than those based on hydrogen bonding or metal-ligand coordination. We present the synthesis and self-assembling properties of a monomer featuring two complementary units, a C60 derivative and an exTTF-based macrocycle, that interact mainly through π-π, charge-transfer, and van der Waals interactions. Thanks to the preorganization in the host part, a remarkable log K(a)=5.1±0.5 in CHCl3 at room temperature is determined for the host-guest couple. In accordance with the large binding constant, the monomer self-assembles in the gas phase, in solution, and in the solid state to form linear supramolecular polymers with a very high degree of polymerization. A MW above 150 kDa has been found experimentally in solution, while in the solid state the monomer forms extraordinarily long, straight, and uniform fibers with lengths reaching several microns. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dual-cavity basket promotes encapsulation in water in an allosteric fashion.

PubMed

Chen, Shigui; Yamasaki, Makoto; Polen, Shane; Gallucci, Judith; Hadad, Christopher M; Badjić, Jovica D

2015-09-30

We prepared dual-cavity basket 1 to carry six (S)-alanine residues at the entrance of its two juxtaposed cavities (289 Å(3)). With the assistance of (1)H NMR spectroscopy and calorimetry, we found that 1 could trap a single molecule of 4 (K1 = 1.45 ± 0.40 × 10(4) M(-1), ITC), akin in size (241 Å(3)) and polar characteristics to nerve agent VX (289 Å(3)). The results of density functional theory calculations (DFT, M06-2X/6-31G*) and experiments ((1)H NMR spectroscopy) suggest that the negative homotropic allosterism arises from the guest forming C-H···π contacts with all three of the aromatic walls of the occupied basket's cavity. In response, the other cavity increases its size and turns rigid to prevent the formation of the ternary complex. A smaller guest 6 (180 Å(3)), akin in size and polar characteristics to soman (186 Å(3)), was also found to bind to dual-cavity 1, although giving both binary [1⊂6] and ternary [1⊂62] complexes (K1 = 7910 M(-1) and K2 = 2374 M(-1), (1)H NMR spectroscopy). In this case, the computational and experimental ((1)H NMR spectroscopy) results suggest that only two aromatic walls of the occupied basket's cavity form C-H···π contacts with the guest to render the singly occupied host flexible enough to undergo additional structural changes necessary for receiving another guest molecule. The structural adaptivity of dual-cavity baskets of type 1 is unique and important for designing multivalent hosts capable of effectively sequestering targeted guests in an allosteric manner to give stable supramolecular polymers.

Supramolecularly Engineered Circular Bivalent Aptamer for Enhanced Functional Protein Delivery.

PubMed

Jiang, Ying; Pan, Xiaoshu; Chang, Jin; Niu, Weijia; Hou, Weijia; Kuai, Hailan; Zhao, Zilong; Liu, Ji; Wang, Ming; Tan, Weihong

2018-06-06

Circular bivalent aptamers (cb-apt) comprise an emerging class of chemically engineered aptamers with substantially improved stability and molecular recognition ability. Its therapeutic application, however, is challenged by the lack of functional modules to control the interactions of cb-apt with therapeutics. We present the design of a β-cyclodextrin-modified cb-apt (cb-apt-βCD) and its supramolecular interaction with molecular therapeutics via host-guest chemistry for targeted intracellular delivery. The supramolecular ensemble exhibits high serum stability and enhanced intracellular delivery efficiency compared to a monomeric aptamer. The cb-apt-βCD ensemble delivers green fluorescent protein into targeted cells with efficiency as high as 80%, or cytotoxic saporin to efficiently inhibit tumor cell growth. The strategy of conjugating βCD to cb-apt, and subsequently modulating the supramolecular chemistry of cb-apt-βCD, provides a general platform to expand and diversify the function of aptamers, enabling new biological and therapeutic applications.

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

NASA Astrophysics Data System (ADS)

Chui, Tin Ki

This thesis described the development of a new type of branched peptidomimetics using a class of previously reported triazole-containing peptidomimetics as the structural motif. The propensity of these new branched peptiomimetics in being an organogelator, forming supramolecular assemblies and recognizing anions and biomolecules was investigated. The quest began with the preparation of two different series of branched peptidomimetics, namely 69-K-aa3 (aa = V or L) and 70-B-aa3. The former series made use of the flexible L-lysine (K) as the branching unit while the latter series was composed of the relatively rigid 3,5-diminobenzoate (B). In each series, the peptidomimetic arms were composed of solely valine (V) or leucine (L). The effects of the identity of the amino acids and the branching units on the gelation and self-assembling properties of these branched bis(tripeptidomimetic)s were investigated. The 69-K-aa3 series was found to exhibit poor solubility in common organic solvents yet it was able to form strong and stable gels in aromatic solvents. The 70-B-aa3 series, on the other hand, was a poor organogelator despite its excellent solubility. Morphological studies using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed the ability of the former to form a hyperbranched 3D network whereas the latter was only capable of forming isolated spherical lumps. Nevertheless, the latter displayed the ability in forming supramolecular polymers as shown from viscometric studies. Solution-to-gel transition temperature measurement of the gels formed by the 69-K-aa3 series and association constants determination by 1H NMR titration experiments for the supramolecular polymerization of the 70-B-aa3 series both suggested that peptidomimetic arms comprised of valine performed better than those made up of leucine in terms of association strength, and such a difference was attributed to the bulkier nature of the leucine side chain. In order to obtain a clearer picture on the mode of association of these two series of branched peptidomimetics, the length of the tripeptidomimetic arms was truncated to a dipeptide, and the amino acid, valine, was used for further studies. Both the two new candidates, 88-K-V2 and 89-B-V2, were shown to dimerize in chloroform as shown from vapor pressure osmometry (VPO) studies. 1H NMR titration experiments indicated a better dimerization strength for the latter candidate due to the intermolecular pi-pi interactions offered by its benzene ring in addition to the intermolecular hydrogen bonding by the amides and triazole units. H/D exchange and 2D NMR experiments, and molecular modeling revealed that 88-K-V2 dimerized through the formation of antiparallel beta-strands whereas formation of parallel beta-strands took place in 89-B-V2. Compound 88-K-V2 was found to form 1:1 complexes with chloride (Ka 640 M-1) and monobasic diethyl phosphate (DEP) ion (Ka 810 M-1) in chloroform. Interestingly, 89-B-V 2 was shown to form the usual 1:1 complex with the former ion (Ka 970 M-1) while forming an unexpected 2:1 complex with the latter with positive cooperativity. It was observed that both the amides and triazole protons were involved in anion-binding. In the 88-K-V2-DEP complex, the host formed a helix-like structure that wrapped around the anion located at the center of the complex as determined by 2D NMR and molecular modeling studies. Finally, further structural modification of 88-K-V2 gave a water-soluble nucleotide-binding tweezer 93-K-R2·4TFA . This tweezer consisted of four arginines (R), two triazole units, two pyrene probes and a small hydrophilic ethanolamine tail. Fluorescence study showed that this tweezer was able to form 1:1 complexes with different nucleotides in water with similar binding strength regardless of the number of phosphate groups present in the nucleotides. Moleular modeling suggested that such a charge-independent binding behavior was due to the similar number 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.

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

PubMed

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.

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

PubMed

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.

White Light Emission from Cucurbituril-Based Host-Guest Interaction in the Solid State: New Function of the Macrocyclic Host.

PubMed

Xia, Yu; Chen, Shiyan; Ni, Xin-Long

2018-04-18

Energy transfer and interchange are central for fabricating white light-emitting organic materials. However, increasing the efficiency of light energy transfer remains a considerable challenge because of the occurrence of "cross talk". In this work, by exploiting the unique photophysical properties of cucurbituril-triggered host-guest interactions, the two complementary luminescent colors blue and yellow for white light emission were independently obtained from a single fluorophore dye rather than energy transfer. Further study suggested that the rigid cavity of cucurbiturils efficiently prevented the aggregation of the dye and improved its thermal stability in the solid state by providing a regular nanosized fence for each encapsulated dye molecule. As a result, a novel macrocycle-assisted supramolecular approach for obtaining solid, white light-emitting organic materials with low cost, high efficiency, and easy scale-up was successfully demonstrated.

Cyclen dithiocarbamate-functionalized silver nanoparticles as a probe for colorimetric sensing of thiram and paraquat pesticides via host-guest chemistry

NASA Astrophysics Data System (ADS)

Rohit, Jigneshkumar V.; Kailasa, Suresh Kumar

2014-11-01

We have developed a simple and rapid colorimetric method for on-site analysis of thiram and paraquat using cyclen dithiocarbamate-functionalized silver nanoparticles (CN-DTC-Ag NPs) as a colorimetric probe. The synthesized CN-DTC-Ag NPs were characterized by UV-Visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy, dynamic light scattering, and transmission electron microscopic techniques. The CN-DTC molecules provide good supramolecular self assembly on the surfaces of Ag NPs to encapsulate thiram and paraquat selectively via "host-guest" chemistry, resulting in red-shift in surface plasmon resonance peak of CN-DTC-Ag NPs from 396 to 530 nm and 510 nm and color change from yellow to pink for thiram and to orange for paraquat, which can be naked-eye detected. The present method shows good linearity in the range of 10.0-20.0 µM and of 50.0-250 µM with limits of detection 2.81 × 10-6 M and 7.21 × 10-6 M for thiram and paraquat, respectively. This method was proved as a promising tool for on-site and real-time monitoring of thiram and paraquat in environmental water, potato, and wheat samples.

Construction of Discrete Pentanuclear Platinum(II) Stacks with Extended Metal-Metal Interactions by Using Phosphorescent Platinum(II) Tweezers.

PubMed

Kong, Fred Ka-Wai; Chan, Alan Kwun-Wa; Ng, Maggie; Low, Kam-Hung; Yam, Vivian Wing-Wah

2017-11-20

Discrete pentanuclear Pt II stacks were prepared by the host-guest adduct formation between multinuclear tweezer-type Pt II complexes. The formation of the Pt II stacks in solution was accompanied by color changes and the turning on of near-infrared emission resulting from Pt⋅⋅⋅Pt and π-π interactions. The X-ray crystal structure revealed the formation of a discrete 1:1 adduct, in which a linear stack of five Pt II centers with extended Pt⋅⋅⋅Pt interactions was observed. Additional binding affinity and stability have been achieved through a multinuclear host-guest system. The binding behaviors can be fine-tuned by varying the spacer between the two Pt II moieties in the guests. This work provides important insights for the construction of discrete higher-order supramolecular metal-ligand aggregates using a tweezer-directed approach. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water-Soluble Pd8L4 Self-assembled Molecular Barrel as an Aqueous Carrier for Hydrophobic Curcumin.

PubMed

Bhat, Imtiyaz Ahmad; Jain, Ruchi; Siddiqui, Mujahuddin M; Saini, Deepak K; Mukherjee, Partha Sarathi

2017-05-01

A tetrafacial water-soluble molecular barrel (1) was synthesized by coordination driven self-assembly of a symmetrical tetrapyridyl donor (L) with a cis-blocked 90° acceptor [cis-(en)Pd(NO 3 ) 2 ] (en = ethane-1,2-diamine). The open barrel structure of (1) was confirmed by single crystal X-ray diffraction. The presence of a hydrophobic cavity with large windows makes it an ideal candidate for encapsulation and carrying hydrophobic drug like curcumin in an aqueous medium. The barrel (1) encapsulates curcumin inside its molecular cavity and protects highly photosensitive curcumin from photodegradation. The photostability of encapsulated curcumin is due to the absorption of a high proportion of the incident photons by the aromatic walls of 1 with a high absorption cross-sectional area, which helps the walls to shield the guest even against sunlight/UV radiations. As compared to free curcumin in water, we noticed a significant increase in solubility as well as cellular uptake of curcumin upon encapsulation inside the water-soluble molecular barrel (1) in aqueous medium. Fluorescence imaging confirmed that curcumin was delivered into HeLa cancer cells by the aqueous barrel (1) with the retention of its potential anticancer activity. While free curcumin is inactive toward cancer cells in aqueous medium at room temperature due to negligible solubility, the determined IC 50 value of ∼14 μM for curcumin in aqueous medium in the presence of the barrel (1) reflects the efficiency of the barrel as a potential curcumin carrier in aqueous medium without any other additives. Thus, two major challenges of increasing the bioavailability and stability of curcumin in aqueous medium even in the presence of UV light have been addressed by using a new supramolecular water-soluble barrel (1) as a drug carrier.

Dihydrogen phosphate-water tape and layers vs dihydrogen phosphate layers tuned by hydrophobic isomeric pyridine-diamine functionalized molecules

NASA Astrophysics Data System (ADS)

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.

Molecular Processing of Polymers with Cyclodextrins

NASA Astrophysics Data System (ADS)

Tonelli, Alan E.

We summarize our recent studies employing the cyclic starch derivatives called cyclodextrins (CDs) to both nanostructure and functionalize polymers. Two important structural characteristics of CDs are taken advantage of to achieve these goals. First the ability of CDs to form noncovalent inclusion complexes (ICs) with a variety of guest molecules, including many polymers, by threading and inclusion into their relatively hydrophobic interior cavities, which are roughly cylindrical with diameters of ˜ 0.5 - 1.0 nm. α-, β-, and γ-CD contain six, seven, and eight α-1,4-linked glucose units, respectively. Warm water washing of polymer-CD-ICs containing polymer guests insoluble in water or treatment with amylase enzymes serves to remove the host CDs and results in the coalescence of the guest polymers into solid samples. When guest polymers are coalesced from the CD-ICs by removing their host CDs, they are observed to solidify with structures, morphologies, and even conformations that are distinct from bulk samples made from their solutions and melts. Molecularly mixed, intimate blends of two or more polymers that are normally immiscible can be obtained from their common CD-ICs, and the phase segregation of incompatible blocks can be controlled (suppressed or increased) in CD-IC coalesced block copolymers. In addition, additives may be more effectively delivered to polymers in the form of their crystalline CD-ICs or soluble CD-rotaxanes. Secondly, the many hydroxyl groups attached to the exterior rims of CDs, in addition to conferring water solubility, provide an opportunity to covalently bond them to polymers either during their syntheses or via postpolymerization reactions. Polymers containing CDs in their backbones or attached to their side chains are observed to more readily accept and retain additives, such as dyes and fragrances. Processing with CDs can serve to both nanostructure and functionalize polymers, leading to greater understanding of their behaviors and to new properties and applications.

Determining association constants from titration experiments in supramolecular chemistry.

PubMed

Thordarson, Pall

2011-03-01

The most common approach for quantifying interactions in supramolecular chemistry is a titration of the guest to solution of the host, noting the changes in some physical property through NMR, UV-Vis, fluorescence or other techniques. Despite the apparent simplicity of this approach, there are several issues that need to be carefully addressed to ensure that the final results are reliable. This includes the use of non-linear rather than linear regression methods, careful choice of stoichiometric binding model, the choice of method (e.g., NMR vs. UV-Vis) and concentration of host, the application of advanced data analysis methods such as global analysis and finally the estimation of uncertainties and confidence intervals for the results obtained. This tutorial review will give a systematic overview of all these issues-highlighting some of the key messages herein with simulated data analysis examples.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

University of California, Berkeley; Lawrence Berkeley National Laboratory; Raymond, Kenneth

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 tomore » 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 increased complexity of synthetic host molecules, most assembly conditions utilize self-assembly to form complex highly-symmetric structures from relatively simple subunits. For supramolecular assemblies able to encapsulate guest molecules, the chemical environment in each assembly--defined by the size, shape, charge, and functional group availability--greatly influences the guest-binding characteristics.[6, 13-17]« less

Simulation optimization of spherical non-polar guest recognition by deep-cavity cavitands

PubMed Central

Wanjari, Piyush P.; Gibb, Bruce C.; Ashbaugh, Henry S.

2013-01-01

Biomimetic deep-cavity cavitand hosts possess unique recognition and encapsulation properties that make them capable of selectively binding a range of non-polar guests within their hydrophobic pocket. Adamantane based derivatives which snuggly fit within the pocket of octa-acid deep cavity cavitands exhibit some of the strongest host binding. Here we explore the roles of guest size and attractiveness on optimizing guest binding to form 1:1 complexes with octa-acid cavitands in water. Specifically we simulate the water-mediated interactions of the cavitand with adamantane and a range of simple Lennard-Jones guests of varying diameter and attractive well-depth. Initial simulations performed with methane indicate hydrated methanes preferentially reside within the host pocket, although these guests frequently trade places with water and other methanes in bulk solution. The interaction strength of hydrophobic guests increases with increasing size from sizes slightly smaller than methane to Lennard-Jones guests comparable in size to adamantane. Over this guest size range the preferential guest binding location migrates from the bottom of the host pocket upwards. For guests larger than adamantane, however, binding becomes less favorable as the minimum in the potential-of-mean force shifts to the cavitand face around the portal. For a fixed guest diameter, the Lennard-Jones well-depth is found to systematically shift the guest-host potential-of-mean force to lower free energies, however, the optimal guest size is found to be insensitive to increasing well-depth. Ultimately our simulations show that adamantane lies within the optimal range of guest sizes with significant attractive interactions to match the most tightly bound Lennard-Jones guests studied. PMID:24359375

Two-Dimensional Nanoporous Networks Formed by Liquid-to-Solid Transfer of Hydrogen-Bonded Macrocycles Built from DNA Bases.

PubMed

Bilbao, Nerea; Destoop, Iris; De Feyter, Steven; González-Rodríguez, David

2016-01-11

We present an approach that makes use of DNA base pairing to produce hydrogen-bonded macrocycles whose supramolecular structure can be transferred from solution to a solid substrate. A hierarchical assembly process ultimately leads to two-dimensional nanostructured porous networks that are able to host size-complementary guests. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dual pH-sensitive supramolecular micelles from star-shaped PDMAEMA based on β-cyclodextrin for drug release.

PubMed

Zhou, Zaishuai; Guo, Feng; Wang, Nairong; Meng, Meng; Li, Guiying

2018-05-23

Star-shaped poly(2-(dimethylamino)ethyl methacrylate) based on β-cyclodextrin (β-CD-(PDMAEMA) 7 ) was synthesized by means of atomic transfer radical polymerization (ATRP). Dual pH-sensitive supramolecular micelles were formed from β-CD-(PDMAEMA) 7 and benzimidazole modified poly(ε-caprolactone) (BM-PCL) through the host-guest interactions between β-CD and benzimidazole. The supramolecular micelles have regular spherical structure with hydrophobic β-CD/BM-PCL as the core and pH-sensitive PDMAEMA as the shell. The hydrophobic PCL as well as the hydrophobic cavity of β-CD can efficiently encapsulate doxorubicin (DOX) with the drug-loading content and entrapment efficiency up to 40% and 86%. The drug release from micelles accelerated when the pH decreased from 7.0 to 2.0 and the temperature increased from 25 °C to 45 °C. MTT assay showed that drug loaded supramolecular micelles exhibited excellent anti-cancer activity than free DOX. These supramolecular micelles have promising potential applications as intelligent nanocarriers in drug delivery system. Copyright © 2018 Elsevier B.V. All rights reserved.

Competitive Self-Assembly Manifests Supramolecular Darwinism in Soft-Oxometalates

NASA Astrophysics Data System (ADS)

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.

Cucurbit[n]uril-Based Microcapsules Self-Assembled within Microfluidic Droplets: A Versatile Approach for Supramolecular Architectures and Materials

PubMed Central

2017-01-01

Conspectus Microencapsulation is a fundamental concept behind a wide range of daily applications ranging from paints, adhesives, and pesticides to targeted drug delivery, transport of vaccines, and self-healing concretes. The beauty of microfluidics to generate microcapsules arises from the capability of fabricating monodisperse and micrometer-scale droplets, which can lead to microcapsules/particles with fine-tuned control over size, shape, and hierarchical structure, as well as high reproducibility, efficient material usage, and high-throughput manipulation. The introduction of supramolecular chemistry, such as host–guest interactions, endows the resultant microcapsules with stimuli-responsiveness and self-adjusting capabilities, and facilitates hierarchical microstructures with tunable stability and porosity, leading to the maturity of current microencapsulation industry. Supramolecular architectures and materials have attracted immense attention over the past decade, as they open the possibility to obtain a large variety of aesthetically pleasing structures, with myriad applications in biomedicine, energy, sensing, catalysis, and biomimicry, on account of the inherent reversible and adaptive nature of supramolecular interactions. As a subset of supramolecular interactions, host–guest molecular recognition involves the formation of inclusion complexes between two or more moieties, with specific three-dimensional structures and spatial arrangements, in a highly controllable and cooperative manner. Such highly selective, strong yet dynamic interactions could be exploited as an alternative methodology for programmable and controllable engineering of supramolecular architectures and materials, exploiting reversible interactions between complementary components. Through the engineering of molecular structures, assemblies can be readily functionalized based on host–guest interactions, with desirable physicochemical characteristics. In this Account, we summarize the current state of development in the field of monodisperse supramolecular microcapsules, fabricated through the integration of traditional microfluidic techniques and interfacial host–guest chemistry, specifically cucurbit[n]uril (CB[n])-mediated host–guest interactions. Three different strategies, colloidal particle-driven assembly, interfacial condensation-driven assembly and electrostatic interaction-driven assembly, are classified and discussed in detail, presenting the methodology involved in each microcapsule formation process. We highlight the state-of-the-art in design and control over structural complexity with desirable functionality, as well as promising applications, such as cargo delivery stemming from the assembled microcapsules. On account of its dynamic nature, the CB[n]-mediated host–guest complexation has demonstrated efficient response toward various external stimuli such as UV light, pH change, redox chemistry, and competitive guests. Herein, we also demonstrate different microcapsule modalities, which are engineered with CB[n] host–guest chemistry and also can be disrupted with the aid of external stimuli, for triggered release of payloads. In addition to the overview of recent achievements and current limitations of these microcapsules, we finally summarize several perspectives on tunable cargo loading and triggered release, directions, and challenges for this technology, as well as possible strategies for further improvement, which will lead to substainitial progress of host–guest chemistry in supramolecular architectures and materials. PMID:28075551

Complexation induced fluorescence and acid-base properties of dapoxyl dye with γ-cyclodextrin: a drug-binding application using displacement assays.

PubMed

Pal, Kaushik; Mallick, Suman; Koner, Apurba L

2015-06-28

Host-guest complexation of dapoxyl sodium sulphonate (DSS), an intramolecular charge transfer dye with water-soluble and non-toxic macrocycle γ-cyclodextrin (γ-CD), has been investigated in a wide pH range. Steady-state absorption, fluorescence and time-resolved fluorescence measurements confirm the positioning of DSS into the hydrophobic cavity of γ-CD. A large fluorescence enhancement ca. 30 times, due to 1 : 2 complex formation and host-assisted guest-protonation have been utilised for developing a method for the utilisation of CD based drug-delivery applications. A simple fluorescence-displacement based approach is implemented at physiological pH for the assessment of binding strength of pharmaceutically useful small drug molecules (ibuprofen, paracetamol, methyl salicylate, salicylic acid, aspirin, and piroxicam) and six important antibiotic drugs (resazurin, thiamphenicol, chloramphenicol, ampicillin, kanamycin, and sorbic acid) with γ-CD.

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

PubMed

Onishi, Yasuhiko; Eshita, Yuki; Ji, Rui-Cheng; Onishi, Masayasu; Kobayashi, Takashi; Mizuno, Masaaki; Yoshida, Jun; Kubota, Naoji

2014-01-01

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.

The Delicate Balance of Preorganisation and Adaptability in Multiply Bonded Host-Guest Complexes.

PubMed

von Krbek, Larissa K S; Achazi, Andreas J; Schoder, Stefan; Gaedke, Marius; Biberger, Tobias; Paulus, Beate; Schalley, Christoph A

2017-02-24

Rigidity and preorganisation are believed to be required for high affinity in multiply bonded supramolecular complexes as they help reduce the entropic penalty of the binding event. This comes at the price that such rigid complexes are sensitive to small geometric mismatches. In marked contrast, nature uses more flexible building blocks. Thus, one might consider putting the rigidity/high-affinity notion to the test. Multivalent crown/ammonium complexes are ideal for this purpose as the monovalent interaction is well understood. A series of divalent complexes with different spacer lengths and rigidities has thus been analysed to correlate chelate cooperativities and spacer properties. Too long spacers reduce chelate cooperativity compared to exactly matching ones. However, in contrast to expectation, flexible guests bind with chelate cooperativities clearly exceeding those of rigid structures. Flexible spacers adapt to small geometric host-guest mismatches. Spacer-spacer interactions help overcome the entropic penalty of conformational fixation during binding and a delicate balance of preorganisation and adaptability is at play in multivalent complexes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanism of host-guest complexation by cucurbituril.

PubMed

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.

Monosaccharides as Versatile Units for Water-Soluble Supramolecular Polymers.

PubMed

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.

Testing electronic structure methods for describing intermolecular H...H interactions in supramolecular chemistry.

PubMed

Casadesús, Ricard; Moreno, Miquel; González-Lafont, Angels; Lluch, José M; Repasky, Matthew P

2004-01-15

In this article a wide variety of computational approaches (molecular mechanics force fields, semiempirical formalisms, and hybrid methods, namely ONIOM calculations) have been used to calculate the energy and geometry of the supramolecular system 2-(2'-hydroxyphenyl)-4-methyloxazole (HPMO) encapsulated in beta-cyclodextrin (beta-CD). The main objective of the present study has been to examine the performance of these computational methods when describing the short range H. H intermolecular interactions between guest (HPMO) and host (beta-CD) molecules. The analyzed molecular mechanics methods do not provide unphysical short H...H contacts, but it is obvious that their applicability to the study of supramolecular systems is rather limited. For the semiempirical methods, MNDO is found to generate more reliable geometries than AM1, PM3 and the two recently developed schemes PDDG/MNDO and PDDG/PM3. MNDO results only give one slightly short H...H distance, whereas the NDDO formalisms with modifications of the Core Repulsion Function (CRF) via Gaussians exhibit a large number of short to very short and unphysical H...H intermolecular distances. In contrast, the PM5 method, which is the successor to PM3, gives very promising results. Our ONIOM calculations indicate that the unphysical optimized geometries from PM3 are retained when this semiempirical method is used as the low level layer in a QM:QM formulation. On the other hand, ab initio methods involving good enough basis sets, at least for the high level layer in a hybrid ONIOM calculation, behave well, but they may be too expensive in practice for most supramolecular chemistry applications. Finally, the performance of the evaluated computational methods has also been tested by evaluating the energetic difference between the two most stable conformations of the host(beta-CD)-guest(HPMO) system. Copyright 2003 Wiley Periodicals, Inc. J Comput Chem 25: 99-105, 2004

Temperature-regulated guest admission and release in microporous materials

DOE PAGES

Li, Gang; Shang, Jin; Gu, Qinfen; ...

2017-06-09

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 Hmore » 2, N 2, Ar and CH 4 on three classes of microporous materials: trapdoor zeolites, supramolecular host calixarenes and metal-organic frameworks. We also demonstrate how temperature can be exploited to achieve appreciable hydrogen and methane storage in such materials without sustained pressure. Our findings also open new avenues for gas sensing and isotope separation.« less

Dual responsive supramolecular hydrogel with electrochemical activity.

PubMed

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.

Ethane-Bridged Bisporphyrin Conformational Changes As an Effective Analytical Tool for Nonenzymatic Detection of Urea in the Physiological Range.

PubMed

Buccolieri, Alessandro; Hasan, Mohammed; Bettini, Simona; Bonfrate, Valentina; Salvatore, Luca; Santino, Angelo; Borovkov, Victor; Giancane, Gabriele

2018-06-05

Conformational switching induced in ethane-bridged bisporphyrins was used as a sensitive transduction method for revealing the presence of urea dissolved in water via nonenzymatic approach. Bisporphyrins were deposited on solid quartz slides by means of the spin-coating method. Molecular conformations of Zn and Ni monometalated bis-porphyrins were influenced by water solvated urea molecules and their fluorescence emission was modulated by the urea concentration. Absorption, fluorescence and Raman spectroscopies allowed the identification of supramolecular processes, which are responsible for host-guest interaction between the active layers and urea molecules. A high selectivity of the sensing mechanism was highlighted upon testing the spectroscopic responses of bis-porphyrin films to citrulline and glutamine used as interfering agents. Additionally, potential applicability was demonstrated by quantifying the urea concentration in real physiological samples proposing this new approach as a valuable alternative analytical procedure to the traditionally used enzymatic methods.

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

PubMed

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.

3D Printing Polymers with Supramolecular Functionality for Biological Applications.

PubMed

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.

Physico-chemical Properties of Supramolecular Complexes of Natural Flavonoids with Biomacromolecules

NASA Astrophysics Data System (ADS)

Barvinchenko, V. M.; Lipkovska, N. O.; Fedyanina, T. V.; Pogorelyi, V. K.

Polyvinylpyrrolidone (a water-soluble biopolymer) and human serum albumin (a globular protein) form supramolecular complexes with natural flavonoids quercetin and rutin in aqueous medium. The interaction with these biomacromolecules (BMM) causes the alteration of flavonoid spectral, protolytic, and other properties; in particular, it essentially increases their solubility. Absorption and solubility measurements revealed the supramolecular compounds of 1:1 stoichiometry for all systems studied. First it was demonstrated experimentally that the interaction with BMM promotes the tautomeric transformation in quercetin molecule. The mechanism of tautomerization via flavonoid molecular structure was discussed. Adsorption of BMM and their supramolecular compounds with flavonoids onto nanosilica was studied as a function of pH, and the properties of the biomacromolecules, flavonoids, and silica surface. It was found that BMM either complexed with quercetin (rutin) or preliminary immobilized on nanosilica increases the flavonoid adsorption.

A Supramolecular Approach for Liver Radioembolization

PubMed Central

Spa, Silvia J.; Welling, Mick M.; van Oosterom, Matthias N.; Rietbergen, Daphne D. D.; Burgmans, Mark C.; Verboom, Willem; Huskens, Jurriaan; Buckle, Tessa; van Leeuwen, Fijs W. B.

2018-01-01

Hepatic radioembolization therapies can suffer from discrepancies between diagnostic planning (scout-scan) and the therapeutic delivery itself, resulting in unwanted side-effects such as pulmonary shunting. We reasoned that a nanotechnology-based pre-targeting strategy could help overcome this shortcoming by directly linking pre-interventional diagnostics to the local delivery of therapy. Methods: The host-guest interaction between adamantane and cyclodextrin was employed in an in vivo pre-targeting set-up. Adamantane (guest)-functionalized macro albumin aggregates (MAA-Ad; d = 18 μm) and (radiolabeled) Cy5 and β-cyclodextrin (host)-containing PIBMA polymers (99mTc-Cy50.5CD10PIBMA39; MW ~ 18.8 kDa) functioned as the reactive pair. Following liver or lung embolization with (99mTc)-MAA-Ad or (99mTc)-MAA (control), the utility of the pre-targeting concept was evaluated after intravenous administration of 99mTc-Cy50.5CD10PIBMA39. Results: Interactions between MAA-Ad and Cy50.5CD10PIBMA39 could be monitored in solution using confocal microscopy and were quantified by radioisotope-based binding experiments. In vivo the accumulation of the MAA-Ad particles in the liver or lungs yielded an approximate ten-fold increase in accumulation of 99mTc-Cy50.5CD10PIBMA39 in these organs (16.2 %ID/g and 10.5 %ID/g, respectively) compared to the control. Pre-targeting with MAA alone was shown to be only half as efficient. Uniquely, for the first time, this data demonstrates that the formation of supramolecular interactions between cyclodextrin and adamantane can be used to drive complex formation in the chemically challenging in vivo environment. Conclusion: The in vivo distribution pattern of the cyclodextrin host could be guided by the pre-administration of the adamantane guest, thereby creating a direct link between the scout-scan (MAA-Ad) and delivery of therapy. PMID:29721086

Interactions of Native Cyclodextrins with Metal Ions and Inorganic Nanoparticles: Fertile Landscape for Chemistry and Materials Science.

PubMed

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 efficient host templates in the construction of nanomaterials with the desired functionality, including the first-in-class devices including sensors and memristors, are highlighted. Finally, CDs as well-known "green" molecular hosts have also been used as ideal functional molecules to improve the solubility, stability, and bioavailability of inorganic nanoparticles. In this regard, we demonstrate various strategies for the preparation of native CDs-modified inorganic nanomaterials such as metal, metal oxide, and semiconductor and magnetic nanoparticles, aiming to take advantage of both the controlled properties of the inorganic core and the controlled properties of the coating molecules. The functionalization of a CD hydrophobic cavity with an inorganic nanoparticle is very prospective for the development of novel catalytic systems and new tools for highly selective and sensitive sensing platforms for various targets.

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

PubMed

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.

Nonlinear optical moiety-doped polymers with improved optical properties for photonic devices

NASA Astrophysics Data System (ADS)

Lee, Myung-Hyun; Kim, Hwan K.; Kim, Hye-Young; Lee, Hyuek J.; Kang, K. H.; Won, Yong Hyub; Jeon, Eunsuk S.; Wu, Jeong W.

1994-05-01

An electro-optic polymer guest-host system has been constructed and demonstrated. The polymer host is a polyimide (PIQ2200) and the guest chromophores are dimethyl (or diethyl) amino alkyl sulfone stilbenes. The alkylated-NLO moieties as guest chromophores have been modified, yielding new alkylated-NLO moieties. The higher content of alkylated-NLO moieties, compared to unmodified NLO moieties, was doped into a polyimide host system due to the improved solubility of new alkylated-NLO moieties. To the 40 wt%, the new alkylated- NLO moiety has been completely dissolved in the preliminary experiment, leading to the increase of refractive index by 0.0016. These polyimide-based guest-host systems exhibited a significant improvement in the thermal stability at high temperatures exceeding 250 degree(s)C. The electro-optic coefficient reported in the present study is 13 pm/V for the 40 wt% DASS-6- doped polymer system poled at the 135 V/micrometers . However, further increase up to 25 pm/V may easily be achieved by increasing the amount of guest moieties and/or the intensity of the poling field. This work presents new materials for photonic switching devices with low operating voltage.

Self-Assembly of a Tripodal Triszwitterion Forms a pH-Switchable Hydrogel that Can Reversibly Encapsulate Hydrophobic Guests in Water.

PubMed

Jana, Poulami; Schmuck, Carsten

2017-01-05

The development of supramolecular smart materials, which exhibit physicochemical structural changes in response to external stimuli is of current interest for various applications. Herein, we have developed the novel tripodal triszwitterion 1, derived from a C 3 -symmetric benzene-1,3,5-tricarboxamide (BTA) core, which forms a thermo-reversible and pH-switchable transparent hydrogel through intermolecular self-complementary zwitterionic interactions at a neutral pH value. The hierarchical supramolecular self-aggregation was fully analyzed by microscopy (AFM, field emission scanning electron microscopy (FESEM)), viscosity, dynamic light scattering (DLS), and rheology studies. Moreover, compound 1 enables to encapsulate hydrophobic guests, such as the dye Nile red in aqueous medium at pH 6, which makes it an interesting candidate for drug delivery and controlled release. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nucleation pathways of clathrate hydrates: effect of guest size and solubility.

PubMed

Jacobson, Liam C; Hujo, Waldemar; Molinero, Valeria

2010-11-04

Understanding the microscopic mechanism of nucleation of clathrate hydrates is important for their use in hydrogen storage, CO(2) sequestration, storage and transport of natural gas, and the prevention of the formation of hydrate plugs in oil and gas pipelines. These applications involve hydrate guests of varied sizes and solubility in water that form different hydrate crystal structures. Nevertheless, molecular studies of the mechanism of nucleation of hydrates have focused on the single class of small hydrophobic guests that stabilize the sI crystal. In this work, we use molecular dynamics simulations with a very efficient coarse-grained model to elucidate the mechanisms of nucleation of clathrate hydrates of four model guests that span a 2 orders of magnitude range in solubility in water and that encompass sizes which stabilize each one a different hydrate structure (sI and sII, with and without occupancy of the dodecahedral cages). We find that the overall mechanism of clathrate nucleation is similar for all guests and involves a first step of formation of blobs, dense clusters of solvent-separated guest molecules that are the birthplace of the clathrate cages. Blobs of hydrophobic guests are rarer and longer-lived than those for soluble guests. For each guest, we find multiple competing channels to form the critical nuclei, filled dodecahedral (5(12)) cages, empty 5(12) cages, and a variety of filled large (5(12)6(n) with n = 2, 3, and 4) clathrate cages. Formation of empty dodecahedra is an important nucleation channel for all but the smallest guest. The empty 5(12) cages are stabilized by the presence of guests from the blob in their first solvation shell. Under conditions of high supercooling, the structure of the critical and subcritical nuclei is mainly determined by the size of the guest and does not reflect the cage composition or ordering of the stable or metastable clathrate crystals.

The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations

DOE PAGES

Hart-Cooper, William M.; Zhao, Chen; Triano, Rebecca M.; ...

2014-11-28

The effect of host structure on the selectivity and mechanism of intramolecular Prins reactions is evaluated using K 12Ga 4L 6 tetrahedral catalysts. The host structure was varied by modifying the structure of the chelating moieties and the size of the aromatic spacers. While variation in chelator substituents was generally observed to affect changes in rate but not selectivity, changing the host spacer afforded differences in efficiency and product diastereoselectivity. An extremely high number of turnovers (up to 840) was observed. Maximum rate accelerations were measured to be on the order of 10 5, which numbers among the largest magnitudesmore » of transition state stabilization measured with a synthetic host-catalyst. Host/guest size effects were observed to play an important role in host-mediated enantioselectivity.« less

Smart Self-Assembled Nanosystem Based on Water-Soluble Pillararene and Rare-Earth-Doped Upconversion Nanoparticles for pH-Responsive Drug Delivery.

PubMed

Li, Haihong; Wei, Ruoyan; Yan, Gui-Hua; Sun, Ji; Li, Chunju; Wang, Haifang; Shi, Liyi; Capobianco, John A; Sun, Lining

2018-02-07

Exploring novel drug delivery systems with good stability and new structure to integrate pillararene and upconversion nanoparticles (UCNPs) into one system continues to be an important challenge. Herein, we report a novel preparation of a supramolecular upconversion nanosystem via the host-guest complexation based on carboxylate-based pillar[5]arene (WP5) and 15-carboxy-N,N,N-trialkylpentadecan-1-ammonium bromide (1)-functionalized UCNPs to produce WP5⊃1-UCNPs that can be loaded with the chemotherapeutic drug doxorubicin (DOX). Importantly, the WP5 on the surface of the drug-loaded nanosystem can be efficiently protonated under acidic conditions, resulting in the collapse of the nanosystem and drug release. Moreover, cellular uptake confirms that the nanosystem can enter human cervical cancer (HeLa) cells, resulting in drug accumulation in the cells. More importantly, cytotoxicity experiments demonstrated the excellent biocompatibility of WP5⊃1-UCNPs without loading DOX and that the nanosystem DOX-WP5⊃1-UCNPs exhibited an ability of killing HeLa cells effectively. We also investigated magnetic resonance imaging and upconversion luminescence imaging, which may be employed as visual imaging agents in cancer diagnosis and treatment. Thus, in the present work, we show a simple yet powerful strategy to combine UCNPs and pillar[5]arene to produce a unified nanosystem for dual-mode bioimaging-guided therapeutic applications.

Functionalized polymers for binding to solutes in aqueous solutions

DOEpatents

Smith, Barbara F.; Robison, Thomas W.

2006-11-21

A functionalized polymer for binding a dissolved molecule in an aqueous solution is presented. The polymer has a backbone polymer to which one or more functional groups are covalently linked. The backbone polymer can be such polymers as polyethylenimine, polyvinylamine, polyallylamine, and polypropylamine. These polymers are generally water-soluble, but can be insoluble when cross-linked. The functional group can be for example diol derivatives, polyol derivatives, thiol and dithiol derivatives, guest-host groups, affinity groups, beta-diphosphonic acids, and beta-diamides

Supramolecular Affinity Chromatography for Methylation-Targeted Proteomics.

PubMed

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.

EPR Studies of the Binding Properties, Guest Dynamics, and Inner-Space Dimensions of a Water-Soluble Resorcinarene Capsule.

PubMed

Ayhan, Mehmet Menaf; Casano, Gilles; Karoui, Hakim; Rockenbauer, Antal; Monnier, Valérie; Hardy, Micaël; Tordo, Paul; Bardelang, David; Ouari, Olivier

2015-11-09

Nitroxide free radicals have been used to study the inner space of one of Rebek's water-soluble capsules. EPR and (1) H NMR spectroscopy, ESI-MS, and DFT calculations showed a preference for the formation of 1:2 complexes. EPR titrations allowed us to determine binding constants (Ka ) in the order of 10(7)  M(-2) . EPR spectral-shape analysis provided information on the guest rotational dynamics within the capsule. The interplay between optimum hydrogen bonding upon capsule formation and steric strain for guest accommodation highlights some degree of flexibility for guest inclusion, particularly at the center of the capsule where the hydrogen bond seam can be barely distorted or slightly disturbed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular Ex plorations: Ex hibiting the Ex tent of Ex tended Cationic Cyclophanes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dale, Edward J.; Vermeulen, Nicolaas A.; Juricek, Michal

Acting as hosts, cationic cyclophanes, consisting of π-electron-poor bipyridinium units, are capable of entering into strong donor–acceptor interactions to form host–guest complexes with various guests when the size and electronic constitution are appropriately matched. A synthetic protocol has been developed that utilizes catalytic quantities of tetrabutylammonium iodide to make a wide variety of cationic pyridinium-based cyclophanes in a quick and easy manner. Members of this class of cationic cyclophanes with boxlike geometries, dubbed ExnBoxm4+ for short, have been prepared by altering a number of variables: (i) n, the number of “horizontal” p-phenylene spacers between adjoining pyridinium units, to modulate themore » “length” of the cavity; (ii) m, the number of “vertical” p-phenylene spacers, to modulate the “width” of the cavity; and (iii) the aromatic linkers, namely, 1,4-di- and 1,3,5-trisubstituted units for the construction of macrocycles (ExBoxes) and macrobicycles (ExCages), respectively. This Account serves as an exploration of the properties that emerge from these structural modifications of the pyridinium-based hosts, coupled with a call for further investigation into the wealth of properties inherent in this class of compounds. By variation of only the aforementioned components, the role of these cationic receptors covers ground that spans (i) synthetic methodology, (ii) extraction and sequestration, (iii) catalysis, (iv) molecular electronics, (v) physical organic chemistry, and (vi) supramolecular chemistry. Ex1Box4+ (or simply ExBox4+) has been shown to be a multipurpose receptor capable of binding a wide range of polycyclic aromatic hydrocarbons (PAHs), while also being a suitable component in switchable mechanically interlocked molecules. Additionally, the electronic properties of some host–guest complexes allow the development of artificial photosystems. Ex2Box4+ boasts the ability to bind both π-electron-rich and -poor aromatic guests in different binding sites located within the same cavity. ExBox24+ forms complexes with C60 in which discrete arrays of aligned fullerenes result in single cocrystals, leading to improved material conductivities. When the substitution pattern of the ExnBox4+ series is changed to 1,3,5-trisubstituted benzenoid cores, the hexacationic cagelike compound, termed ExCage6+, exhibits different kinetics of complexation with guests of varying sizes—a veritable playground for physical organic chemists. The organization of functionality with respect to structure becomes valuable as the number of analogues continues to grow. With each of these minor structural modifications, a wealth of properties emerge, begging the question as to what discoveries await and what properties will be realized with the continued exploration of this area of supramolecular chemistry based on a unique class of receptor molecules.« less

Supramolecular Ex plorations: Ex hibiting the Ex tent of Ex tended Cationic Cyclophanes

DOE PAGES

Dale, Edward J.; Vermeulen, Nicolaas A.; Juricek, Michal; ...

2016-01-19

Acting as hosts, cationic cyclophanes, consisting of π-electron-poor bipyridinium units, are capable of entering into strong donor–acceptor interactions to form host–guest complexes with various guests when the size and electronic constitution are appropriately matched. A synthetic protocol has been developed that utilizes catalytic quantities of tetrabutylammonium iodide to make a wide variety of cationic pyridinium-based cyclophanes in a quick and easy manner. Members of this class of cationic cyclophanes with boxlike geometries, dubbed ExnBoxm4+ for short, have been prepared by altering a number of variables: (i) n, the number of “horizontal” p-phenylene spacers between adjoining pyridinium units, to modulate themore » “length” of the cavity; (ii) m, the number of “vertical” p-phenylene spacers, to modulate the “width” of the cavity; and (iii) the aromatic linkers, namely, 1,4-di- and 1,3,5-trisubstituted units for the construction of macrocycles (ExBoxes) and macrobicycles (ExCages), respectively. This Account serves as an exploration of the properties that emerge from these structural modifications of the pyridinium-based hosts, coupled with a call for further investigation into the wealth of properties inherent in this class of compounds. By variation of only the aforementioned components, the role of these cationic receptors covers ground that spans (i) synthetic methodology, (ii) extraction and sequestration, (iii) catalysis, (iv) molecular electronics, (v) physical organic chemistry, and (vi) supramolecular chemistry. Ex1Box4+ (or simply ExBox4+) has been shown to be a multipurpose receptor capable of binding a wide range of polycyclic aromatic hydrocarbons (PAHs), while also being a suitable component in switchable mechanically interlocked molecules. Additionally, the electronic properties of some host–guest complexes allow the development of artificial photosystems. Ex2Box4+ boasts the ability to bind both π-electron-rich and -poor aromatic guests in different binding sites located within the same cavity. ExBox24+ forms complexes with C60 in which discrete arrays of aligned fullerenes result in single cocrystals, leading to improved material conductivities. When the substitution pattern of the ExnBox4+ series is changed to 1,3,5-trisubstituted benzenoid cores, the hexacationic cagelike compound, termed ExCage6+, exhibits different kinetics of complexation with guests of varying sizes—a veritable playground for physical organic chemists. The organization of functionality with respect to structure becomes valuable as the number of analogues continues to grow. With each of these minor structural modifications, a wealth of properties emerge, begging the question as to what discoveries await and what properties will be realized with the continued exploration of this area of supramolecular chemistry based on a unique class of receptor molecules.« less

Recognition-mediated activation of therapeutic gold nanoparticles inside living cells

NASA Astrophysics Data System (ADS)

Kim, Chaekyu; Agasti, Sarit S.; Zhu, Zhengjiang; Isaacs, Lyle; Rotello, Vincent M.

2010-11-01

Supramolecular chemistry provides a versatile tool for the organization of molecular systems into functional structures and the actuation of these assemblies for applications through the reversible association between complementary components. Use of this methodology in living systems, however, represents a significant challenge owing to the chemical complexity of cellular environments and lack of selectivity of conventional supramolecular interactions. Herein, we present a host-guest system featuring diaminohexane-terminated gold nanoparticles (AuNP-NH2) and complementary cucurbit[7]uril (CB[7]). In this system, threading of CB[7] on the particle surface reduces the cytotoxicity of AuNP-NH2 through sequestration of the particle in endosomes. Intracellular triggering of the therapeutic effect of AuNP-NH2 was then achieved through the administration of 1-adamantylamine (ADA), removing CB[7] from the nanoparticle surface, causing the endosomal release and concomitant in situ cytotoxicity of AuNP-NH2. This supramolecular strategy for intracellular activation provides a new tool for potential therapeutic applications.

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

PubMed

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.

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

PubMed

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.

Flying Cages in Traveling Wave Ion Mobility: Influence of the Instrumental Parameters on the Topology of the Host-Guest Complexes

NASA Astrophysics Data System (ADS)

Carroy, Glenn; Lemaur, Vincent; Henoumont, Céline; Laurent, Sophie; De Winter, Julien; De Pauw, Edwin; Cornil, Jérôme; Gerbaux, Pascal

2018-01-01

Supramolecular mass spectrometry has emerged in the last decade as an orthogonal method to access, at the molecular level, the structures of noncovalent complexes extracted from the condensed phase to the rarefied gas phase using electrospray ionization. It is often considered that the soft nature of the ESI source confers to the method the capability to generate structural data comparable to those in the condensed phase. In the present paper, using the ammonium ion/cucurbituril combination as a model system, we investigate using ion mobility and computational chemistry the influence of the instrumental parameters on the topology, i.e., internal versus external association, of gaseous host/guest complex ions. MS and theoretical data are confronted to condensed phase data derived from nuclear magnetic resonance spectroscopy to assess whether the instrumental parameters can play an insidious role when trying to derive condensed phase data from mass spectrometry results. [Figure not available: see fulltext.

Encapsulation of an adamantane-doxorubicin prodrug in pH-responsive polysaccharide capsules for controlled release.

PubMed

Luo, Guo-Feng; Xu, Xiao-Ding; Zhang, Jing; Yang, Juan; Gong, Yu-Hui; Lei, Qi; Jia, Hui-Zhen; Li, Cao; Zhuo, Ren-Xi; Zhang, Xian-Zheng

2012-10-24

Supramolecular microcapsules (SMCs) with the drug-loaded wall layers for pH-controlled drug delivery were designed and prepared. By using layer-by-layer (LbL) technique, the SMCs were constructed based on the self-assembly between polyaldenhyde dextran-graft-adamantane (PAD-g-AD) and carboxymethyl dextran-graft-β-CD (CMD-g-β-CD) on CaCO(3) particles via host-guest interaction. Simultaneously, adamantine-modified doxorubicin (AD-Dox) was also loaded on the LbL wall via host-guest interaction. The in vitro drug release study was carried out at different pHs. Because the AD groups were linked with PAD (PAD-g-AD) or Dox (AD-Dox) by pH-cleavable hydrazone bonds, AD moieties can be removed under the weak acidic condition, leading to destruction of SMCs and release of Dox. The pH-controlled drug release can enhance the uptake by tumor cells and thus achieve improved cancer therapy efficiency.

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

NASA Astrophysics Data System (ADS)

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.

Supramolecular Inclusion in Cyclodextrins: A Pictorial Spectroscopic Demonstration

ERIC Educational Resources Information Center

Haldar, Basudeb; Mallick, Arabinda; Chattopadhyay, Nitin

2008-01-01

A spectroscopic experiment is presented that reveals that the hydrophobically end-modified water-soluble polymeric fluorophore, pyrene end-capped poly(ethylene oxide) (PYPY), interacts differently with [alpha], [beta], and [gamma]-cyclodextrins (CD) to form supramolecular inclusion complexes. The emission spectrum of PYPY in aqueous solution shows…

Supracolloidal Architectures Self-Assembled in Microdroplets.

PubMed

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.

Host-guest inclusion system of glycyrrhetic acid with polyamine-β-cyclodextrin: Preparation, characterization, and anticancer activity

NASA Astrophysics Data System (ADS)

Shen, Zhi; Qin, Qi; Liao, Xiali; Yang, Bo

2017-12-01

The inclusion complexation behaviors of glycyrrhetic acid (CTA) with four polyamine-modified β-cyclodextrins (CDs) have been investigated by 1H and 2D NMR, thermal gravimetric analysis, X-ray power diffraction and scanning electron microscopy. The results showed that Glycyrrhetic acid was encapsulated into the cavity of cyclodextrin to form the complexes with 1:1 stoichiometry. The water solubility of GTA was significantly enhanced by inclusion complexation with polyamine-modified β-cyclodextrins. The calculated IC50 values indicated that the antitumor activities of inclusion complexes were better than that of GTA. Satisfactory aqueous solubility, along with high thermal stability of inclusion complexes will be potentially useful for their application on the formulation design of natural medicine.

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

PubMed

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.

Water soluble biocompatible vesicles based on polysaccharides and oligosaccharides inclusion complexes for carotenoid delivery.

PubMed

Polyakov, Nikolay E; Kispert, Lowell D

2015-09-05

Since carotenoids are highly hydrophobic, air- and light-sensitive hydrocarbon compounds, developing methods for increasing their bioavailability and stability towards irradiation and reactive oxygen species is an important goal. Application of inclusion complexes of "host-guest" type with polysaccharides and oligosaccharides such as arabinogalactan, cyclodextrins and glycyrrhizin minimizes the disadvantages of carotenoids when these compounds are used in food processing (colors and antioxidant capacity) as well as for production of therapeutic formulations. Cyclodextrin complexes which have been used demonstrated enhanced storage stability but suffered from poor solubility. Polysaccharide and oligosaccharide based inclusion complexes play an important role in pharmacology by providing increased solubility and stability of lipophilic drugs. In addition they are used as drug delivery systems to increase absorption rate and bioavailability of the drugs. In this review we summarize the existing data on preparation methods, analysis, and chemical reactivity of carotenoids in inclusion complexes with cyclodextrin, arabinogalactan and glycyrrhizin. It was demonstrated that incorporation of carotenoids into the "host" macromolecule results in significant changes in their physical and chemical properties. In particular, polysaccharide complexes show enhanced photostability of carotenoids in water solutions. A significant decrease in the reactivity towards metal ions and reactive oxygen species in solution was also detected. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dynamic effects in friction and adhesion through cooperative rupture and formation of supramolecular bonds.

PubMed

Blass, Johanna; Albrecht, Marcel; Bozna, Bianca L; Wenz, Gerhard; Bennewitz, Roland

2015-05-07

We introduce a molecular toolkit for studying the dynamics in friction and adhesion from the single molecule level to effects of multivalency. As experimental model system we use supramolecular bonds established by the inclusion of ditopic adamantane connector molecules into two surface-bound cyclodextrin molecules, attached to a tip of an atomic force microscope (AFM) and to a flat silicon surface. The rupture force of a single bond does not depend on the pulling rate, indicating that the fast complexation kinetics of adamantane and cyclodextrin are probed in thermal equilibrium. In contrast, the pull-off force for a group of supramolecular bonds depends on the unloading rate revealing a non-equilibrium situation, an effect discussed as the combined action of multivalency and cantilever inertia effects. Friction forces exhibit a stick-slip characteristic which is explained by the cooperative rupture of groups of host-guest bonds and their rebinding. No dependence of friction on the sliding velocity has been observed in the accessible range of velocities due to fast rebinding and the negligible delay of cantilever response in AFM lateral force measurements.

Nanoparticles of adaptive supramolecular networks self-assembled from nucleotides and lanthanide ions.

PubMed

Nishiyabu, Ryuhei; Hashimoto, Nozomi; Cho, Ten; Watanabe, Kazuto; Yasunaga, Takefumi; Endo, Ayataka; Kaneko, Kenji; Niidome, Takuro; Murata, Masaharu; Adachi, Chihaya; Katayama, Yoshiki; Hashizume, Makoto; Kimizuka, Nobuo

2009-02-18

Amorphous nanoparticles of supramolecular coordination polymer networks are spontaneously self-assembled from nucleotides and lanthanide ions in water. They show intrinsic functions such as energy transfer from nucleobase to lanthanide ions and excellent performance as contrast enhancing agents for magnetic resonance imaging (MRI). Furthermore, adaptive inclusion properties are observed in the self-assembly process: functional materials such as fluorescent dyes, metal nanoparticles, and proteins are facilely encapsulated. Dyes in these nanoparticles fluoresce in high quantum yields with a single exponential decay, indicating that guest molecules are monomerically wrapped in the network. Gold nanoparticles and ferritin were also wrapped by the supramolecular shells. In addition, these nucleotide/lanthanide nanoparticles also serve as scaffolds for immobilizing enzymes. The adaptive nature of present supramolecular nanoparticles provides a versatile platform that can be utilized in a variety of applications ranging from material to biomedical sciences. As examples, biocompatibility and liver-directing characteristics in in vivo tissue localization experiments are demonstrated.

Folic-Acid-Targeted Self-Assembling Supramolecular Carrier for Gene Delivery.

PubMed

Liao, Rongqiang; Yi, Shouhui; Liu, Manshuo; Jin, Wenling; Yang, Bo

2015-07-27

A targeting gene carrier for cancer-specific delivery was successfully developed through a "multilayer bricks-mortar" strategy. The gene carrier was composed of adamantane-functionalized folic acid (FA-AD), an adamantane-functionalized poly(ethylene glycol) derivative (PEG-AD), and β-cyclodextrin-grafted low-molecular-weight branched polyethylenimine (PEI-CD). Carriers produced by two different self-assembly schemes, involving either precomplexation of the PEI-CD with the FA-AD and PEG-AD before pDNA condensation (Method A) or pDNA condensation with the PEI-CD prior to addition of the FA-AD and PEG-AD to engage host-guest complexation (Method B) were investigated for their ability to compact pDNA into nanoparticles. Cell viability studies show that the material produced by the Method A assembly scheme has lower cytotoxicity than branched PEI 25 kDa (PEI-25KD) and that the transfection efficiency is maintained. These findings suggest that the gene carrier, based on multivalent host-guest interactions, could be an effective, targeted, and low-toxicity carrier for delivering nucleic acid to target cells. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable Pickering Emulsions with Environmentally Responsive Hairy Silica Nanoparticles.

PubMed

Liu, Min; Chen, Xiaoli; Yang, Zongpeng; Xu, Zhou; Hong, Liangzhi; Ngai, To

2016-11-30

Surface modification of the nanoparticles using surface anchoring of amphiphilic polymers offers considerable scope for the design of a wide range of brush-coated hybrid nanoparticles with tunable surface wettability that may serve as new class of efficient Pickering emulsifiers. In the present study, we prepared mixed polymer brush-coated nanoparticles by grafting ABC miktoarm star terpolymers consisting of poly(ethylene glycol), polystyrene, and poly[(3-triisopropyloxysilyl)propyl methacrylate] (μ-PEG-b-PS-b-PIPSMA) on the surface of silica nanoparticles. The wettability of the as-prepared nanoparticles can be precisely tuned by a change of solvent or host-guest complexation. 1 H NMR result confirmed that such wettability change is due to the reorganization of the polymer chain at the grafted layer. We show that this behavior can be used for stabilization and switching between water-in-oil (W/O) and oil-in-water (O/W) emulsions. For hairy particles initially dispersed in oil, W/O emulsions were always obtained with collapsed PEG chains and mobile PS chains at the grafted layer. However, initially dispersing the hairy particles in water resulted in O/W emulsions with collapsed PS chains and mobile PEG chains. When a good solvent for both PS and PEG blocks such as toluene was used, W/O emulsions were always obtained no matter where the hairy particles were dispersed. The wettability of the mixed polymer brush-coated silica particles can also be tuned by host-guest complexation between PEG block and α-CD. More importantly, our result showed that surprisingly the resultant mixed brush-coated hairy nanoparticles can be employed for the one-step production of O/W/O multiple emulsions that are not attainable from conventional Pickering emulsifiers. The functionalized hairy silica nanoparticles at the oil-water interface can be further linked together utilizing poly(acrylic acid) as the reversible linker to form supramolecular colloidosomes, which show pH-dependent release of cargo.

Supramolecular control of transition metal complexes in water by a hydrophobic cavity: a bio-inspired strategy.

PubMed

Bistri, Olivia; Reinaud, Olivia

2015-03-14

Supramolecular chemistry in water is a very challenging research area. In biology, water is the universal solvent where transition metal ions play major roles in molecular recognition and catalysis. In enzymes, it participates in substrate binding and/or activation in the heart of a pocket defined by the folded protein. The association of a hydrophobic cavity with a transition metal ion is thus a very appealing strategy for controlling the metal ion properties in the very competitive water solvent. Various systems based on intrinsically water-soluble macrocyclic structures such as cyclodextrins, cucurbituryls, and metallo-cages have been reported. Others use calixarenes and resorcinarenes functionalized with hydrophilic substituents. One approach for connecting a metal complex to these cavities is to graft a ligand for metal ion binding at their edge. Early work with cyclodextrins has shown Michaelis-Menten like catalysis displaying enhanced kinetics and substrate-selectivity. Remarkable examples of regio- and stereo-selective transformation of substrates have been reported as well. Dynamic two-phase systems for transition metal catalysis have also been developed. They rely on either water-transfer of the metal complex through ligand embedment or synergistic coordination of a metal ion and substrate hosting. Another strategy consists in using metallo-cages, which provide a well-defined hydrophobic space, to stabilize metal complexes in water. When the cages can host simultaneously a substrate and a reactive metal complex, size- and regio-selective catalysis was obtained. Finally, construction of a polydentate coordination site closely interlocked with a calixarene or resorcinarene macrocycle has been shown to be a very fruitful strategy for obtaining metal complexes with remarkable hosting properties. For each of these systems, the synergism resulting from the biomimetic association of a hydrophobic cavity and a metal ion is discussed within the objective of developing new tools for either selective molecular recognition (with analytical perspectives) or performant catalysis, in water.

Multiple conformations of benzil in resorcinarene-based supramolecular host matrixes.

PubMed

Ma, Bao-Qing; Zhang, Yuegang; Coppens, Philip

2003-11-28

Six supramolecular complexes incorporating benzil as a guest, CMCR*bipy*benzil (alpha) 1 (CMCR = C-methylcalix[4]resorcinarene), CMCR*bipy*benzil (beta) 2, CMCR*2bpe*benzil*ethanol 3 (bpe = trans-1,4-bis(pyridyl)ethylene), CMCR*2bpe*benzil*2H2O 4, CMCR.2bpeh*benzil*ethanol 5 (bpeh = bis-(1-pyridin-4-yl-ethylidene)-hydrazine), and CECR*2bpe.benzil 6 (CECR = C-ethylcalix[4]resorcinarene), have been synthesized by hydrothermal and conventional methods and characterized by X-ray diffraction. Resorcinarene adopts a boat conformation in 1-4 and a bowl conformation in 5 and 6. Compounds 1-4 show a brick-wall-like framework, in which two benzil molecules are incorporated. For 5, bpeh spacers link CMCR molecules to give a one-dimensional wavelike polymer in which one benzil guest is embedded within the polymer cavity. Complex 6 forms a carcerand-like capsule in which two benzil guests are encapsulated. The O=C-C=O torsion angles vary from 91.8 to 139.3 degrees and correlate with the length of the central C-C bond. The benzil concentration, which is approximately 6.2 mol/L in the neat crystals, varies between 1.01 and 1.51 mol/L in the structures studied, corresponding to a 6-fold dilution. The benzil molecules are disordered in the larger cavities of 4 and 5. The two benzoyl fragments are almost perpendicular in 3, which has the next largest cavity size when solvent volume is excluded, whereas a nearly trans-coplanar conformation occurs for the cavity with the smallest volume in 6.

Formation of a Fluorous/Organic Biphasic Supramolecular Octopus Assembly for Enhanced Porphyrin Phosphorescence in Air

DOE PAGES

Yang, Chi; Arvapally, Ravi K.; Tekarli, Sammer M.; ...

2015-03-03

The trinuclear triangle-shaped system [tris{3,5-bis(heptafluoropropyl)-1,2,4-triazolatosilver(I)}] (1) and the multi-armed square-shaped metalloporphyrin PtOEP or the free porphyrin base H2OEP serve as excellent octopus hosts (OEP=2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine). Coupling of the fluorous/organic molecular octopi 1 and H2OEP or PtOEP by strong quadrupole-quadrupole and metal- interactions affords the supramolecular assemblies [1PtOEP] or [1H(2)OEP] (2a), which feature nanoscopic cavities surrounding the upper triangular and lower square cores. The fluorous/organic biphasic configuration of [1PtOEP] leads to an increase in the phosphorescence of PtOEP under ambient conditions. Guest molecules can be included in the biphasic double-octopus assembly in three different site-selective modes.

A Three-Dimensional Capsule-Like Carbon Nanocage as a Novel Segment Model of Capped Zigzag [12,0] Carbon Nanotubes: Synthesis, Characterization, and Complexation with C70.

PubMed

Du, Pingwu

2018-05-17

Herein we report the synthesis, photophysical, and supramolecular properties of a novel three-dimensional capsule-like hexa-peri-hexabenzocoronene (HBC)-containing carbon nanocage, tripodal-[2]HBC, which represents the first synthetic model of the capped zigzag [12,0] carbon nanotubes (CNTs). Tripodal-[2]HBC was achieved by rationally designed palladium-catalyzed coupling of triborylhexabenzocoronene and L-shaped cyclohexane units, followed by nickel-mediated C-Br/C-Br coupling and the subsequent aromatization of the cyclohexane moieties. The physical properties of tripodal-[2]HBC and its supramolecular host-guest interaction with C70 were further studied by UV-vis and fluorescence spectroscopy. Theoretical calculations reveal that the strain energy of tripodal-[2]HBC is as high as 55.2 kcal mol-1. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Proton Conduction in Tröger's Base Linked Poly(crown ether)s.

PubMed

Patel, Hasmukh A; Selberg, John; Salah, Dhafer; Chen, Haoyuan; Liao, Yijun; Nalluri, Siva Krishna Mohan; Farha, Omar K; Snurr, Randall Q; Rolandi, Marco; Stoddart, J Fraser

2018-06-05

Exactly 50 years ago, the ground-breaking discovery of dibenzo[18]crown-6 (DB18C6) by Charles Pedersen, led to the use of DB18C6 as a receptor in supramolecular chemistry and a host in host‒guest chemistry. We have demonstrated proton conductivity in Tröger's base-linked polymers through hydrogen-bonded networks formed from adsorbed water molecules on the oxygen atoms of DB18C6 under humid conditions. Tröger's base-linked polymers - poly(TBL‒DB18C6)-t and poly(TBL‒DB18C6)-c - synthesized by the in situ alkylation and cyclization of either trans- or cis-di(aminobenzo) [18]crown-6 at room temperature have been isolated as high molecular weight polymers. The macromolecular structures of the isomeric poly(TBL‒DB18C6)s have been established by spectroscopic techniques and size-exclusion chromatography. The excellent solubility of these polymers in chloroform allows the formation of free-standing membranes which are thermally stable and also show stability under aqueous conditions. The hydrophilic nature of the DB18C6 building blocks in the polymer facilitates retention of the water as confirmed by water-vapor adsorption isotherms which show a 23 wt% water uptake. The adsorbed water is retained even after reducing the relative humidity to 25 %. The proton conductivity of poly(TBL‒DB18C6)-t which is found to be 1.4 x 10‒4 mS cm‒1 in a humid environment, arises from the hydrogen bonding and the associated proton hopping mechanism, as supported by a modeling study. In addition to proton conductivity, the Tröger's base-linked polymers reported here promise a wide range of applications where the sub-nanometer-sized cavities of the crown ethers and the robust film-forming ability are the governing factors in dictating their properties.

Supramolecular Organocatalysis in Water Mediated by Macrocyclic Compounds

NASA Astrophysics Data System (ADS)

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bowman-James, Kristin

The effectiveness of three popular supramolecular strategies to selectively target negatively charged ions (anions) was evaluated. Ions of interest included oxo anions, particularly sulfate, that hamper nuclear waste remediation. Three objectives were pursued using a simple building block strategies and by strategically placing anion-binding sites at appropriate positions on organic host molecules. The goal of the first objective was to assess the influence of secondary, tertiary and quaternized amines on binding tetrahedral anions using mixed amide/amine macrocyclic and urea/amine hosts containing aromatic or heteroaromatic spacers. Objective 2 focused on the design of ion pair hosts, using mixed macrocyclic anion hostsmore » joined through polyether linkages. Objective 3 was to explore the synthesis of new metal-linked extended macrocyclic frameworks to leverage anion binding. Key findings were that smaller 24-membered macrocycles provided the most complementary binding for sulfate ion and mixed urea/amine chelates showed enhanced binding over amide corollaries in addition to being highly selective for SO 4 2- in the presence of small quantities of water. In addition to obtaining prototype metal-linked macrocyclic anion hosts, a new dipincer ligand was designed that can be used to link macrocyclic or other supramolecular hosts in extended frameworks. When the tetraamide-based pincers are bound to two metal ions, an interesting phenomenon occurs. Upon deprotonation of the amides, two new protons appear between adjacent carbonyl pairs on the ligand, which may modify the chemistry, and metal-metal interactions in the complexes. Gel formation occurred for some of these extended hosts, and the physical properties are currently under investigation. The new tetracarboxamide-based pincers can also provide basic frameworks for double macrocycles capable of binding ion pairs as well as for binding metal ions and exploring intermetallic interactions through 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.« less

Organic Nanoflowers from a Wide Variety of Molecules Templated by a Hierarchical Supramolecular Scaffold.

PubMed

Negrón, Luis M; Díaz, Tanya L; Ortiz-Quiles, Edwin O; Dieppa-Matos, Diómedes; Madera-Soto, Bismark; Rivera, José M

2016-03-15

Nanoflowers (NFs) are flowered-shaped particles with overall sizes or features in the nanoscale. Beyond their pleasing aesthetics, NFs have found a number of applications ranging from catalysis, to sensing, to drug delivery. Compared to inorganic based NFs, their organic and hybrid counterparts are relatively underdeveloped mostly because of the lack of a reliable and versatile method for their construction. We report here a method for constructing NFs from a wide variety of biologically relevant molecules (guests), ranging from small molecules, like doxorubicin, to biomacromolecules, like various proteins and plasmid DNA. The method relies on the encapsulation of the guests within a hierarchically structured particle made from supramolecular G-quadruplexes. The size and overall flexibility of the guests dictate the broad morphological features of the resulting NFs, specifically, small and rigid guests favor the formation of NFs with spiky petals, while large and/or flexible guests promote NFs with wide petals. The results from experiments using confocal fluorescence microscopy, and scanning electron microscopy provides the basis for the proposed mechanism for the NF formation.

Solid state manipulation of lornoxicam for cocrystals--physicochemical characterization.

PubMed

Nijhawan, Monika; Santhosh, A; Babu, P R Sathesh; Subrahmanyam, C V S

2014-09-01

Lornoxicam is an analgesic and anti-inflammatory drug of choice and belongs to Class II (low solubility) of BCS (Biopharmaceutical Classification System). Thus bioavailabilities problems are predominant. Through crystal engineering approach, a method was developed for obtaining multi-component cocrystals of lornoxicam using pharmaceutically acceptable compounds as guests. Lornoxicam guest-free form was obtained from solution crystallization. Supramolecular synthon approach indicated that lornoxicam was in orthorhombic form. Further presence of intermolecular hydrogen bonding with layered structures was identified. Solvent drop grinding method permitted the formation of cocrystals of lornoxicam with catechol, resorcinol, benzoic acid, hydroxyquinone and 2,4 dihydroxy benzoic acid, all are capable of forming hydrogen bonding. Lornoxicam cocrystals exhibited the difference in melting points and decomposition characteristics. The analysis of infrared (IR) indicated the shifting of characteristic bands of lornoxicam. The XPRD (X-Ray Powder Diffraction) pattern indicated the crystallinity of cocrystals and significant difference in 2θ value of intense peaks. Differential scanning calorimetry spectra of cocrystals denoted the changes in fusion endotherms, which are in agreements with melting points. The pH solubility profile of lornoxicam showed sigmoidal curve, which substantiated the pKa-dependent solubility. Lornoxicam cocrystals also exhibited a similar pH-solubility profile. Thus pairing of lornoxicam and coformers in the solution at high pH media was assumed. The in vitro dissolution studies of cocrystals were conducted at pH 4.0. The rapid rate of dissolution of cocrystals was observed in initial 10 min. The extent of dissolution was enhanced by 20% on account of cocrystallization. The lornoxicam cocrystals were obtained with improved physicochemical characteristics.

Encapsulation of a rhodamine dye within a bile acid binding protein: toward water processable functional bio host-guest materials.

PubMed

Tomaselli, Simona; Giovanella, Umberto; Pagano, Katiuscia; Leone, Giuseppe; Zanzoni, Serena; Assfalg, Michael; Meinardi, Francesco; Molinari, Henriette; Botta, Chiara; Ragona, Laura

2013-10-14

New strategies are requested for the preparation of bioinspired host-guest complexes to be employed in technologically relevant applications, as sensors and optoelectronic devices. We report here a new approach employing a single monomeric protein as host for the strongly fluorescent rhodamine dye. The selected protein, belonging to the intracellular lipid binding protein family, fully encapsulates one rhodamine molecule inside its cavity forming a host-guest complex stabilized by H and π-hydrogen bonds, a salt bridge, and favorable hydrophobic contacts, as revealed by the NMR derived structural model. The protein-dye solutions are easily processable and form homogeneous thin films exhibiting excellent photophysical and morphological properties, as derived from photoluminescence and AFM data. The obtained results represent the proof of concept of the viability of this bio host-guest system for the development of bioinspired optoelectronic devices.

Solubilization and stabilization of macular carotenoids by water soluble oligosaccharides and polysaccharides.

PubMed

Apanasenko, Irina E; Selyutina, Olga Yu; Polyakov, Nikolay E; Suntsova, Lyubov P; Meteleva, Elizaveta S; Dushkin, Alexander V; Vachali, Preejith; Bernstein, Paul S

2015-04-15

Xanthophyll carotenoids zeaxanthin and lutein play a special role in the prevention and treatment of visual diseases. These carotenoids are not produced by the human body and must be consumed in the diet. On the other hand, extremely low water solubility of these carotenoids and their instability restrict their practical application as components of food or medicinal formulations. Preparation of supramolecular complexes of zeaxanthin and lutein with glycyrrhizic acid, its disodium salt and the natural polysaccharide arabinogalactan allows one to minimize the aforementioned disadvantages when carotenoids are used in food processing as well as for production of therapeutic formulations with enhanced solubility and stability. In the present study, the formation of supramolecular complexes was investigated by NMR relaxation, surface plasmon resonance (SPR) and optical absorption techniques. The complexes increase carotenoid solubility more than 1000-fold. The kinetics of carotenoid decay in reactions with ozone molecules, hydroperoxyl radicals and metal ions were measured in water and organic solutions, and significant increases in oxidation stability of lutein and zeaxanthin in arabinogalactan and glycyrrhizin complexes were detected. Copyright © 2014 Elsevier Inc. All rights reserved.

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

PubMed

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.

Solubility profiles, hydration and desolvation of curcumin complexed with γ-cyclodextrin and hydroxypropyl-γ-cyclodextrin

NASA Astrophysics Data System (ADS)

Shityakov, Sergey; Salmas, Ramin Ekhteiari; Durdagi, Serdar; Roewer, Norbert; Förster, Carola; Broscheit, Jens

2017-04-01

In this study, we investigated curcumin (CUR) solubility profiles and hydration/desolvation effects of this substance formulated with γ-cyclodextrin (γ-CD) and hydroxypropyl-γ-cyclodextrin (HP-γ-CD) excipients. The CUR/HP-γ-CD complex was found to be more stable in solution with the highest apparent stability constant for CUR/HP-γ-CD (Kc = 1.58*104 M-1) as the more soluble form in distilled water. The in silico calculations, including molecular docking, Monte Carlo (MC), and molecular dynamics (MD) simulations, indicated that water molecules play an important role in host-guest complexation mediating the CUR binding to cyclodextrins via hydrogen bond formations. The CUR hydration/desolvation effects contributed to the complex formation by elevating the CUR binding affinity to both CDs. The CUR/HP-γ-CD complex after the CUR hydration was determined with a minimal Gibbs free energy of binding (ΔGbind = -9.93 kcal*mol-1) due to the major hydrophobic (vdW) forces. Overall, the results of this study can aid a development of cyclodextrin-based drug delivery vectors, signifying the importance of water molecules during the formulation processes.

Incorporating Bacteria as a Living Component in Supramolecular Self-Assembled Monolayers through Dynamic Nanoscale Interactions.

PubMed

Sankaran, Shrikrishnan; Kiren, Mustafa Can; Jonkheijm, Pascal

2015-01-01

Supramolecular assemblies, formed through noncovalent interactions, has become particularly attractive to develop dynamic and responsive architectures to address living systems at the nanoscale. Cucurbit[8]uril (CB[8]), a pumpkin shaped macrocylic host molecule, has been successfully used to construct various self-assembled architectures for biomedical applications since it can simultaneously bind two aromatic guest molecules within its cavity. Such architectures can also be designed to respond to external stimuli. Integrating living organisms as an active component into such supramolecular architectures would add a new dimension to the capabilities of such systems. To achieve this, we have incorporated supramolecular functionality at the bacterial surface by genetically modifying a transmembrane protein to display a CB[8]-binding motif as part of a cystine-stabilized miniprotein. We were able to confirm that this supramolecular motif on the bacterial surface specifically binds CB[8] and forms multiple intercellular ternary complexes leading to aggregation of the bacterial solution. We performed various aggregation experiments to understand how CB[8] interacts with this bacterial strain and also demonstrate that it can be chemically reversed using a competitor. To confirm that this strain can be incorporated with a CB[8] based architecture, we show that the bacterial cells were able to adhere to CB[8] self-assembled monolayers (SAMs) on gold and still retain considerable motility for several hours, indicating that the system can potentially be used to develop supramolecular bacterial biomotors. The bacterial strain also has the potential to be combined with other CB[8] based architectures like nanoparticles, vesicles and hydrogels.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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.

Self-encapsulation of [MII(phen)2(H2O)2]2+ (M=Co, Zn) in one-dimensional nanochannels of [MII(H2O)6(BTC)2]4- (M=Co, Cu, Mn): a high HQ/CAT ratio catalyst for hydroxylation of phenols.

PubMed

Bi, Jianhong; Kong, Lingtao; Huang, Zixiang; Liu, Jinhuai

2008-06-02

Four novel three-dimensional (3D) microporous supramolecular compounds containing nanosized channels, namely, [Co(phen)2(H2O)2]2[Co(H2O)6].2BTC.21.5H2O (1), [Co(phen)2(H2O)2]2[Cu(H2O)6].2BTC.21.5H2O (2), [Co(phen)2(H2O)2]2[Mn(H2O)6].2BTC.18H2O (3), and [Zn(phen)2(H2O)2]2[Mn(H2O)6].2BTC.22.5H2O (4), were synthesized from 1,3,5-benzenetricarboxylate (BTC), 1,10-phenanthroline (phen), and the transition-metal salt(s) by self-assembly. Single-crystal X-ray structural analysis showed that the resulting 3D microporous supramolecular frameworks consist of a two-dimensional (2D) hydrogen-bonded host framework of [MII(H2O)6(BTC)2]4- (M=Co for 1, Cu for 2, Mn for 3, 4) with rectangular-shaped cavities containing [MII(phen)2(H2O)2]2+ (M=Co for 1-3, Zn for 4) guests. The guest complex is encapsulated in the 2D hydrogen-bonded host framework by hydrogen bonding and aromatic pi-pi stacking interactions, forming the 3D hydrogen-bonded framework. The catalytic activities of 1, 2, 3, and 4 were studied using hydroxylation of phenols with 30% aqueous H2O2 as a test reaction. The compounds displayed a good phenol conversion ratio and excellent channel selectivity in the hydroxylation reaction, with a maximum hydroquinone (HQ)/catechol (CAT) ratio of 3.9.

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

PubMed Central

Poorghorban, Masoomeh; Das, Umashankar; Alaidi, Osama; Chitanda, Jackson M; Michel, Deborah; Dimmock, Jonathan; Verrall, Ronald; Grochulski, Pawel; Badea, Ildiko

2015-01-01

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 structural features, supporting the formation of the host–guest complexes. Complexes of NC 2067 with CDgemini surfactants formed nanoparticles having sizes of 100–200 nm. NC 2067 retained its anticancer activity in the complex with CDgemini surfactant for different drug-to-carrier mole ratios, with an IC50 (half-maximal inhibitory concentration) value comparable to that for NC 2067 without the carrier. Conclusion The formation of host–guest complexes of NC 2067 with CD or CDgemini surfactant has been confirmed and hence the CDgemini surfactant shows good potential to be used as a delivery system for anticancer agents. PMID:25609956

Switchable host-guest systems on surfaces.

PubMed

Yang, Ying-Wei; Sun, Yu-Long; Song, Nan

2014-07-15

CONSPECTUS: For device miniaturization, nanotechnology follows either the "top-down" approach scaling down existing larger-scale devices or the "bottom-up' approach assembling the smallest possible building blocks to functional nanoscale entities. For synthetic nanodevices, self-assembly on surfaces is a superb method to achieve useful functions and enable their interactions with the surrounding world. Consequently, adaptability and responsiveness to external stimuli are other prerequisites for their successful operation. Mechanically interlocked molecules such as rotaxanes and catenanes, and their precursors, that is, molecular switches and supramolecular switches including pseudorotaxanes, are molecular machines or prototypes of machines capable of mechanical motion induced by chemical signals, biological inputs, light or redox processes as the external stimuli. Switching of these functional host-guest systems on surfaces becomes a fundamental requirement for artificial molecular machines to work, mimicking the molecular machines in nature, such as proteins and their assemblies operating at dynamic interfaces such as the surfaces of cell membranes. Current research endeavors in material science and technology are focused on developing either a new class of materials or materials with novel/multiple functionalities by shifting host-guest chemistry from solution phase to surfaces. In this Account, we present our most recent attempts of building monolayers of rotaxanes/pseudorotaxanes on surfaces, providing stimuli-induced macroscopic effects and further understanding on the switchable host-guest systems at interfaces. Biocompatible versions of molecular machines based on synthetic macrocycles, such as cucurbiturils, pillararenes, calixarenes, and cyclodextrins, have been employed to form self-assembled monolayers of gates on the surfaces of mesoporous silica nanoparticles to regulate the controlled release of cargo/drug molecules under a range of external stimuli, such as light, pH variations, competitive binding, and enzyme. Rotaxanes have also been assembled onto the surfaces of gold nanodisks and microcantilevers to realize active molecular plasmonics and synthetic molecular actuators for device fabrication and function. Pillararenes have been successfully used to control and aid the synthesis of gold nanoparticles, semiconducting quantum dots, and magnetic nanoparticles. The resulting organic-inorganic hydrid nanomaterials have been successfully used for controlled self-assembly, herbicide sensing and detection, pesticide removal, and so forth, taking advantage of the selective binding of pillarenes toward target molecules. Cyclodextrins have also been successfully functionalized onto the surface of gold nanoparticles to serve as recycling extractors for C60. Many interesting prototypes of nanodevices based on synthetic macrocycles and their host-guest chemistry have been constructed and served for different potential applications. This Account will be a summary of the efforts made mainly by us, and others, on the host-guest chemistry of synthetic macrocyclic compounds on the surfaces of different solid supports.

Design of a flexible organometallic tecton: host-guest chemistry with picric acid and self-assembly of platinum macrocycles.

PubMed

Jana, Achintya; Bhowmick, Sourav; Kaur, Supreet; Kashyap, Hemant K; Das, Neeladri

2017-02-14

The synthesis and characterization of a new pyrazine-based "flexible" and ditopic platinum(ii) organometallic molecule (3) is being reported. Flexibility in this molecule is due to the presence of ether functional groups that bridge the rigid core and periphery. Due to the presence of square planar Pt(ii) centers at the two ends, the molecule's potential to act as an acceptor building block in the construction of metallamacrocycles was tested. Upon reaction of 3 with various dicarboxylates in a 1 : 1 stoichiometric ratio, [2 + 2] self-assembled neutral metallacycles (M1-M3) were obtained in high yields. M1-M3 were characterized using multinuclear NMR, high resolution mass spectrometry and elemental analyses. The shape and dimensions of these supramolecular structures were also confirmed by optimizing the geometry using the density functional theory (DFT) approach. Computational studies suggest that M1-M3 are nanoscalar macrocyles. Furthermore, using isothermal titration calorimetry (ITC), it was shown that 3 can bind with picric acid (PA) to yield a 3·(PA) 2 host-guest complex. The magnitude of the binding constant indicates that 3 has significant affinity for PA.

GSH- and pH-responsive drug delivery system constructed by water-soluble pillar[5]arene and lysine derivative for controllable drug release.

PubMed

Wu, Xuan; Li, Yan; Lin, Chen; Hu, Xiao-Yu; Wang, Leyong

2015-04-21

Novel GSH- and pH-responsive supramolecular vesicles constructed by an amphiphilic inclusion complex formed from water-soluble pillar[5]arene and lysine derivative have been successfully developed, which can efficiently encapsulate anticancer drug MTZ and show rapid MTZ-release in a simulated acidic tumor environment with high GSH concentration, and exhibit potent antitumor activity.

Kinetic and thermodynamic consequences of the substitution of SMe for OMe substituents of cryptophane hosts on the binding of neutral and cationic guests.

PubMed

Garcia, Chantal; Humilière, Delphine; Riva, Nathalie; Collet, André; Dutasta, Jean-Pierre

2003-06-21

To investigate the origin of the high selectivity of cryptophane-E (1) towards Me3NH+, Me4N+, and CHCl3, and particularly to discriminate the different contributions that stabilize the supramolecular complexes, we have synthesized the new cryptophane 2 bearing six MeS groups instead of MeO groups in 1. This led to a decrease of the negative charge density in the equatorial region of 2 without affecting notably the size of the molecular cavity. The binding properties of 1 and 2 towards the three guests were examined in solution and showed a slight decrease of the deltaGa favoring the complexes of 1, accompanied by a significant modification of the deltaHa vs. deltaSa balance. The binding of the ammonium guests to 1 and 2 was strongly entropy driven, while that of CHCl3 was purely enthalpy driven. A combination of spectroscopic and computational techniques was used to assign the main intermolecular interactions that occurred during the inclusion process. The neutral CHCl3 molecule is more stabilized in the less negatively charged CTV cap of 1. The different behavior towards the ammonium cations can be explained in term of interactions with the electronegative heteroatoms and cation-pi interactions. Moreover, this study revealed a considerable slowing down of the guest exchange kinetics with host 2, for which the association and dissociation rates are reduced by a factor 10(3) to 10(4) with respect to 1. For example, at room temperature, the Me4N+@2 complex exhibits a half-life of ca. 2 years, instead of a few hours for the corresponding complex of 1.

Versatile assembly of p-carboxylatocalix[4]arene-O-alkyl ethers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennedy, Stuart; Teat, Simon J.; Dalgarno, Scott J.

Crystallisation of lower-rim tetra-O-alkylated p-carboxylatocalix[4]arenes from pyridine results in the formation of both bi-layer and pillar type supramolecular motifs. Full alkylation at the calixarene lower rim has significant influence over the supramolecular self-assembly motif, including preclusion of pyridine guest molecules from the calixarene cavity in the solid state.

A Glycyrrhetinic Acid-Modified Curcumin Supramolecular Hydrogel for liver tumor targeting therapy

PubMed Central

Chen, Guoqin; Li, Jinliang; Cai, Yanbin; Zhan, Jie; Gao, Jie; Song, Mingcai; Shi, Yang; Yang, Zhimou

2017-01-01

Curcumin (Cur), a phenolic anti-oxidant compound obtained from Curcuma longa plant, possesses a variety of therapeutic properties. However, it is suffered from its low water solubility and low bioavailability property, which seriously restricts its clinical application. In this study, we developed a glycyrrhetinic acid (GA) modified curcumin supramolecular pro-gelator (GA-Cur) and a control compound Nap-Cur by replacing GA with the naphthylacetic acid (Nap). Both compounds showed good water solubility and could form supramolecular gels by disulfide bond reduction triggered by glutathione (GSH) in vitro. Both formed gels could sustainedly release Cur in buffer solutions. We also investigated the cytotoxicity of pro-gelators to HepG2 cells by a MTT assay and determined the cellular uptake behaviours of them by fluorescence microscopy and LC-MS. Due to the over expression of GA receptor in liver cancer cells, our pro-gelator of GA-Cur showed an enhanced cellular uptake and better inhibition capacity to liver tumor cells than Nap-Cur. Therefore, the GA-Cur could significantly inhibit HepG2 cell growth. Our study provides a novel nanomaterial for liver tumor chemotherapy. PMID:28281678

A Glycyrrhetinic Acid-Modified Curcumin Supramolecular Hydrogel for liver tumor targeting therapy

NASA Astrophysics Data System (ADS)

Chen, Guoqin; Li, Jinliang; Cai, Yanbin; Zhan, Jie; Gao, Jie; Song, Mingcai; Shi, Yang; Yang, Zhimou

2017-03-01

Curcumin (Cur), a phenolic anti-oxidant compound obtained from Curcuma longa plant, possesses a variety of therapeutic properties. However, it is suffered from its low water solubility and low bioavailability property, which seriously restricts its clinical application. In this study, we developed a glycyrrhetinic acid (GA) modified curcumin supramolecular pro-gelator (GA-Cur) and a control compound Nap-Cur by replacing GA with the naphthylacetic acid (Nap). Both compounds showed good water solubility and could form supramolecular gels by disulfide bond reduction triggered by glutathione (GSH) in vitro. Both formed gels could sustainedly release Cur in buffer solutions. We also investigated the cytotoxicity of pro-gelators to HepG2 cells by a MTT assay and determined the cellular uptake behaviours of them by fluorescence microscopy and LC-MS. Due to the over expression of GA receptor in liver cancer cells, our pro-gelator of GA-Cur showed an enhanced cellular uptake and better inhibition capacity to liver tumor cells than Nap-Cur. Therefore, the GA-Cur could significantly inhibit HepG2 cell growth. Our study provides a novel nanomaterial for liver tumor chemotherapy.

Clathrate formation and phase equilibria in the thiourea-bromoform system

NASA Astrophysics Data System (ADS)

Chekhova, G. N.; Shubin, Yu. V.; Pinakov, D. V.; Alferova, N. I.

2008-07-01

Phase equilibria in the thiourea (host)-bromoform (guest) binary system were studied by physicochemical analysis methods over the temperature range 270 455 K. The stoichiometry and stability region were determined for the channel-type compound CHBr3 · 2.40(2)(NH2)2CS; the compound was observed for the first time. When heated, the clathrate incongruently decomposed at 424.0 ± 0.8 K to rhombic thiourea and the guest component. The solubility isotherm of the thiourea-bromoform-acetic acid system was studied to find that the compound was thermodynamically stable at 293 K over the range of guest component concentrations 100 35 wt %. A decrease in its content in an equilibrium mother liquor resulted in the appearance of X-ray diffraction reflections of the initial host α polymorph. Rhombohedral cell parameters were determined (space group R-3 c, a = 15.89(1) Å, c = 12.40(1) Å, V = 2711(6) Å3, d calcd = 2.000 g/cm3, and d expt = 1.98(2) g/cm3). The mode of packing of bromoform molecules was compared with the organization of the guest subsystem in inclusion compounds formed by the substances studied.

Mechanochemical Preparation of Stable Sub-100 nm γ-Cyclodextrin:Buckminsterfullerene (C60) Nanoparticles by Electrostatic or Steric Stabilization.

PubMed

Van Guyse, Joachim F R; de la Rosa, Victor R; Hoogenboom, Richard

2018-02-21

Buckminster fullerene (C 60 )'s main hurdle to enter the field of biomedicine is its low bioavailability, which results from its extremely low water solubility. A well-known approach to increase the water solubility of C 60 is by complexation with γ-cyclodextrins. However, the formed complexes are not stable in time as they rapidly aggregate and eventually precipitate due to attractive intermolecular forces, a common problem in inclusion complexes of cyclodextrins. In this study we attempt to overcome the attractive intermolecular forces between the complexes by designing custom γ-cyclodextrin (γCD)-based supramolecular hosts for C 60 that inhibit the aggregation found in native γCD-C 60 complexes. The approach entails the introduction of either repulsive electrostatic forces or increased steric hindrance to prevent aggregation, thus enhancing the biomedical application potential of C 60 . These modifications have led to new sub-100 nm nanostructures that show long-term stability in solution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inclusion complex from cyclodextrin-grafted hyaluronic acid and pseudo protein as biodegradable nano-delivery vehicle for gambogic acid.

PubMed

Ji, Ying; Shan, Shuo; He, Mingyu; Chu, Chih-Chang

2017-10-15

β-Cyclodextrin can form inclusion complex with a series of guest molecules including phenyl moieties, and has gained considerable popularity in the study of supramolecular nanostructure. In this study, a biodegradable nanocomplex (HA(CD)-4Phe4 nanocomplex) was developed from β-cyclodextrin grafted hyaluronic acid (HA) and phenylalanine based poly(ester amide). The phenylalanine based poly(ester amide) is a biodegradable pseudo protein which provides the encapsulation capacity for gambogic acid (GA), a naturally-derived chemotherapeutic which has been effectively employed to treat multidrug resistant tumor. The therapeutic potency of free GA is limited due to its poor solubility in water and the lack of tumor-selective toxicity. The nanocomplex carrier enhanced the solubility and availability of GA in aqueous media, and the HA component enabled the targeted delivery to tumor cells with overexpression of CD44 receptors. In the presence of hyaluronidase, the release of GA from the nanocomplex was significantly accelerated, due to the enzymatic biodegradation of the carrier. Compared to free GA, GA-loaded nanocomplex exhibited improved cytotoxicity in MDA-MB-435/MDR multidrug resistant melanoma cells, and induced enhanced level of apoptosis and mitochondrial depolarization, at low concentration of GA (1-2µM). The nanocomplex enhanced the therapeutic potency of GA, especially when diluted in physiological environment. In addition, suppressed matrix metalloproteinase activity was also detected in MDA-MB-435/MDR cells treated by GA-loaded nanocomplex, which demonstrated its potency in the inhibition of tumor metastasis. The in vitro data suggested that HA(CD)-4Phe4 nanocomplex could provide a promising alternative in the treatment of multidrug resistant tumor cells. Gambogic acid (GA), naturally derived from genus Garcinia trees, exhibited significant cytotoxic activity against multiple types of tumors with resistance to traditional chemotherapeutics. Unfortunately, the poor solubility of GA in conventional pharmaceutical solvents and non-targeted distribution in normal tissues greatly limited its therapeutic potency. To overcome the challenges, we develop a nanoplatform from the supramolecular assembly of β-cyclodextrin grafted hyaluronic acid (HA) and phenylalanine based pseudo protein. The pseudo protein in the nanocomplex provided the hydrophobic interaction and loading capacity for GA, while the HA component targeted the overexpressed CD44 receptor and improved the selective endocytosis in multidrug resistant melanoma cells. The supramolecular nanocomplex provide a promising platform for the delivery of hydrophobic chemotherapeutics to improve the bioavailability and efficiency. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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 Disassembly of Facially Amphiphilic Dendrimer Assemblies in Response to Physical, Chemical, and Biological Stimuli

PubMed Central

2015-01-01

Conspectus Supramolecular assemblies formed from spontaneous self-assembly of amphiphilic macromolecules are explored as biomimetic architectures and for applications in areas such as sensing, drug delivery, and diagnostics. Macromolecular assemblies are usually preferred, compared with their simpler small molecule counterparts, due to their low critical aggregate concentrations (CAC) and high thermodynamic stability. This Account focuses on the structural and functional aspects of assemblies formed from dendrimers, specifically facially amphiphilic dendrons that form micelle or inverse micelle type supramolecular assemblies depending on the nature of the solvent medium. The micelle type assemblies formed from facially amphiphilic dendrons sequester hydrophobic guest molecules in their interiors. The stability of these assemblies is dependent on the relative compatibility of the hydrophilic and hydrophobic functionalities with water, often referred to as hydrophilic–lipophilic balance (HLB). Disruption of the HLB, using an external stimulus, could lead to disassembly of the aggregates, which can then be utilized to cause an actuation event, such as guest molecule release. Studying these possibilities has led to (i) a robust and general strategy for stimulus-induced disassembly and molecular release and (ii) the introduction of a new approach to protein-responsive supramolecular disassembly. The latter strategy provides a particularly novel avenue for impacting biomedical applications. Most of the stimuli-sensitive supramolecular assemblies have been designed to be responsive to factors such pH, temperature, and redox conditions. The reason for this interest stems from the fact that certain disease microenvironments have aberrations in these factors. However, these variations are the secondary imbalances in biology. Imbalances in protein activity are the primary reasons for most, if not all, human pathology. There have been no robust strategies in stimulus-responsive assemblies that respond to these variations. The facially amphiphilic dendrimers provide a unique opportunity to explore this possibility. Similarly, the propensity of these molecules to form inverse micelles in apolar solvents and thus bind polar guest molecules, combined with the fact that these assemblies do not thermodynamically equilibrate in biphasic mixtures, was used to predictably simplify peptide mixtures. The structure–property relationships developed from these studies have led to a selective and highly sensitive detection of peptides in complex mixtures. Selectivity in peptide extraction was achieved using charge complementarity between the peptides and the hydrophilic components present in inverse micellar interiors. These findings will have implications in areas such as proteomics and biomarker detection. PMID:24937682

Solid-state studies and antioxidant properties of the γ-cyclodextrin·fisetin inclusion compound.

PubMed

Pais, Joana M; Barroca, Maria João; Marques, Maria Paula M; Almeida Paz, Filipe A; Braga, Susana S

2017-01-01

Fisetin is a natural antioxidant with a wide range of nutraceutical properties, including antidiabetic, neuroprotecting, and suppression or prevention of tumors. The present work describes the preparation of a water-soluble, solid inclusion compound of fisetin with gamma-cyclodextrin (γ-CD), a cyclic oligosaccharide approved for human consumption. A detailed physicochemical analysis of the product is carried out using elemental analysis, powder X-ray diffraction (PXRD), Raman, infrared and 13 C{ 1 H} CP-MAS NMR spectroscopies, and thermal analysis (TGA) to verify fisetin inclusion and to present a hypothetical structural arrangement for the host-guest units. The antioxidant activity of the γ-CD·fisetin inclusion compound is evaluated by the DPPH assay.

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

NASA Astrophysics Data System (ADS)

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.

Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H 2 production

DOE PAGES

Tian, Jia; Xu, Zi-Yue; Zhang, Dan-Wei; ...

2016-05-10

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 polyoxometalatesmore » (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.« less

Supramolecular complex of a fused zinc phthalocyanine-zinc porphyrin dyad assembled by two imidazole-C60 units: ultrafast photoevents.

PubMed

Follana-Berná, Jorge; Seetharaman, Sairaman; Martín-Gomis, Luis; Charalambidis, Georgios; Trapali, Adelais; Karr, Paul A; Coutsolelos, Athanassios G; Fernández-Lázaro, Fernando; D'Souza, Francis; Sastre-Santos, Ángela

2018-03-14

A new zinc phthalocyanine-zinc porphyrin dyad (ZnPc-ZnP) fused through a pyrazine ring has been synthesized as a receptor for imidazole-substituted C 60 (C 60 Im) electron acceptor. Self-assembly via metal-ligand axial coordination and the pertinent association constants in solution were determined by 1 H-NMR, UV-Vis and fluorescence titration experiments at room temperature. The designed host was able to bind up to two C 60 Im electron acceptor guest molecules to yield C 60 Im:ZnPc-ZnP:ImC 60 donor-acceptor supramolecular complex. The spectral data showed that the two binding sites behave independently with binding constants similar in magnitude. Steady-state fluorescence studies were indicative of an efficient singlet-singlet energy transfer from zinc porphyrin to zinc phthalocyanine within the fused dyad. Accordingly, the transient absorption studies covering a wide timescale of femto-to-milli seconds revealed ultrafast energy transfer from 1 ZnP* to ZnPc (k EnT ∼ 10 12 s -1 ) in the fused dyad. Further, a photo induced electron transfer was observed in the supramolecularly assembled C 60 Im:ZnPc-ZnP:ImC 60 donor-acceptor complex leading to charge separated states, which persisted for about 200 ns.

Energetics of phosphate binding to ammonium and guanidinium containing metallo-receptors in water.

PubMed

Tobey, Suzanne L; Anslyn, Eric V

2003-12-03

The design and synthesis of receptors containing a Cu(II) binding site with appended ammonium groups (1) and guanidinium groups (2), along with thermodynamics analyses of anion binding, are reported. Both receptors 1 and 2 show high affinities (10(4) M(-1)) and selectivities for phosphate over other anions in 98:2 water:methanol at biological pH. The binding of the host-guest pairs is proposed to proceed through ion-pairing interactions between the charged functional groups on both the host and the guest. The affinities and selectivities for oxyanions were determined using UV/vis titration techniques. Additionally, thermodynamic investigations indicate that the 1:phosphate complex is primarily entropy driven, while the 2:phosphate complex displays both favorable enthalpy and entropy changes. The thermodynamic data for binding provide a picture of the roles of the host, guest, counterions, and solvent. The difference in the entropy and enthalpy driving forces for the ammonium and guanidinium containing hosts are postulated to derive primarily from differences in the solvation shell of these two groups.

Polynuclear Aromatic Hydrocarbons with Curved Surfaces: Buckyballs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sygula, Andrzej

The discovery of a new allotropic form of elemental carbon – the fullerenes – and subsequently other novel forms of elemental carbon with pyramidalized surfaces, most notably single-walled and multi-walled carbon nanotubes, introduced a novel structural motif to the polycyclic aromatic hydrocarbons (PAHs) with nonplanar surfaces. Our research program supported by BES DOE grant DE-FG02-04ER15514 has dealt with the synthesis, structural studies, and chemistry of the novel curved-surface PAHs with carbon frameworks structurally related to fullerenes. They are referred to as “buckybowls”. We prepared several new buckybowls and, even more importantly, developed the efficient, gram-scale synthetic methodologies for the preparationmore » of small buckybowls, most notably corannulene (C20H10) and its derivatives. In addition, the employment of the corannulene-based synthons previously developed in our laboratory led to a number of highly nonplanar molecular architectures with two or more corannulene subunits with a potential for the applications as novel materials in separation sciences, nanoelectronics, photovoltaics and catalysis. In collaboration with Professor Angelici (Iowa State) we prepared and characterized several transition metal complexes of corannulene, providing the first structural characterization of η6 metal complexes of buckybowls by a single crystal X-ray diffraction. In addition to the definitive structural characterization of the complexes we demonstrated that the (η6-C6Me6)Ru2+ unit in some relatively stable complexes activate the corannulene ligand to react with proper nucleophiles suggesting that such complexex may be used in catalysis. (Section C). We have explored the efficiency of the dispersion-based interactions of curved-surface conjugated carbon networks by high-level computational models. We showed that the curvature of such networks does not reduce the van der Waals attractions as compared to the planar systems of similar size. We than concentrated on the design, synthesis and testing of the previously unknown molecular receptors with corannulene pincers which are capable of forming the strong ball-and-socket inclusion complexes with fullerenes in solution and in the solid state. Buckycatcher I (a molecular receptor with two corannulene pincers preorganized on a tetrabensocyclooctatetraene tether) inclusion complexes with fullerenes provided the first experimental evidence for the importance of concave-convex π – π interactions in the supramolecular chemistry of fullerene carbon cages with buckybowls. C60@Buckycatcher I has become the prototypical supramolecular system formed by the relatively weak (on the atom-to-atom bases) and has been extensively used by the computational community to test the quality of the theoretical models. In addition, Buckycatcher I shows an exceptional ability to adopt other guest molecules and several its inclusion complexes and/or solvates have been structurally characterized. These unusual structures show the potential of the buckycatchers to be tested as novel organic materials. “Intelligent design” of molecular receptors with corannulene receptors using computational approach allowing for a priori prediction of their binding potentials led to the preparation of other buckycatchers. Both bi- and tridentate corannulene pincers were tested and two of the bidentate receptors (Buckycatchers II and III) exhibited the outstanding affinity toward fullerenes, significantly exciding Buckycatcher I performance. Careful tailoring of the tethers resulted in the optimization of binding energies of the receptors with guest carbon cages and in the reduction of the entropy/solvation penalties. Practical preparation of dicorannulenopentacene opens a new avenue for the synthesis of a pool of bis-corannulene receptors possessing polar groups on their dibenzobarrelene tether. The polar “anchors” can be used to attach these efficient fullerene receptors to solid supports in order to modify their surfaces with the potential applications in separation sciences, catalysis and photovoltaic materials. additionally, the presence of such groups will improve the solubility of the receptors in polar solvents, expanding the scope of their supramolecular chemistry in solutions. Rigorous studies of thermodynamics of host-guest association of molecular clips and tweezers in organic solvents with C60/C70 inclusion complexes with Buckycatcher I as a model system have provided a full set of thermodynamical data including ΔG, ΔH, and –TΔS, for the formation of the inclusion complexes over a range of temperatures and in several solvents. Both 1H NMR and Isothermal Calorimetry (ITC) titrations provide virtually identical association constants, confirming the reliability of the results. WE have shown that thermodynamics of the host-guest complex formation is more complicated than anticipated and proposed by the existing computational models. These data are of premium importance for the testing of the computational solvation models and for a deeper understanding of the supramolecular interactions in organic solvents.« less

A supramolecular nanoparticle system based on β-cyclodextrin-conjugated poly-l-lysine and hyaluronic acid for co-delivery of gene and chemotherapy agent targeting hepatocellular carcinoma.

PubMed

Xiong, Qingqing; Cui, Mangmang; Bai, Yang; Liu, Yuanyuan; Liu, Di; Song, Tianqiang

2017-07-01

A novel supramolecular nanoparticle system with core-shell structure was designed based on β-cyclodextrin-conjugated poly-l-lysine (PLCD) and hyaluronic acid for co-delivery of gene and chemotherapy agent targeting hepatocellular carcinoma (HCC). PLCD was synthesized by the conjugation of monoaldehyde activated β-cyclodextrin with poly-l-lysine via Shiff's base reaction. Doxorubicin, as a model therapeutic drug, was included into the hydrophobic cavity of β-cyclodextrin in PLCD through host-guest interaction. OligoRNA, as a model gene, was further condensed into the inclusion complexes by electrostatic interaction to form oligoRNA and doxorubicin co-loaded supramolecular nanoparticle system. Hyaluronic acid, which is often over-expressed by HCC cells, was coated on the surface of the above nanoparticles to construct HCC-targeted nanoparticle system. These nanoparticles had regular spherical shape with classic "core-shell" structure, and their size and zeta potential were 195.8nm and -22.7mV, respectively. The nanoparticles could effectively deliver doxorubicin and oligoRNA into HCC cells via CD44 receptor-mediated endocytosis and significantly inhibit the cell proliferation. In the nude mice bearing MHCC-97H tumor, the nanoparticles could be efficiently accumulated in the tumor, suggesting their strong hepatoma-targeting capability. These findings demonstrated that this novel supramolecular nanoparticle system had a promising potential for combining gene therapy and chemotherapy to treat HCC. Copyright © 2017 Elsevier B.V. All rights reserved.

A molecular dynamics study of ethanol-water hydrogen bonding in binary structure I clathrate hydrate with CO2

NASA Astrophysics Data System (ADS)

Alavi, Saman; Ohmura, Ryo; Ripmeester, John A.

2011-02-01

Guest-host hydrogen bonding in clathrate hydrates occurs when in addition to the hydrophilic moiety which causes the molecule to form hydrates under high pressure-low temperature conditions, the guests contain a hydrophilic, hydrogen bonding functional group. In the presence of carbon dioxide, ethanol clathrate hydrate has been synthesized with 10% of large structure I (sI) cages occupied by ethanol. In this work, we use molecular dynamics simulations to study hydrogen bonding structure and dynamics in this binary sI clathrate hydrate in the temperature range of 100-250 K. We observe that ethanol forms long-lived (>500 ps) proton-donating and accepting hydrogen bonds with cage water molecules from both hexagonal and pentagonal faces of the large cages while maintaining the general cage integrity of the sI clathrate hydrate. The presence of the nondipolar CO2 molecules stabilizes the hydrate phase, despite the strong and prevalent alcohol-water hydrogen bonding. The distortions of the large cages from the ideal form, the radial distribution functions of the guest-host interactions, and the ethanol guest dynamics are characterized in this study. In previous work through dielectric and NMR relaxation time studies, single crystal x-ray diffraction, and molecular dynamics simulations we have observed guest-water hydrogen bonding in structure II and structure H clathrate hydrates. The present work extends the observation of hydrogen bonding to structure I hydrates.

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

PubMed

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.

Molecular tweezers with varying anions: a comparative study.

PubMed

Dutt, Som; Wilch, Constanze; Gersthagen, Thomas; Talbiersky, Peter; Bravo-Rodriguez, Kenny; Hanni, Matti; Sánchez-García, Elsa; Ochsenfeld, Christian; Klärner, Frank-Gerrit; Schrader, Thomas

2013-07-05

Selective binding of the phosphate-substituted molecular tweezer 1a to protein lysine residues was suggested to explain the inhibition of certain enzymes and the aberrant aggregation of amyloid petide Aβ42 or α-synuclein, which are assumed to be responsible for Alzheimer's and Parkinson's disease, respectively. In this work we systematically investigated the binding of four water-soluble tweezers 1a-d (substituted by phosphate, methanephosphonate, sulfate, or O-methylenecarboxylate groups) to amino acids and peptides containing lysine or arginine residues by using fluorescence spectroscopy, NMR spectroscopy, and isothermal titration calorimetry (ITC). The comparison of the experimental results with theoretical data obtained by a combination of QM/MM and ab initio(1)H NMR shift calculations provides clear evidence that the tweezers 1a-c bind the amino acid or peptide guest molecules by threading the lysine or arginine side chain through the tweezers' cavity, whereas in the case of 1d the guest molecule is preferentially positioned outside the tweezer's cavity. Attractive ionic, CH-π, and hydrophobic interactions are here the major binding forces. The combination of experiment and theory provides deep insight into the host-guest binding modes, a prerequisite to understanding the exciting influence of these tweezers on the aggregation of proteins and the activity of enzymes.

Stimuli Responsive Systems Constructed Using Cucurbit[n]uril-Type Molecular Containers

PubMed Central

2015-01-01

Conspectus This Account focuses on stimuli responsive systems that function in aqueous solution using examples drawn from the work of the Isaacs group using cucurbit[n]uril (CB[n]) molecular containers as key recognition elements. Our entry into the area of stimuli responsive systems began with the preparation of glycoluril derived molecular clips that efficiently distinguish between self and nonself by H-bonds and π–π interactions even within complex mixtures and therefore undergo self-sorting. We concluded that the selectivity of a wide variety of H-bonded supramolecular assemblies was higher than previously appreciated and that self-sorting is not exceptional behavior. This lead us to examine self-sorting within the context of CB[n] host–guest chemistry in water. We discovered that CB[n] homologues (CB[7] and CB[8]) display remarkably high binding affinity (Ka up to 1017 M–1) and selectivity (ΔΔG) toward their guests, which renders CB[n]s prime components for the construction of stimuli responsive host–guest systems. The CB[7]·adamantaneammonium ion complex, which is particularly privileged (Ka = 4.2 × 1012 M–1), was introduced by us as a stimulus to trigger constitutional changes in multicomponent self-sorting systems. For example, we describe how the free energy associated with the formation of host–guest complexes of CB[n]-type receptors can drive conformational changes of included guests like triazene–arylene foldamers and cationic calix[4]arenes, as well as induced conformational changes (e.g., ammonium guest size dependent homotropic allostery, metal ion triggered folding, and heterochiral dimerization) of the hosts themselves. Many guests display large pKa shifts within their CB[n]–guest complexes, which we used to promote pH controlled guest swapping and thermal trans-to-cis isomerization of azobenzene derivatives. We also used the high affinity and selectivity of CB[7] toward its guests to outcompete an enzyme (bovine carbonic anhydrase) for a two-faced inhibitor, which allowed stimuli responsive regulation of enzymatic activity. These results prompted us to examine the use of CB[n]-type receptors in both in vitro and in vivo biological systems. We demonstrated that adamantaneammonium ion can be used to intracellularly sequester CB[7] from gold nanoparticles passivated with hexanediammonium ion·CB[7] complexes and thereby trigger cytotoxicity. CB[7] derivatives bearing a biotin targeting group enhance the cytotoxicity of encapsulated oxaliplatin toward L1210FR cells. Finally, acyclic CB[n]-type receptors function as solubilizing excipients for insoluble drugs for drug delivery purposes and as a broad spectrum reversal agent for the neuromuscular blocking agents rocuronium, vecuronium, and cis-atracurium in rats. The work highlights the great potential for integration of CB[n]-type receptors with biological systems. PMID:24785941

Laser damage threshold of gelatin and a copper phthalocyanine doped gelatin optical limiter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brant, M.C.; McLean, D.G.; Sutherland, R.L.

1996-12-31

The authors demonstrate optical limiting in a unique guest-host system which uses neither the typical liquid or solid host. Instead, they dope a gelatin gel host with a water soluble Copper (II) phthalocyaninetetrasulfonic acid, tetrasodium salt (CuPcTs). They report on the gelatin`s viscoelasticity, laser damage threshold, and self healing of this damage. The viscoelastic gelatin has mechanical properties quite different than a liquid or solid. The authors` laser measurements demonstrate that the single shot damage threshold of the undoped gelatin host increases with decreasing gelatin concentration. The gelatin also has a much higher laser damage threshold than a stiff acrylic.more » Unlike brittle solids, the soft gelatin self heals from laser induced damage. Optical limiting test also show the utility of a gelatin host doped with CuPcTs. The CuPcTs/gelatin matrix is not damaged at incident laser energies 5 times the single shot damage threshold of the gelatin host. However, at this high laser energy the CuPcTs is photo bleached at the beam waist. The authors repair photo bleached sites by annealing the CuPcTs/gelatin matrix.« less

Preparation of C.I. Pigment 52:1 anion-pillared layered double hydroxide and the thermo- and photostability of the resulting intercalated material

NASA Astrophysics Data System (ADS)

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.

Formation of supramolecular clusters at the interface of zeolite X following the adsorption of rare-earth cations and their impact on the macroscopic properties of the zeolite.

PubMed

Guzzinati, Roberta; Sarti, Elena; Catani, Martina; Costa, Valentina; Pagnoni, Antonella; Martucci, Annalisa; Rodeghero, Elisa; Capitani, Donatella; Pietrantonio, Massimiliana; Cavazzini, Alberto; Pasti, Luisa

2018-05-18

The adsorption behavior of neodymium (Nd3+) and yttrium (Y3+) cations on synthetic FAU zeolite 13X in its sodium form (Na13X) has been investigated by means of an approach based on both macroscopic (namely, adsorption isotherm determination and thermal analysis) and microscopic measurements (including solid-state NMR spectroscopy and X-ray powder diffraction). The multidisciplinary study has revealed some unexpected features. Firstly, adsorption constants of cations are not correlated to their ionic radii (or hydration enthalpy). The adsorption constant of Y3+ on Na13X was indeed about twice that of Nd3+, which is the opposite of what could be expected based on the size of the cations. In addition, adsorption was accompanied by partial dealumination of the zeolite framework. The extent of dealumination changed depending on exchanged cations. It was more significant on the Nd-exchanged zeolite than on the Y-exchanged one. The most interesting finding of this study, however, is the presence of supramolecular clusters composed of water, Nd3+, residual sodium ions and extraframework aluminum at the interface of Nd-exchanged zeolite. The hypothesis that these host-guest complexes are responsible of the significantly different behavior exhibited by Na13X towards the adsorption/desorption of Nd3+ and Y3+ has been formulated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reaction of nitrosonium cation with resorc[4]arenes activated by supramolecular control: covalent bond formation.

PubMed

Ghirga, Francesca; D'Acquarica, Ilaria; Delle Monache, Giuliano; Mannina, Luisa; Molinaro, Carmela; Nevola, Laura; Sobolev, Anatoly P; Pierini, Marco; Botta, Bruno

2013-07-19

Resorc[4]arenes 1 and 2, which previously proved to entrap NO(+) cation within their cavities under conditions of host-to-guest excess, were treated with a 10-fold excess of NOBF4 salt in chloroform. Kinetic and spectral UV-visible analyses revealed the formation of isomeric 1:2 complexes as a direct evolution of the previously observed event. Accordingly, three-body 1-(NO(+))2 and 2-(NO(+))2 adducts were built by MM and fully optimized by DFT calculations at the B3LYP/6-31G(d) level of theory. Notably, covalent nitration products 4, 5 and 6, 7 were obtained by reaction of NOBF4 salt with host 1 and 2, respectively, involving macrocycle ring-opening and insertion of a nitro group in one of the four aromatic rings. In particular, compounds 4 and 6, both containing a trans-double bond in the place of the methine bridge, were oxidized to aldehydes 5 and 7, respectively, after addition of water to the reaction mixture. Calculation of the charge and frontier orbitals of the aromatic donor (HOMO) and the NO(+) acceptor (LUMO) clearly suggests an ipso electrophilic attack by a first NO(+) unit on the resorcinol ring, mediated by the second NO(+) unit.

Fluorescent pseudorotaxanes of a quinodicarbocyanine dye with gamma cyclodextrin

NASA Astrophysics Data System (ADS)

Bernstein, Olivia M.; McGee, Tiffany E.; Silzel, Lisa E.; Silzel, John W.

2018-01-01

Spectrophotometric titration of buffered solutions of gamma cyclodextrin (γCD) and 1,1‧-diethyl,2,2‧-dicarbocyanine (DDI) demonstrates extension of the known 1:2 host:guest complex to form a previously unreported 2:2 complex near the γCD solubility limit. Though DDI is predominantly hosted as a non-fluorescent H-aggregate, both complexes exist in respective equilibria with two secondary complexes hosting unaggregated DDI as 1:1 and 2:1 complexes. The 2:1 complex exhibits significant fluorescence emission, with a quantum yield six times that of DDI in organic solvents, but ten times lower than that of an analogous indodicarbocyanine. Fragment Molecular Orbital calculations suggest that the 2:1 complex has the tail-to-tail conformation, and that solvent access to the dye strongly favors photoisomerization. In the host-guest complex, γCD limits solvent access to the dye and hinders rotation of the quinolyl terminal groups, but nevertheless pairwise rotation of methine carbons within the γCD cavity likely remains as a significant nonradiative relaxation pathway for the excited state.

Photoinduced fluorescence activation and nitric oxide release with biocompatible polymer nanoparticles.

PubMed

Deniz, Erhan; Kandoth, Noufal; Fraix, Aurore; Cardile, Venera; Graziano, Adriana C E; Lo Furno, Debora; Gref, Ruxandra; Raymo, Françisco M; Sortino, Salvatore

2012-12-03

A viable strategy to encapsulate a fluorophore/photochrome dyad and a nitric oxide photodonor within supramolecular assemblies of a cyclodextrin-based polymer in water was developed. The two photoresponsive guests do not interact with each other within their supramolecular container and can be operated in parallel under optical control. Specifically, the dyad permits the reversible switching of fluorescence on a microsecond timescale for hundreds of cycles, and the photodonor enables the irreversible release of nitric oxide. Furthermore, these supramolecular assemblies cross the membrane of human melanoma cancer cells and transport their cargo in the cytosol. The fluorescence of one component allows the visualization of the labeled cells, and its switchable character could, in principle, be used to acquire super-resolution images, while the release of nitric oxide from the other induces significant cell mortality. Thus, our design logic for the construction of biocompatible nanoparticles with dual functionality might evolve into the realization of valuable photoresponsive probes for imaging and therapeutic applications. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective isolation of gold facilitated by second-sphere coordination with α-cyclodextrin.

PubMed

Liu, Zhichang; Frasconi, Marco; Lei, Juying; Brown, Zachary J; Zhu, Zhixue; Cao, Dennis; Iehl, Julien; Liu, Guoliang; Fahrenbach, Albert C; Botros, Youssry Y; Farha, Omar K; Hupp, Joseph T; Mirkin, Chad A; Fraser Stoddart, J

2013-01-01

Gold recovery using environmentally benign chemistry is imperative from an environmental perspective. Here we report the spontaneous assembly of a one-dimensional supramolecular complex with an extended {[K(OH₂)₆][AuBr₄](α-cyclodextrin)₂}n chain superstructure formed during the rapid co-precipitation of α-cyclodextrin and KAuBr₄ in water. This phase change is selective for this gold salt, even in the presence of other square-planar palladium and platinum complexes. From single-crystal X-ray analyses of six inclusion complexes between α-, β- and γ-cyclodextrins with KAuBr₄ and KAuCl₄, we hypothesize that a perfect match in molecular recognition between α-cyclodextrin and [AuBr₄](-) leads to a near-axial orientation of the ion with respect to the α-cyclodextrin channel, which facilitates a highly specific second-sphere coordination involving [AuBr₄](-) and [K(OH₂)₆](+) and drives the co-precipitation of the 1:2 adduct. This discovery heralds a green host-guest procedure for gold recovery from gold-bearing raw materials making use of α-cyclodextrin-an inexpensive and environmentally benign carbohydrate.

Insights into the multi-equilibrium, superstructure system based on β-cyclodextrin and a highly water soluble guest.

PubMed

De Paula, Elgte Elmin B; De Sousa, Frederico B; Da Silva, Júlio César C; Fernandes, Flaviana R; Melo, Maria Norma; Frézard, Frédéric; Grazul, Richard M; Sinisterra, Rubén D; Machado, Flávia C

2012-12-15

Pentamidine isethionate (PNT) is an antiprotozoal active in many cases of leishmaniasis, despite the present limitations including high toxicity and parenteral administration. In the present work, a PNT encapsulation strategy into β-cyclodextrin cavity at 1:1 and 2:1 (βCD:PNT) molar ratios was used in order to improve the drug's physical and chemical properties. Combining thermodynamic and structural approaches such as isothermal titration calorimetry (ITC), electrospray ionization mass spectrometry (ESI-MS) and nuclear magnetic resonance ((1)H NMR, and ROESY) the inclusion process and the thermodynamics parameters were identified. ITC and ESI-MS experimental data suggest the simultaneous formation of different supramolecular complexes in solution. Moreover, NMR data are in accordance with these results, suggesting a deep inclusion of PNT into the βCD cavity, through correlations observed in 2D ROESY contour maps. The systems were also characterized by FTIR, TG/DTA and SEM. These techniques indicate the formation of inclusion complex in the solid state. In vivo PNT activity was evaluated orally in mice. The inclusion complex showed a significant reduction of parasite load compared to free PNT. Copyright © 2012 Elsevier B.V. All rights reserved.

Study on effect of L-arginine on solubility and dissolution of Zaltoprofen: Preparation and characterization of binary and ternary cyclodextrin inclusion complexes

NASA Astrophysics Data System (ADS)

Sherje, Atul P.; Patel, Forum; Murahari, Manikanta; Suvarna, Vasanti; Patel, Kavitkumar

2018-02-01

The present study demonstrated the binary and ternary complexes of Zaltoprofen (ZPF) with β-CD and HP-β-CD. The products were characterized using solubility, in vitro dissolution, and DSC studies. The mode of interaction of guest and host was revealed through 1H NMR and FT-IR studies. A significant increase was noticed in the stability constant (Kc) and complexation efficiency (CE) of β-CD and HP-β-CD due to addition of L-Arg in ternary complexes. The ternary complexes showed greater increase in solubility and dissolution of ZPF than binary complexes. Thus, ternary system of ZPF could be an innovative approach for its solubility and dissolution enhancement.

Reversible manipulation of the G-quadruplex structures and enzymatic reactions through supramolecular host–guest interactions

PubMed Central

Tian, Tian; Song, Yanyan; Wei, Lai; Wang, Jiaqi; Fu, Boshi; He, Zhiyong; Yang, Xi-Ran; Wu, Fan; Xu, Guohua; Liu, Si-Min; Li, Conggang

2017-01-01

Abstract Supramolecular chemistry addresses intermolecular forces and consequently promises great flexibility and precision. Biological systems are often the inspirations for supramolecular research. The G-quadruplex (G4) belongs to one of the most important secondary structures in nucleic acids. Until recently, the supramolecular manipulation of the G4 has not been reported. The present study is the first to disclose a supramolecular switch for the reversible control of human telomere G4s. Moreover, this supramolecular switch has been successfully used to manipulate an enzymatic reaction. Using various methods, we show that cucurbit[7]uril preferably locks and encapsulates the positively charged piperidines of Razo through supramolecular interactions. They can switch the conformations of the DNA inhibitor between a flexible state and the rigid G4 and are therefore responsible for the reversible control of the thrombin activity. Thus, our findings open a promising route and exhibit potential applications in future studies of chemical biology. PMID:28115627

Characterization of Cyclodextrin/Volatile Inclusion Complexes: A Review.

PubMed

Kfoury, Miriana; Landy, David; Fourmentin, Sophie

2018-05-17

Cyclodextrins (CDs) are a family of cyclic oligosaccharides that constitute one of the most widely used molecular hosts in supramolecular chemistry. Encapsulation in the hydrophobic cavity of CDs positively affects the physical and chemical characteristics of the guests upon the formation of inclusion complexes. Such a property is interestingly employed to retain volatile guests and reduce their volatility. Within this scope, the starting crucial point for a suitable and careful characterization of an inclusion complex is to assess the value of the formation constant (K f ), also called stability or binding constant. This task requires the application of the appropriate analytical method and technique. Thus, the aim of the present paper is to give a general overview of the main analytical tools used for the determination of K f values for CD/volatile inclusion complexes. This review emphasizes on the advantages, inconvenients and limits of each applied method. A special attention is also dedicated to the improvement of the current methods and to the development of new techniques. Further, the applicability of each technique is illustrated by a summary of data obtained from the literature.

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

PubMed

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.

Supra-molecular inclusion complexation of ionic liquid 1-butyl-3-methylimidazolium octylsulphate with α- and β-cyclodextrins

NASA Astrophysics Data System (ADS)

Banjare, Manoj Kumar; Behera, Kamalakanta; Satnami, Manmohan L.; Pandey, Siddharth; Ghosh, Kallol K.

2017-12-01

Host-guest complexation between ionic liquid (IL) 1-butyl-3-methylimidazolium octylsulphate [Bmim][OS] and cyclodextrins (α- and β- CDs) have been studied. Surface tension, conductivity measurements revealed the formation of 1:1 (M) stoichiometry for inclusion complexes (ICs) and further confirmed by UV-Visible and FT-IR results. The nature of the complexes has been established using interfacial and thermodynamic parameters. The aggregation number, Stern-Volmer constants, association constants were obtained from fluorescence quenching and Benesi-Hildebrand methods. The critical micelle concentration (cmc) and association constants of [Bmim][OS] are higher for β-CD as compared to α-CD. FT-IR spectra indicated that CDs and [Bmim][OS] could from ICs with stoichiometry 1:1 (M).

Rotational and constitutional dynamics of caged supramolecules

PubMed Central

Kühne, Dirk; Klappenberger, Florian; Krenner, Wolfgang; Klyatskaya, Svetlana; Ruben, Mario; Barth, Johannes V.

2010-01-01

The confinement of molecular species in nanoscale environments leads to intriguing dynamic phenomena. Notably, the organization and rotational motions of individual molecules were controlled by carefully designed, fully supramolecular host architectures. Here we use an open 2D coordination network on a smooth metal surface to steer the self-assembly of discrete trimeric guest units, identified as noncovalently bound dynamers. Each caged chiral supramolecule performs concerted, chirality-preserving rotary motions within the template honeycomb pore, which are visualized and quantitatively analyzed using temperature-controlled scanning tunneling microscopy. Furthermore, with higher thermal energies, a constitutional system dynamics appears, which is revealed by monitoring repetitive switching events of the confined supramolecules’ chirality signature, reflecting decay and reassembly of the caged units. PMID:21098303

pH Control on the Sequential Uptake and Release of Organic Cations by Cucurbit[7]uril.

PubMed

Mikulu, Lukas; Michalicova, Romana; Iglesias, Vivian; Yawer, Mirza A; Kaifer, Angel E; Lubal, Premysl; Sindelar, Vladimir

2017-02-16

Cucurbit[7]uril (CB7) is a macrocycle with the ability to form the most stable supramolecular complexes in water ever reported for an artificial receptor. Its use for the design of advanced functional materials is, however, very limited because there is no example of a fully reversible CB7 based supramolecular complex enabling repetitious dissociation/association controlled by external stimuli. We report the synthesis of a new ferrocene amino acid that forms with CB7 a 1:1 inclusion complex that is stable in submicromolar concentration at low pH but dissociates at high pH. This reversible process was used for the sequential uptake and release of bispyridinium and antraquinone guests by CB7, which is controlled by adjusting the pH of the solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Resolving the problem of trapped water in binding cavities: prediction of host-guest binding free energies in the SAMPL5 challenge by funnel metadynamics

NASA Astrophysics Data System (ADS)

Bhakat, Soumendranath; Söderhjelm, Pär

2017-01-01

The funnel metadynamics method enables rigorous calculation of the potential of mean force along an arbitrary binding path and thereby evaluation of the absolute binding free energy. A problem of such physical paths is that the mechanism characterizing the binding process is not always obvious. In particular, it might involve reorganization of the solvent in the binding site, which is not easily captured with a few geometrically defined collective variables that can be used for biasing. In this paper, we propose and test a simple method to resolve this trapped-water problem by dividing the process into an artificial host-desolvation step and an actual binding step. We show that, under certain circumstances, the contribution from the desolvation step can be calculated without introducing further statistical errors. We apply the method to the problem of predicting host-guest binding free energies in the SAMPL5 blind challenge, using two octa-acid hosts and six guest molecules. For one of the hosts, well-converged results are obtained and the prediction of relative binding free energies is the best among all the SAMPL5 submissions. For the other host, which has a narrower binding pocket, the statistical uncertainties are slightly higher; longer simulations would therefore be needed to obtain conclusive results.

Construction of single-crystalline supramolecular networks of perchlorinated hexa-peri-hexabenzocoronene on Au(111)

NASA Astrophysics Data System (ADS)

Zhang, Yi; Zhang, Yanfang; Li, Geng; Lu, Jianchen; Lin, Xiao; Tan, Yuanzhi; Feng, Xinliang; Du, Shixuan; Müllen, Klaus; Gao, Hong-Jun

2015-03-01

The self-assembly of the perchlorinated hexa-peri-hexabenzocoronene (PCHBC) molecules on Au(111) has been studied by a low temperature scanning tunneling microscopy (STM) combining with density functional theory based first principle calculations. Highly ordered supramolecular networks with single domains limited by the terraces are formed on Au(111) substrate. High resolution images of the PCHBC molecules, confirmed by first principle simulations, are obtained. It reveals the close-packed arrangement of the PCHBC molecules on Au(111). The calculated charge distribution of PCHBC molecules shows the existence of attractive halogen-halogen interaction between neighboring molecules. Compared with the disordered adsorption of hexa-peri-hexabenzocoronene on Au(111), we conclude that the formation of attractive ClCl interactions between neighbors is the key factor to form the highly ordered, close-packed networks. Due to the steric hindrance resulted from the peripheral chlorine atoms, the PCHBC molecule is contorted and forms the doubly concave conformation, which is different from the hexa-peri-hexabenzocoronene with a planar structure. By using this supramolecular network as a template, we deposited C60 molecules on it at room temperature with low coverage. The STM images taken at low temperature show that the C60 molecules are mono-dispersed on the networks and adsorb on top of the PCHBC molecules, forming a typical concave-convex host-guest system.

Intercalation of paracetamol into the hydrotalcite-like host

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kovanda, Frantisek, E-mail: Frantisek.Kovanda@vscht.cz; Maryskova, Zuzana; Kovar, Petr

2011-12-15

Hydrotalcite-like compounds are often used as host structures for intercalation of various anionic species. The product intercalated with the nonionic, water-soluble pharmaceuticals paracetamol, N-(4-hydroxyphenyl)acetamide, was prepared by rehydration of the Mg-Al mixed oxide obtained by calcination of hydrotalcite-like precursor at 500 Degree-Sign C. The successful intercalation of paracetamol molecules into the interlayer space was confirmed by powder X-ray diffraction and infrared spectroscopy measurements. Molecular simulations showed that the phenolic hydroxyl groups of paracetamol interact with hydroxide sheets of the host via the hydroxyl groups of the positively charged sites of Al-containing octahedra; the interlayer water molecules are located mostly nearmore » the hydroxide sheets. The arrangement of paracetamol molecules in the interlayer is rather disordered and interactions between neighboring molecules cause their tilting towards the hydroxide sheets. Dissolution tests in various media showed slower release of paracetamol intercalated in the hydrotalcite-like host in comparison with tablets containing the powdered pharmaceuticals. - Graphical abstract: Molecular simulations showed disordered arrangement of paracetamol molecules in the interlayer; most of the interlayer water molecules are located near the hydroxide sheets. Black-Small-Square Highlights: Black-Right-Pointing-Pointer Paracetamol was intercalated in Mg-Al hydrotalcite-like host by rehydration/reconstruction procedure. Black-Right-Pointing-Pointer Paracetamol phenolic groups interact with positively charged sites in hydroxide sheets. Black-Right-Pointing-Pointer Molecular simulations showed disordered arrangement of guest molecules in the interlayer. Black-Right-Pointing-Pointer Slower release of paracetamol intercalated in the hydrotalcite-like host was observed.« less

Supramolecular Complexation of Carbohydrates for the Bioavailability Enhancement of Poorly Soluble Drugs.

PubMed

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.

Guest-tuned spin crossover in flexible supramolecular assemblies templated by a halide (Cl -, Br - or I - )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darawsheh, M. D.; Barrios, L. A.; Roubeau, O.

Ligand 1,3-bis(3-(pyridin-2-yl)-1H-pyrazol-5-yl)benzene, L, forms mononuclear spin crossover complexes [FeL 3] 2+ with pendant arms that cause them to dimerize through numerous intermolecular interactions forming supramolecular (X@[FeL 3] 2) 3+ cations. Finally, hey have the flexibility to encapsulate Cl -, Br - or I -, which allow tuning the magnetic properties, in the solid state and in solution.

Guest-tuned spin crossover in flexible supramolecular assemblies templated by a halide (Cl -, Br - or I - )

DOE PAGES

Darawsheh, M. D.; Barrios, L. A.; Roubeau, O.; ...

2016-12-05

Ligand 1,3-bis(3-(pyridin-2-yl)-1H-pyrazol-5-yl)benzene, L, forms mononuclear spin crossover complexes [FeL 3] 2+ with pendant arms that cause them to dimerize through numerous intermolecular interactions forming supramolecular (X@[FeL 3] 2) 3+ cations. Finally, hey have the flexibility to encapsulate Cl -, Br - or I -, which allow tuning the magnetic properties, in the solid state and in solution.

Responsive Guest Encapsulation of Dynamic Conjugated Microporous Polymers.

PubMed

Xu, Lai; Li, Youyong

2016-06-30

The host-guest complexes of conjugated microporous polymers encapsulating C60 and dye molecules have been investigated systematically. The orientation of guest molecules inside the cavities, have different terms: inside the open cavities of the polymer, or inside the cavities formed by packing different polymers. The host backbone shows responsive dynamic behavior in order to accommodate the size and shape of incoming guest molecule or guest aggregates. Simulations show that the host-guest binding of conjugated polymers is stronger than that of non-conjugated polymers. This detailed study could provide a clear picture for the host-guest interaction for dynamic conjugated microporous polymers. The mechanism obtained could guide designing new conjugated microporous polymers.

Micrometer-level naked-eye detection of caesium particulates in the solid state

NASA Astrophysics Data System (ADS)

Mori, Taizo; Akamatsu, Masaaki; Okamoto, Ken; Sumita, Masato; Tateyama, Yoshitaka; Sakai, Hideki; Hill, Jonathan P.; Abe, Masahiko; Ariga, Katsuhiko

2013-02-01

Large amounts of radioactive material were released from the Fukushima Daiichi nuclear plant in Japan, contaminating the local environment. During the early stages of such nuclear accidents, iodine I-131 (half-life 8.02 d) is usually detectable in the surrounding atmosphere and bodies of water. On the other hand, in the long-term, soil and water contamination by Cs-137, which has a half-life of 30.17 years, is a serious problem. In Japan, the government is planning and carrying out radioactive decontamination operations not only with public agencies but also non-governmental organizations, making radiation measurements within Japan. If caesium (also radiocaesium) could be detected by the naked eye then its environmental remediation would be facilitated. Supramolecular material approaches, such as host-guest chemistry, are useful in the design of high-resolution molecular sensors and can be used to convert molecular-recognition processes into optical signals. In this work, we have developed molecular materials (here, phenols) as an optical probe for caesium cation-containing particles with implementation based on simple spray-on reagents and a commonly available fluorescent lamp for naked-eye detection in the solid state. This chemical optical probe provides a higher spatial resolution than existing radioscopes and gamma-ray cameras.

Spectral study and protein labeling of inclusion complex between dye and calixarene sulfonate.

PubMed

Fei, Xuening; Zhang, Yong; Zhu, Sen; Liu, Lijuan; Yu, Lu

2013-05-01

The host-guest inclusion complex of calix[6]arene sulfonate (SCA6) with thiazole orange (TO) formed in aqueous solution was studied. Absorption and fluorescence techniques were used for the analysis of this inclusion complex. The addition of calixarene sulfonate leads to a decrease in both absorption and fluorescence intensity of the dye, indicating that the inclusion complex was formed. Simultaneously, the inclusion phenomenon of another cyanine dye, Cy3, with calixarene sulfonate was investigated. The stability constant of the two complexes was determined, and the results were compared. The water solubility of TO dye was increased in the presence of calixarene sulfonate, and further protein labeling experiments suggested that this TO-SCA6 complex can act as a fluorescent probe for labeling of biomolecules.

Promising applications in drug delivery systems of a novel β-cyclodextrin derivative obtained by green synthesis.

PubMed

García, Agustina; Leonardi, Darío; Lamas, María C

2016-01-15

An efficient and green method has been developed for the synthesis of succinyl-β-cyclodextrin in aqueous media obtaining very good yield. Acidic groups have been introduced in the synthesized carrier molecule to improve the guest-host affinity. To evaluate the suitability of the novel excipient focused to develop oral dosage forms, albendazole, a BSC class II compound, was chosen as a model drug. The β-cyclodextrin derivative and the inclusion complex were thoroughly characterized in solution and solid state by phase solubility studies, FT-IR spectroscopy, SEM, XRD, ESI-MS, DSC, 1D (1)H NMR, 1D (13)C NMR, selective 1D TOCSY, 2D COSY, 2D HSQC, 2D HMBC and ROESY NMR spectroscopy. Phase solubility studies indicated that both of them β-cyclodextrin and succinyl-β-cyclodextrin formed 1:1 inclusion complexes with albendazole, and the stability constants were 68M(-1) (β-cyclodextrin), 437M(-1) (succinyl-β-cyclodextrin), respectively. Water solubility and dissolution rate of albendazole were significantly improved in complex forms. Thus, the succinyl-β-cyclodextrin derivative could be a promising excipient to design oral dosage forms. Copyright © 2015 Elsevier Ltd. All rights reserved.

Macrocyclic Receptor for Precious Gold, Platinum, or Palladium Coordination Complexes.

PubMed

Liu, Wenqi; Oliver, Allen G; Smith, Bradley D

2018-06-06

Two macrocyclic tetralactam receptors are shown to selectively encapsulate anionic, square-planar chloride and bromide coordination complexes of gold(III), platinum(II), and palladium(II). Both receptors have a preorganized structure that is complementary to its precious metal guest. The receptors do not directly ligate the guest metal center but instead provide an array of arene π-electron donors that interact with the electropositive metal and hydrogen-bond donors that interact with the outer electronegative ligands. This unique mode of supramolecular recognition is illustrated by six X-ray crystal structures showing receptor encapsulation of AuCl 4 - , AuBr 4 - , PtCl 4 -2 , or Pd 2 Cl 6 -2 . In organic solution, the 1:1 association constants correlate with specific supramolecular features identified in the solid state. Technical applications using these receptors are envisioned in a wide range of fields that involve precious metals, including mining, recycling, catalysis, nanoscience, and medicine.

Supramolecular latching system based on ultrastable synthetic binding pairs as versatile tools for protein imaging.

PubMed

Kim, Kyung Lock; Sung, Gihyun; Sim, Jaehwan; Murray, James; Li, Meng; Lee, Ara; Shrinidhi, Annadka; Park, Kyeng Min; Kim, Kimoon

2018-04-27

Here we report ultrastable synthetic binding pairs between cucurbit[7]uril (CB[7]) and adamantyl- (AdA) or ferrocenyl-ammonium (FcA) as a supramolecular latching system for protein imaging, overcoming the limitations of protein-based binding pairs. Cyanine 3-conjugated CB[7] (Cy3-CB[7]) can visualize AdA- or FcA-labeled proteins to provide clear fluorescence images for accurate and precise analysis of proteins. Furthermore, controllability of the system is demonstrated by treating with a stronger competitor guest. At low temperature, this allows us to selectively detach Cy3-CB[7] from guest-labeled proteins on the cell surface, while leaving Cy3-CB[7] latched to the cytosolic proteins for spatially conditional visualization of target proteins. This work represents a non-protein-based bioimaging tool which has inherent advantages over the widely used protein-based techniques, thereby demonstrating the great potential of this synthetic system.

Synthesis of Cyclic Porphyrin Trimers through Alkyne Metathesis Cyclooligomerization and Their Host–Guest Binding Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Chao; Long, Hai; Jin, Yinghua

2016-06-17

Cyclic porphyrin trimers were synthesized through one-step cyclooligomerization via alkyne metathesis from diyne monomers. These macrocycles show interesting host-guest binding interactions with fullerenes, selectively binding C70 (6 x 103 M-1) over C60 and C84 (no binding observed). The fullerene-encapsulated host-guest complex can undergo guest or host exchange in the presence of another guest (2,4,6-tri(4-pyridyl)-1,3,5-triazine) or host (cage COP5) molecule with higher binding affinity.

Infrared spectroscopic study of SO₄²⁻ ions included in M'₂M''(SeO₄)₂⋅6H₂O (Me'=K, NH₄⁺; M''=Mg, Co, Ni, Cu, Zn) and NH₄⁺ ions included in K₂M(XO₄)₂⋅6H₂O (X=S, Se; M''=Mg, Co, Ni, Cu, Zn).

PubMed

Marinova, D; Karadjova, V; Stoilova, D

2015-01-05

Infrared spectra of Tutton compounds, M'₂M''(SeO₄)₂⋅6H₂O (M'=K, NH₄⁺; M''=Mg, Co, Ni, Cu, Zn; X=S, Se), as well as those of SO₄²⁻ guest ions included in selenate host lattices and of NH4(+) guest ions included in potassium host lattices are presented and discussed in the regions of ν₃ and ν₁ of SO₄²⁻ guest ions, ν₄ of NH₄⁺ guest ions and water librations. The SO₄²⁻ guest ions matrix-isolated in selenate matrices (approximately 2 mol%) exhibit three bands corresponding to ν₃ and one band corresponding to ν₁ in good agreement with the low site symmetry C₁ of the host selenate ions. When the larger SO₄²⁻ ions are replaced by the smaller SO₄²⁻ ions the mean values of the asymmetric stretching modes ν₃ of the included SO₄²⁻ ions are slightly shifted to lower frequencies as compared to those of the same ions in the neat sulfate compounds due to the smaller repulsion potential of the selenate matrices (larger unit-cell volumes of the selenates). It has been established that the extent of energetic distortion of the sulfate ions matrix-isolated in the ammonium selenates as deduced from the values of Δν₃ and Δν₃/νc is stronger than that of the same ions matrix-isolated in the potassium selenates due to the formation of hydrogen bonds between the SO₄²⁻ guest ions with both the water molecules in the host compounds and the NH₄⁺ host ions (for example, Δν₃ of the sulfate guest ions have values of 30 and 51 cm(-1) in the nickel potassium and ammonium compounds, and 33 and 49 cm(-1) in the zinc potassium and ammonium compounds, respectively). The infrared spectra of ammonium doped potassium sulfate matrices show three bands corresponding to Δν₄ of the included ammonium ions in agreement with the low site symmetry C₁ of the host potassium ions. However, the inclusion of ammonium ions in selenate matrices (with exception of the magnesium compound) leads to the appearance of four bands in the region of ν₄. At that stage of our knowledge we assume that some kind of disorder of the ammonium ions included in selenate lattices occurs due to the different proton acceptor capability of the SO₄²⁻ and SO₄²⁻ ions. The latter ions are known to exhibit stronger proton acceptor abilities. This fact will facilitate the formation of polyfurcate hydrogen bonds of the ammonium ions in the selenate matrices, thus leading to increasing in the coordination number of these ions, i.e. to a disorder of the ammonium guest ions. The strength of the hydrogen bonds formed in the title Tutton compounds as well as that of the hydrogen bonds in potassium compounds containing isomorphously included ammonium ions as deduced from the wavenumbers of the water librations are also discussed. The bands corresponding to water librations in the spectra of the mixed crystals K₁.₈(NH₄)₀.₂M(XO₄)₂⋅6H₂O (M=Mg, Co, Ni, Cu, Zn; X=S, Se) broaden and shift to lower frequencies as compared to those of the potassium host compounds, thus indicating that weaker hydrogen bonds are formed in the mixed crystals. These spectroscopic findings are owing to the decrease in the proton acceptor capacity of the SO₄²⁻ and SO₄²⁻ ions due to the formation of hydrogen bonds between the host anions and the guest ammonium cations additionally to water molecules (anti-cooperative or proton acceptor competitive effect). Furthermore, the band shifts in the spectra of the selenate matrices are generally larger than those observed in the spectra of the respective sulfates due to the stronger proton acceptor ability of the selenate ions. Copyright © 2014 Elsevier B.V. All rights reserved.

Infrared spectroscopic study of SO42- ions included in M‧2M‧‧(SeO4)2ṡ6H2O (Me‧ = K, NH4+; M‧‧ = Mg, Co, Ni, Cu, Zn) and NH4+ ions included in K2M(XO4)2ṡ6H2O (X = S, Se; M‧‧ = Mg, Co, Ni, Cu, Zn)

NASA Astrophysics Data System (ADS)

Marinova, D.; Karadjova, V.; Stoilova, D.

2015-01-01

Infrared spectra of Tutton compounds, M‧2M‧‧(XO4)2ṡ6H2O (M‧ = K, NH4+; M‧‧ = Mg, Co, Ni, Cu, Zn; X = S, Se), as well as those of SO42- guest ions included in selenate host lattices and of NH4+ guest ions included in potassium host lattices are presented and discussed in the regions of ν3 and ν1 of SO42- guest ions, ν4 of NH4+ guest ions and water librations. The SO42- guest ions matrix-isolated in selenate matrices (approximately 2 mol%) exhibit three bands corresponding to ν3 and one band corresponding to ν1 in good agreement with the low site symmetry C1 of the host selenate ions. When the larger SeO42- ions are replaced by the smaller SO42- ions the mean values of the asymmetric stretching modes νbar3 of the included SO42- ions are slightly shifted to lower frequencies as compared to those of the same ions in the neat sulfate compounds due to the smaller repulsion potential of the selenate matrices (larger unit-cell volumes of the selenates). It has been established that the extent of energetic distortion of the sulfate ions matrix-isolated in the ammonium selenates as deduced from the values of Δν3 and Δν3/νc is stronger than that of the same ions matrix-isolated in the potassium selenates due to the formation of hydrogen bonds between the SO42- guest ions with both the water molecules in the host compounds and the NH4+ host ions (for example, Δν3 of the sulfate guest ions have values of 30 and 51 cm-1 in the nickel potassium and ammonium compounds, and 33 and 49 cm-1 in the zinc potassium and ammonium compounds, respectively). The infrared spectra of ammonium doped potassium sulfate matrices show three bands corresponding to Δν4 of the included ammonium ions in agreement with the low site symmetry C1 of the host potassium ions. However, the inclusion of ammonium ions in selenate matrices (with exception of the magnesium compound) leads to the appearance of four bands in the region of ν4. At that stage of our knowledge we assume that some kind of disorder of the ammonium ions included in selenate lattices occurs due to the different proton acceptor capability of the SO42- and SeO42- ions. The latter ions are known to exhibit stronger proton acceptor abilities. This fact will facilitate the formation of polyfurcate hydrogen bonds of the ammonium ions in the selenate matrices, thus leading to increasing in the coordination number of these ions, i.e. to a disorder of the ammonium guest ions. The strength of the hydrogen bonds formed in the title Tutton compounds as well as that of the hydrogen bonds in potassium compounds containing isomorphously included ammonium ions as deduced from the wavenumbers of the water librations are also discussed. The bands corresponding to water librations in the spectra of the mixed crystals K1.8(NH4)0.2M(XO4)2ṡ6H2O (M = Mg, Co, Ni, Cu, Zn; X = S, Se) broaden and shift to lower frequencies as compared to those of the potassium host compounds, thus indicating that weaker hydrogen bonds are formed in the mixed crystals. These spectroscopic findings are owing to the decrease in the proton acceptor capacity of the SO42- and SeO42- ions due to the formation of hydrogen bonds between the host anions and the guest ammonium cations additionally to water molecules (anti-cooperative or proton acceptor competitive effect). Furthermore, the band shifts in the spectra of the selenate matrices are generally larger than those observed in the spectra of the respective sulfates due to the stronger proton acceptor ability of the selenate ions.

Fluorescence detecting of paraquat using host-guest chemistry with cucurbit[8]uril

PubMed Central

Sun, Shiguo; Li, Fusheng; Liu, Fengyu; Wang, Jitao; Peng, Xiaojun

2014-01-01

Paraquat (PQ) is one of the most widely used herbicides in the world, which has a good occupational safety record when used properly. While, it presents high mortality index after intentional exposure. Accidental deaths and suicides from PQ ingestion are relatively common in developing countries with an estimated 300,000 deaths occurring in the Asia–Pacific region alone each year, and there are no specific antidotes. Good predictors of outcome and prognosis may be plasma and urine testing within the first 24 h of intoxication. A fluorescence enhancement of approximately 30 times was seen following addition of PQ to a solution of the supramolecular compound 2MB@CB[8], which comprised two methylene blue (MB) molecules within one cucurbit[8]uril (CB[8]) host molecule. The fluorescence intensity was linearly proportional to the amount of PQ added over the concentration range 2.4 × 10−10 M–2.5 × 10−4 M. The reaction also occurred in living cells and within live mice. PMID:24389647

Fluorescence detecting of paraquat using host-guest chemistry with cucurbit[8]uril

NASA Astrophysics Data System (ADS)

Sun, Shiguo; Li, Fusheng; Liu, Fengyu; Wang, Jitao; Peng, Xiaojun

2014-01-01

Paraquat (PQ) is one of the most widely used herbicides in the world, which has a good occupational safety record when used properly. While, it presents high mortality index after intentional exposure. Accidental deaths and suicides from PQ ingestion are relatively common in developing countries with an estimated 300,000 deaths occurring in the Asia-Pacific region alone each year, and there are no specific antidotes. Good predictors of outcome and prognosis may be plasma and urine testing within the first 24 h of intoxication. A fluorescence enhancement of approximately 30 times was seen following addition of PQ to a solution of the supramolecular compound 2MB@CB[8], which comprised two methylene blue (MB) molecules within one cucurbit[8]uril (CB[8]) host molecule. The fluorescence intensity was linearly proportional to the amount of PQ added over the concentration range 2.4 × 10-10 M-2.5 × 10-4 M. The reaction also occurred in living cells and within live mice.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Chi; Arvapally, Ravi K.; Tekarli, Sammer M.

The trinuclear triangle-shaped system [tris{3,5-bis(heptafluoropropyl)-1,2,4-triazolatosilver(I)}] (1) and the multi-armed square-shaped metalloporphyrin PtOEP or the free porphyrin base H2OEP serve as excellent octopus hosts (OEP=2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine). Coupling of the fluorous/organic molecular octopi 1 and H2OEP or PtOEP by strong quadrupole-quadrupole and metal- interactions affords the supramolecular assemblies [1PtOEP] or [1H(2)OEP] (2a), which feature nanoscopic cavities surrounding the upper triangular and lower square cores. The fluorous/organic biphasic configuration of [1PtOEP] leads to an increase in the phosphorescence of PtOEP under ambient conditions. Guest molecules can be included in the biphasic double-octopus assembly in three different site-selective modes.

Solid-State Molecular Nanomagnet Inclusion into a Magnetic Metal-Organic Framework: Interplay of the Magnetic Properties.

PubMed

Mon, Marta; Pascual-Álvarez, Alejandro; Grancha, Thais; Cano, Joan; Ferrando-Soria, Jesús; Lloret, Francesc; Gascon, Jorge; Pasán, Jorge; Armentano, Donatella; Pardo, Emilio

2016-01-11

Single-ion magnets (SIMs) are the smallest possible magnetic devices and are a controllable, bottom-up approach to nanoscale magnetism with potential applications in quantum computing and high-density information storage. In this work, we take advantage of the promising, but yet insufficiently explored, solid-state chemistry of metal-organic frameworks (MOFs) to report the single-crystal to single-crystal inclusion of such molecular nanomagnets within the pores of a magnetic MOF. The resulting host-guest supramolecular aggregate is used as a playground in the first in-depth study on the interplay between the internal magnetic field created by the long-range magnetic ordering of the structured MOF and the slow magnetic relaxation of the SIM. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular interaction of methotrexate with cucurbit[7]uril and analytical application

NASA Astrophysics Data System (ADS)

Chang, Yin-Xia; Zhang, Xiang-Mei; Duan, Xue-Chao; Liu, Fan; Du, Li-Ming

2017-08-01

The supramolecular interaction between cucurbit[7]uril (CB[7]) as the host and the anti-cancer drug methotrexate (MTX) as the guest was studied using fluorescence spectroscopy, UV-visible absorption spectroscopy, 1H NMR, 2D NOESY, and theoretical calculations. The experimental results confirmed the formation of 1:2 inclusion complex with CB[7] and indicated a simple and sensitive competitive method for the fluorescence detection of MTX. It was found that the fluorescence intensities of CB[7]-palmatine, CB[7]-berberine and CB[7]-coptisine were quenched linearly upon the addition of MTX. The linear ranges obtained in the detection of MTX were 0.1-15 μg mL- 1, 0.2-15 μg mL- 1, and 0.4-15 μg mL- 1 with detection limits of 0.03 μg mL-1, 0.06 μg mL-1, and 0.13 μg mL-1, respectively. This method can be used for the determination of MTX in biological fluids. These results suggested that cucurbit[7]uril is a promising drug carrier for targeted MTX delivery and monitoring, with improved efficacy and reduced toxicity in normal tissues.

Highly efficient drug delivery nanosystem via L-phenylalanine triggering based on supramolecular polymer micelles.

PubMed

Dong, Haiqing; Li, Yongyong; Wen, Huiyun; Xu, Meng; Liu, Lijian; Li, Zhuoquan; Guo, Fangfang; Shi, Donglu

2011-03-16

An intelligent drug delivery nanosystem has been developed based on biodegradable supramolecular polymer micelles (SMPMs). The drug release can be triggered from SMPMs responsively by a bioactive agent, L-phenylalanine in a controlled fashion. The SMPMs are constructed from ethylcellulose-graft-poly(ε-caprolactone) (EC-g-PCL) and α-cyclodextrin (α-CD) derivate via host-guest and hydrophobic interactions. It has been found that these SMPMs have disassembled rapidly in response to an additional L-phenylalanine, due to great affinity discrepancy to α-CD between L-phenylalanine and PCL. Experiments have been carried out on trigger-controlled in vitro drug release of the SMPMs loaded with a model porphyrin based photosensitizer THPP. The result shows that the SMPMs released over 85% THPP in 6 h, which is two orders magnitudes faster than that of control. Also investigated is the photodynamic therapy (PDT) of THPP-loaded SMPMs with and without L-phenylalanine on MCF-7 carcinoma cell line. An effective trigger-concentration dependent lethal effect has been found showing promise in clinical photodynamic therapy. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Medicinal facilities to B16F10 melanoma cells for distant metastasis control with a supramolecular complex by DEAE-dextran-MMA copolymer/paclitaxel.

PubMed

Eshita, Yuki; Ji, Rui-Cheng; Onishi, Masayasu; Kobayashi, Takashi; Mizuno, Masaaki; Yoshida, Jun; Kubota, Naoji; Onishi, Yasuhiko

2015-02-01

The resistance of cancer cells to chemotherapeutic drugs (MDR) is a major problem to be solved. A supramolecular DEAE-dextran-MMA copolymer (DDMC)/paclitaxel (PTX) complex was obtained by using PTX as the guest and DDMC as the host having 50-300 nm in diameter. The drug resistance of B16F10 melanoma cells to paclitaxel was observed, but there is no drug resistance of melanoma cells to the DDMC/PTX complex in vitro. The cell death rate was determined using Michaelis-Menten kinetics, as the DDMC/PTX complex promoted allosteric supramolecular reaction to tubulin. The DDMC/PTX complex showed a very superior anti-cancer activity to paclitaxel alone in vivo. The median survival time (MST) of the saline, PTX, DDMC/PTX4 (particle size, 50 nm), and DDMC/PTX5 (particle size, 290 nm) groups were 120 h (T/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 the twofold effectiveness of PTX alone (p < 0.036). Histochemical analysis indicated that the administration of DDMC/PTX complex decreased distant metastasis and increased the survival of mice. A mouse of DDMC/PTX4 group in vivo was almost curing after small dermatorrhagia owing to its anti-angiogenesis, and it will be the hemorrhagic necrotic symptom of tumor by the release of "tumor necrosis factor alpha (TNF-α)" cytokine. As the result, the medicinal action of the DDMC/PTX complex will suppress the tumor-associated action of M2 macrophages and will control the metastasis of cancer cells.

Host-guest chemistry for tuning colloidal solubility, self-organization and photoconductivity of inorganic-capped nanocrystals

NASA Astrophysics Data System (ADS)

Bodnarchuk, Maryna I.; Yakunin, Sergii; Piveteau, Laura; Kovalenko, Maksym V.

2015-12-01

Colloidal inorganic nanocrystals (NCs), functionalized with inorganic capping ligands, such as metal chalcogenide complexes (MCCs), have recently emerged as versatile optoelectronic materials. As-prepared, highly charged MCC-capped NCs are dispersible only in highly polar solvents, and lack the ability to form long-range ordered NC superlattices. Here we report a simple and general methodology, based on host-guest coordination of MCC-capped NCs with macrocyclic ethers (crown ethers and cryptands), enabling the solubilization of inorganic-capped NCs in solvents of any polarity and improving the ability to form NC superlattices. The corona of organic molecules can also serve as a convenient knob for the fine adjustment of charge transport and photoconductivity in films of NCs. In particular, high-infrared-photon detectivities of up to 3.3 × 1011 Jones with a fast response (3 dB cut-off at 3 kHz) at the wavelength of 1,200 nm were obtained with films of PbS/K3AsS4/decyl-18-crown-6 NCs.

Characterization, phase solubility and molecular modeling of α-cyclodextrin/pyrimethamine inclusion complex

NASA Astrophysics Data System (ADS)

Araujo, Marcia Valeria Gaspar de; Macedo, Osmir F. L.; Nascimento, Cristiane da Cunha; Conegero, Leila Souza; Barreto, Ledjane Silva; Almeida, Luis Eduardo; Costa, Nivan Bezerra da; Gimenez, Iara F.

2009-02-01

An inclusion complex between the dihydrofolate reductase inhibitor pyrimethamine (PYR) and α-cyclodextrin (α-CD) was prepared and characterized. From the phase-solubility diagram, a linear increase of PYR solubility was verified as a function of α-CD concentration, suggesting the formation of a soluble complex. A 1:1 host-guest stoichiometry can be proposed according to the Job's plot, obtained from the difference of PYR fluorescence intensity in the presence and absence of α-CD. Differential scanning calorimetry (DSC) measurements provided additional evidences of complexation such as the absence of the endothermic peak assigned to the melting of the drug. The inclusion mode characterized by two-dimensional 1H NMR spectroscopy (ROESY) involves penetration of the p-chlorophenyl ring into the α-CD cavity, in agreement to the orientation optimized by molecular modeling methods.

Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework

PubMed Central

Lu, Zhenzhong; Godfrey, Harry G. W.; da Silva, Ivan; Cheng, Yongqiang; Savage, Mathew; Tuna, Floriana; McInnes, Eric J. L.; Teat, Simon J.; Gagnon, Kevin J.; Frogley, Mark D.; Manuel, Pascal; Rudić, Svemir; Ramirez-Cuesta, Anibal J.; Easun, Timothy L.; Yang, Sihai; Schröder, Martin

2017-01-01

Hydrogen bonds dominate many chemical and biological processes, and chemical modification enables control and modulation of host–guest systems. Here we report a targeted modification of hydrogen bonding and its effect on guest binding in redox-active materials. MFM-300(VIII) {[VIII2(OH)2(L)], LH4=biphenyl-3,3′,5,5′-tetracarboxylic acid} can be oxidized to isostructural MFM-300(VIV), [VIV2O2(L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(VIII) shows the second highest CO2 uptake capacity in metal-organic framework materials at 298 K and 1 bar (6.0 mmol g−1) and involves hydrogen bonding between the OH group of the host and the O-donor of CO2, which binds in an end-on manner, =1.863(1) Å. In contrast, CO2-loaded MFM-300(VIV) shows CO2 bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique ···c.g.phenyl interaction [3.069(2), 3.146(3) Å]. The macroscopic packing of CO2 in the pores is directly influenced by these primary binding sites. PMID:28194014

Perspectives of host faculty and trainees on international visiting faculty to paediatric academic departments in East Africa

PubMed Central

Russ, Christiana M; Ganapathi, Lakshmi; Marangu, Diana; Silverman, Melanie; Kija, Edward; Bakeera-Kitaka, Sabrina; Laving, Ahmed

2016-01-01

Background Investments in faculty exchanges to build physician workforce capacity are increasing. Little attention has been paid to the expectations of host institution faculty and trainees. This prospective qualitative research study explored faculty and resident perspectives about guest faculty in paediatric departments in East Africa, asking (1) What are the benefits and challenges of hosting guest faculty, (2) What factors influence the effectiveness of faculty visits and (3) How do host institutions prepare for faculty visits? Methods We recruited 36 faculty members and residents from among four paediatric departments in East Africa to participate in semistructured interviews which were audio recorded and transcribed. Data were qualitatively analysed using principles of open coding and thematic analysis. We achieved saturation of themes. Results Benefits of faculty visits varied based on the size and needs of host institutions. Emergent themes included the importance of guest faculty time commitment, and mutual preparation to ensure that visit goals and scheduling met host needs. We documented conflicts that developed around guest emotional responses and ethical approaches to clinical resource limitations, which some hosts tried to prepare for and mitigate. Imbalance in resources led to power differentials; some hosts sought partnerships to re-establish control over the process of having guests. Conclusions We identified that guest faculty can assist paediatric institutions in building capacity; however, effective visits require: (1) mutually agreed on goals with appropriate scheduling, visit length and commitment to ensure that the visits meet the host's needs, (2) careful selection and preparation of guest faculty to meet the host's goals, (3) emotional preparation by prospective guests along with host orientation to clinical work in the host's setting and (4) attention to funding sources for the visit and mitigation of resulting power differentials. PMID:28588960

Observation of interstitial molecular hydrogen in clathrate hydrates.

PubMed

Grim, R Gary; Barnes, Brian C; Lafond, Patrick G; Kockelmann, Winfred A; Keen, David A; Soper, Alan K; Hiratsuka, Masaki; Yasuoka, Kenji; Koh, Carolyn A; Sum, Amadeu K

2014-09-26

The current knowledge and description of guest molecules within clathrate hydrates only accounts for occupancy within regular polyhedral water cages. Experimental measurements and simulations, examining the tert-butylamine + H2 + H2O hydrate system, now suggest that H2 can also be incorporated within hydrate crystal structures by occupying interstitial sites, that is, locations other than the interior of regular polyhedral water cages. Specifically, H2 is found within the shared heptagonal faces of the large (4(3)5(9)6(2)7(3)) cage and in cavities formed from the disruption of smaller (4(4)5(4)) water cages. The ability of H2 to occupy these interstitial sites and fluctuate position in the crystal lattice demonstrates the dynamic behavior of H2 in solids and reveals new insight into guest-guest and guest-host interactions in clathrate hydrates, with potential implications in increasing overall energy storage properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemically armed mercenary ants protect fungus-farming societies.

PubMed

Adams, Rachelle M M; Liberti, Joanito; Illum, Anders A; Jones, Tappey H; Nash, David R; Boomsma, Jacobus J

2013-09-24

The ants are extraordinary in having evolved many lineages that exploit closely related ant societies as social parasites, but social parasitism by distantly related ants is rare. Here we document the interaction dynamics among a Sericomyrmex fungus-growing ant host, a permanently associated parasitic guest ant of the genus Megalomyrmex, and a raiding agro-predator of the genus Gnamptogenys. We show experimentally that the guest ants protect their host colonies against agro-predator raids using alkaloid venom that is much more potent than the biting defenses of the host ants. Relatively few guest ants are sufficient to kill raiders that invariably exterminate host nests without a cohabiting guest ant colony. We also show that the odor of guest ants discourages raider scouts from recruiting nestmates to host colonies. Our results imply that Sericomyrmex fungus-growers obtain a net benefit from their costly guest ants behaving as a functional soldier caste to meet lethal threats from agro-predator raiders. The fundamentally different life histories of the agro-predators and guest ants appear to facilitate their coexistence in a negative frequency-dependent manner. Because a guest ant colony is committed for life to a single host colony, the guests would harm their own interests by not defending the host that they continue to exploit. This conditional mutualism is analogous to chronic sickle cell anemia enhancing the resistance to malaria and to episodes in human history when mercenary city defenders offered either net benefits or imposed net costs, depending on the level of threat from invading armies.

Crystal structure of the co-crystal fac-tri-aqua-tris(thio-cyanato-κN)iron(III)-2,3-di-methyl-pyrazine (1/3).

PubMed

Kucheriv, Olesia I; Shylin, Sergii I; Ilina, Tetiana A; Dechert, Sebastian; Gural'skiy, Il'ya A

2015-04-01

In the crystal of the title compound, [Fe(NCS)3(H2O)3]·3C6H8N2, the Fe(III) cation is located on a threefold rotation axis and is coordinated by three N atoms of the thiocyanate anions and three water mol-ecules in a fac arrangement, forming a slightly distorted N3O3 octa-hedron. Stabilization within the crystal structure is provided by O-H⋯N hydrogen bonds; the H atoms from coordinating water mol-ecules act as donors to the N atoms of guest 2,3-di-methyl-pyrazine mol-ecules, leading to a three-dimensional supra-molecular framework.

Crystal engineering of a zwitterionic drug to neutral cocrystals: a general solution for floxacins.

PubMed

Gunnam, Anilkumar; Suresh, Kuthuru; Ganduri, Ramesh; Nangia, Ashwini

2016-10-18

The transformation of zwitterionic Sparfloxacin (SPX) to the neutral form is achieved by cocrystallization. Neutral forms of drugs are important for higher membrane permeability, while zwitterions are more soluble in water. The twin advantages of higher solubility/dissolution rate and good stability of neutral SPX are achieved in a molecular cocrystal compared to its zwitterionic SPX hydrate. The amine-phenol supramolecular synthon drives cocrystal formation, with the paraben ester acting as a "proton migrator" for the ionic to neutral transformation.

Topological analysis of void space in phosphate frameworks: Assessing storage properties for the environmentally important guest molecules and ions: CO 2, H 2O, UO 2, PuO 2, U, Pu, Sr 2+, Cs +, CH 4, and H 2

DOE PAGES

Cramer, Alisha J.; Cole, Jacqueline M.

2016-06-27

The entrapment of environmentally important materials to enable containment of polluting wastes from industry or energy production, storage of alternative fuels, or water sanitation, is of vital and immediate importance. Many of these materials are small molecules or ions that can be encapsulated via their adsorption into framework structures to create a host-guest complex. This is an ever-growing field of study and, as such, the search for more suitable porous materials for environmental applications is fundamental to progress. However, many industrial areas that require the use of adsorbents are fraught with practical challenges such as high temperatures, rapid gas expansion,more » radioactivity, or repetitive gas cycling, that the host material must withstand. Inorganic phosphates have a proven history of rigid structures, thermal stability, and are suspected to possess good resistance to radiation over geologic time scales. Furthermore, various experimental studies have established their ability to adsorb small molecules, such as water. In light of this, all known crystal structures of phosphate frameworks with meta- (P 3O 9) or ultra- (P 5O 14) stoichiometries are combined in a data-mining survey together with all theoretically possible structures of Ln aP bO c (where a, b, c are any integer, and Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, or Tm) that are statistically likely to form. Topological patterns within these framework structures are used to assess their suitability for hosting a variety of small guest molecules or ions that are important for environmental applications: CO 2, H 2O, UO 2, PuO 2, U, Pu, Sr 2+, Cs +, CH 4 and H 2. A range of viable phosphate-based host-guest complexes are identified from this data-mining and pattern-based structural analysis. Moreover, distinct topological preferences for hosting such guests are found, and metaphosphate stoichiometries are generally preferred over ultraphosphate configurations.« less

Supramolecular curcumin-barium prodrugs for formulating with ceramic particles.

PubMed

Kamalasanan, Kaladhar; Anupriya; Deepa, M K; Sharma, Chandra P

2014-10-01

A simple and stable curcumin-ceramic combined formulation was developed with an aim to improve curcumin stability and release profile in the presence of reactive ceramic particles for potential dental and orthopedic applications. For that, curcumin was complexed with barium (Ba(2+)) to prepare curcumin-barium (BaCur) complex. Upon removal of the unbound curcumin and Ba(2+) by dialysis, a water-soluble BaCur complex was obtained. The complex was showing [M+1](+) peak at 10,000-20,000 with multiple fractionation peaks of MALDI-TOF-MS studies, showed that the complex was a supramolecular multimer. The (1)H NMR and FTIR studies revealed that, divalent Ba(2+) interacted predominantly through di-phenolic groups of curcumin to form an end-to-end complex resulted in supramolecular multimer. The overall crystallinity of the BaCur was lower than curcumin as per XRD analysis. The complexation of Ba(2+) to curcumin did not degrade curcumin as per HPLC studies. The fluorescence spectrum was blue shifted upon Ba(2+) complexation with curcumin. Monodisperse nanoparticles with size less than 200dnm was formed, out of the supramolecular complex upon dialysis, as per DLS, and upon loading into pluronic micelles the size was remaining in similar order of magnitude as per DLS and AFM studies. Stability of the curcumin was improved greater than 50% after complexation with Ba(2+) as per UV/Vis spectroscopy. Loading of the supramloecular nanoparticles into pluronic micelles had further improved the stability of curcumin to approx. 70% in water. These BaCur supramolecule nanoparticles can be considered as a new class of prodrugs with improved solubility and stability. Subsequently, ceramic nanoparticles with varying chemical composition were prepared for changing the material surface reactivity in terms of the increase in, degradability, surface pH and protein adsorption. Further, these ceramic particles were combined with curcumin prodrug formulations and optimized the curcumin release properties in the combined formulations. Our proof concept study shows that, the conversion of curcumin to a metal-organic supramolecular prodrug improved the solubility, stability and release profile of curcumin. The prodrug approach with the micellisation strategy appears to be more appropriate to deliver intact curcumin in the presence of ceramic particles of varying surface reactivity. Copyright © 2014 Elsevier B.V. All rights reserved.

Computational phase diagrams of noble gas hydrates under pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Teeratchanan, Pattanasak, E-mail: s1270872@sms.ed.ac.uk; Hermann, Andreas, E-mail: a.hermann@ed.ac.uk

2015-10-21

We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-I{sub h}, ice-I{sub c}, ice-II, and C{sub 0} interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogenmore » hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C{sub 0} water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C{sub 0} hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.« less

Synthesis and characterization of protocatechuic acid-loaded gadolinium-layered double hydroxide and gold nanocomposite for theranostic application

NASA Astrophysics Data System (ADS)

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.

Reversible Self-Assembly of Water-Soluble Gold(I) Complexes.

PubMed

Aguiló, Elisabet; Moro, Artur J; Gavara, Raquel; Alfonso, Ignacio; Pérez, Yolanda; Zaccaria, Francesco; Guerra, Célia Fonseca; Malfois, Marc; Baucells, Clara; Ferrer, Montserrat; Lima, João Carlos; Rodríguez, Laura

2018-02-05

The reaction of the gold polymers containing bipyridyl and terpyridyl units, [Au(C≡CC 15 H 10 N 3 )] n and [Au(C≡CC 10 H 7 N 2 )] n , with the water-soluble phosphines 1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane gives rise to the formation of four gold(I) alkynyl complexes that self-assemble in water (H 2 O) and dimethyl sulfoxide (DMSO), through different intermolecular interactions, with an impact on the observed luminescence displayed by the supramolecular assemblies. A detailed analysis carried out by NMR studies performed in different DMSO/deuterated H 2 O mixtures indicates the presence of two different assembly modes in the aggregates: (i) chain assemblies, which are based mainly on aurophilic interactions, and (ii) stacked assemblies, which are based on Au···π and π···π interactions. These different supramolecular environments can also be detected by their intrinsic optical properties (differences in absorption and emission spectra) and are predicted by the changes in the relative binding energy from density functional theory calculations carried out in DMSO and H 2 O. Small-angle X-ray scattering (SAXS) experiments performed in the same mixture of solvents are in agreement with the formation of aggregates in all cases. The aromatic units chosen, bipyridine and terpyridine, allow the use of external stimuli to reversibly change the aggregation state of the supramolecular assemblies. Interaction with the Zn 2+ cation is observed to disassemble the aggregates, while encapsulating agents competing for Zn 2+ complexation revert the process to the aggregation stage, as verified by SAXS and NMR. The adaptive nature of the supramolecular assemblies to the metal-ion content is accompanied by significant changes in the absorption and emission spectra, signaling the aggregation state and also the content on Zn 2+ .

pH-Responsive Mesoporous Silica and Carbon Nanoparticles for Drug Delivery

PubMed Central

Gisbert-Garzarán, Miguel; Manzano, Miguel; Vallet-Regí, María

2017-01-01

The application of nanotechnology to medicine constitutes a major field of research nowadays. In particular, the use of mesoporous silica and carbon nanoparticles has attracted the attention of numerous researchers due to their unique properties, especially when applied to cancer treatment. Many strategies based on stimuli-responsive nanocarriers have been developed to control the drug release and avoid premature release. Here, we focus on the use of the subtle changes of pH between healthy and diseased areas along the body to trigger the release of the cargo. In this review, different approximations of pH-responsive systems are considered: those based on the use of the host-guest interactions between the nanocarriers and the drugs, those based on the hydrolysis of acid-labile bonds and those based on supramolecular structures acting as pore capping agents. PMID:28952481

Chemically armed mercenary ants protect fungus-farming societies

PubMed Central

Adams, Rachelle M. M.; Liberti, Joanito; Illum, Anders A.; Jones, Tappey H.; Nash, David R.; Boomsma, Jacobus J.

2013-01-01

The ants are extraordinary in having evolved many lineages that exploit closely related ant societies as social parasites, but social parasitism by distantly related ants is rare. Here we document the interaction dynamics among a Sericomyrmex fungus-growing ant host, a permanently associated parasitic guest ant of the genus Megalomyrmex, and a raiding agro-predator of the genus Gnamptogenys. We show experimentally that the guest ants protect their host colonies against agro-predator raids using alkaloid venom that is much more potent than the biting defenses of the host ants. Relatively few guest ants are sufficient to kill raiders that invariably exterminate host nests without a cohabiting guest ant colony. We also show that the odor of guest ants discourages raider scouts from recruiting nestmates to host colonies. Our results imply that Sericomyrmex fungus-growers obtain a net benefit from their costly guest ants behaving as a functional soldier caste to meet lethal threats from agro-predator raiders. The fundamentally different life histories of the agro-predators and guest ants appear to facilitate their coexistence in a negative frequency-dependent manner. Because a guest ant colony is committed for life to a single host colony, the guests would harm their own interests by not defending the host that they continue to exploit. This conditional mutualism is analogous to chronic sickle cell anemia enhancing the resistance to malaria and to episodes in human history when mercenary city defenders offered either net benefits or imposed net costs, depending on the level of threat from invading armies. PMID:24019482

Investigation of Cyclodextrin-Based Nanosponges for Solubility and Bioavailability Enhancement of Rilpivirine.

PubMed

Rao, Monica R P; Chaudhari, Jagruti; Trotta, Francesco; Caldera, Fabrizio

2018-06-04

Rilpivrine is BCS class II drug used for treatment of HIV infection. The drug has low aqueous solubility (0.0166 mg/ml) and dissolution rate leading to low bioavailability (32%). Aim of this work was to enhance solubility and dissolution of rilpivirine using beta-cyclodextrin-based nanosponges. These nanosponges are biocompatible nanoporous particles having high loading capacity to form supramolecular inclusion and non-inclusion complexes with hydrophilic and lipophilic drugs for solubility enhancement. Beta-cyclodextrin was crosslinked with carbonyl diimidazole and pyromellitic dianhydride to prepare nanosponges. The nanosponges were loaded with rilpivirine by solvent evaporation method. Binary and ternary complexes of drug with β-CD, HP-β-CD, nanosponges, and tocopherol polyethylene glycol succinate were prepared and characterized by phase solubility, saturation solubility in different media, in vitro dissolution, and in vivo pharmacokinetics. Spectral analysis by Fourier transform infrared spectroscopy, powder X-ray diffraction, and differential scanning calorimetry was performed. Results obtained from spectral characterization confirmed inclusion complexation. Phase solubility studies indicated stable complex formation. Saturation solubility was found to be 10-13-folds higher with ternary complexes in distilled water and 12-14-fold higher in 0.1 N HCl. Solubility enhancement was evident in biorelevant media. Molecular modeling studies revealed possible mode of entrapment of rilpivirine within β-CD cavities. A 3-fold increase in dissolution with ternary complexes was observed. Animal studies revealed nearly 2-fold increase in oral bioavailability of rilpivirine. It was inferred that electronic interactions, hydrogen bonding, and van der Waals forces are involved in the supramolecular interactions.

Stimuli-controlled self-assembly of diverse tubular aggregates from one single small monomer

NASA Astrophysics Data System (ADS)

Shi, Qixun; Javorskis, Tomas; Bergquist, Karl-Erik; Ulčinas, Artūras; Niaura, Gediminas; Matulaitienė, Ieva; Orentas, Edvinas; Wärnmark, Kenneth

2017-04-01

The design and synthesis of new stimuli-responsive hydrogen-bonding monomers that display a diversity of self-assembly pathways is of central importance in supramolecular chemistry. Here we describe the aggregation properties of a simple, intrinsically C2-symmetric enantiopure bicyclic cavity compound bearing a terminally unsubstituted ureidopyrimidinone fragment fused with a pyrrole moiety in different solvents and in the absence and presence of C60 and C70 guests. The tetrameric cyclic aggregate is selectively obtained in chlorinated solvents, where only part of the available hydrogen bonding sites are utilized, whereas in toluene or upon addition of C70 guests, further aggregation into tubular supramolecular polymers is achieved. The open-end cyclic assemblies rearrange into a closed-shell capsule upon introduction of C60 with an accompanied symmetry breaking of the monomer. Our study demonstrates that a C60 switch can be used to simultaneously control the topology and occupancy of tubular assemblies resulting from the aggregation of small monomers.

Self-Association Process of a Peptide in Solution: From β-Sheet Filaments to Large Embedded Nanotubes

PubMed Central

Valéry, C.; Artzner, F.; Robert, B.; Gulick, T.; Keller, G.; Grabielle-Madelmont, C.; Torres, M.-L.; Cherif-Cheikh, R.; Paternostre, M.

2004-01-01

Lanreotide is a synthetic octapeptide used in the therapy against acromegaly. When mixed with pure water at 10% (w/w), Lanreotide (acetate salt) forms liquid crystalline and monodisperse nanotubes with a radius of 120 Å. The molecular and supramolecular organization of these structures has been determined in a previous work as relying on the lateral association of 26 β-sheet filaments made of peptide noncovalent dimers, the basic building blocks. The work presented here has been devoted to the corresponding self-association mechanisms, through the characterization of the Lanreotide structures formed in water, as a function of peptide (acetate salt) concentration (from 2% to 70% (w/w)) and temperature (from 15°C to 70°C). The corresponding states of water were also identified and quantified from the thermal behavior of water in the Lanreotide mixtures. At room temperature and below 3% (w/w) Lanreotide acetate in water, soluble aggregates were detected. From 3% to 20% (w/w) long individual and monodisperse nanotubes crystallized in a hexagonal lattice were evidenced. Their molecular and supramolecular organizations are identical to the ones characterized for the 10% (w/w) sample. Heating induces the dissolution of the nanotubes into soluble aggregates of the same structural characteristics as the room temperature ones. The solubilization temperature increases from 20°C to 70°C with the peptide concentration and reaches a plateau between 15% and 25% (w/w) in peptide. These aggregates are proposed to be the β-sheet filaments that self-associate to build the walls of the nanotubes. Above 20% (w/w) of Lanreotide acetate in water, polydisperse embedded nanotubes are formed and the hexagonal lattice is lost. These embedded nanotubes exhibit the same molecular and supramolecular organizations as the individual monodisperse nanotubes formed at lower peptide concentration. The embedded nanotubes do not melt in the range of temperature studied indicating a higher thermodynamic stability than individual nanotubes. In parallel, the thermal behaviors of water in mixtures containing 2–80% (w/w) in peptide have been studied by differential scanning calorimetry, and three different types of water were characterized: 1), bulk water melting at 0°C, 2), nonfreezing water, and 3), interfacial water melting below 0°C. The domains of existence and coexistence of these different water states are related to the different Lanreotide supramolecular structures. All these results were compiled into a binary Lanreotide-water phase diagram and allowed to propose a self-association mechanism of Lanreotide filaments into monodisperse individual nanotubes and embedded nanotubes. PMID:15041685

Aniline-containing guests recognized by α,α',δ,δ'-tetramethyl-cucurbit[6]uril host.

PubMed

Lin, Rui-Lian; Fang, Guo-Sheng; Sun, Wen-Qi; Liu, Jing-Xin

2016-12-13

The host-guest complexation of symmetrical α,α',δ,δ'-tetramethyl-cucurbit[6]uril (TMeQ[6]) and cucurbit[7]uril (Q[7]) with a series of aniline-containing guests has been investigated by various experimental techniques including NMR, ITC, and X-ray crystallography. Experimental results indicate that both TMeQ[6] and Q[7] hosts can encapsulate aniline-containing guests to form stable inclusion complexes. However, the oval cavity of TMeQ[6] is more complementary in size and shape to the aromatic ring of the guests than the spherical cavity of Q[7]. Shielding and deshielding effects of the aromatic ring on guests lead to the remarkable chemical shifts of the TMeQ[6] host protons. The rotational restriction of the guests in the oval cavity of TMeQ[6] results in the large negative values of entropy. The X-ray crystal structure of the 1:1 inclusion complex between TMeQ[6] and N,N'-diethyl-benzene-1,4-diamine unambiguously reveals that the aromatic ring of the guest resides in the oval cavity of TMeQ[6].

NMR Investigation of Chloromethane Complexes of Cryptophane-A and Its Analogue with Butoxy Groups

PubMed Central

2014-01-01

Host–guest complexes between cryptophane-A as host and dichloromethane and chloroform as guests are investigated using 1H and 13C NMR spectroscopy. Moreover, a related cryptophane, with the methoxy groups replaced by butoxy units (cryptophane-But), and its complexes with the same guests were also studied. Variable temperature spectra showed effects of chemical exchange between the free and bound guests, as well as of conformational exchange of the host. The guest exchange was studied quantitatively by exchange spectroscopy or line shape analysis. Extraction of kinetic and thermodynamic parameters led to the characterization of the affinity between guests and hosts. On the other hand, the host exchange was investigated by means of 13C Carr–Purcell–Meiboom–Gill (CPMG) relaxation dispersion which aims at the determination of the transverse relaxation rate R2, the inverse of the transverse relaxation time T2, as a function of the repetition of the π pulses in a CPMG train. The variation of the measured transverse relaxation rate with the repetition rate νCPMG indicated conformational exchange occurring on the microsecond–millisecond time scale. Structural information was obtained through measurements of cross-relaxation rates, both within the host and between the host and the guest protons. The NMR results were supported by DFT calculations. PMID:24472055

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

PubMed

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.

Conjugated Porphyrin Dimers: Cooperative Effects and Electronic Communication in Supramolecular Ensembles with C60.

PubMed

Moreira, Luis; Calbo, Joaquín; Aragó, Juan; Illescas, Beatriz M; Nierengarten, Iwona; Delavaux-Nicot, Béatrice; Ortí, Enrique; Martín, Nazario; Nierengarten, Jean-François

2016-11-30

Two new conjugated porphyrin-based systems (dimers 3 and 4) endowed with suitable crown ethers have been synthesized as receptors for a fullerene-ammonium salt derivative (1). Association constants in solution have been determined by UV-vis titration experiments in CH 2 Cl 2 at room temperature. The designed hosts are able to associate up to two fullerene-based guest molecules and present association constants as high as ∼5 × 10 8 M -1 . Calculation of the allosteric cooperative factor α for supramolecular complexes [3·1 2 ] and [4·1 2 ] showed a negative cooperative effect in both cases. The interactions accounting for the formation of the associates are based, first, on the complementary ammonium-crown ether interaction and, second, on the π-π interactions between the porphyrin rings and the C 60 moieties. Theoretical calculations have evidenced a significant decrease of the electron density in the porphyrin dimers 3 and 4 upon complexation of the first C 60 molecule, in good agreement with the negative cooperativity found in these systems. This negative effect is partially compensated by the stabilizing C 60 -C 60 interactions that take place in the more stable syn-disposition of [4·1 2 ].

Host-guest chemistry for tuning colloidal solubility, self-organization and photoconductivity of inorganic-capped nanocrystals.

PubMed

Bodnarchuk, Maryna I; Yakunin, Sergii; Piveteau, Laura; Kovalenko, Maksym V

2015-12-09

Colloidal inorganic nanocrystals (NCs), functionalized with inorganic capping ligands, such as metal chalcogenide complexes (MCCs), have recently emerged as versatile optoelectronic materials. As-prepared, highly charged MCC-capped NCs are dispersible only in highly polar solvents, and lack the ability to form long-range ordered NC superlattices. Here we report a simple and general methodology, based on host-guest coordination of MCC-capped NCs with macrocyclic ethers (crown ethers and cryptands), enabling the solubilization of inorganic-capped NCs in solvents of any polarity and improving the ability to form NC superlattices. The corona of organic molecules can also serve as a convenient knob for the fine adjustment of charge transport and photoconductivity in films of NCs. In particular, high-infrared-photon detectivities of up to 3.3 × 10(11) Jones with a fast response (3 dB cut-off at 3 kHz) at the wavelength of 1,200 nm were obtained with films of PbS/K3AsS4/decyl-18-crown-6 NCs.

Coordination-Driven Syntheses of Compact Supramolecular Metallacycles toward Extended Metallo-organic Stacked Supramolecular Assemblies.

PubMed

Lescop, Christophe

2017-04-18

One important concept associated with supramolecular chemistry is supramolecular self-assembly, which deals with the way discrete individual components interact via intermolecular interactions in order to build, upon their spontaneous association, high order functional assemblies. The accumulation of these very simple and localized noncovalent interactions (such as H-bonding, dipole-dipole, hydrophobic/hydrophilic, van der Waals, π-π, π-CH, etc.) is ubiquitous in the complexity of natural systems (such as DNA, proteins, membranes, micelles, etc.). It can also be transposed to the directed synthesis of intricate artificial scaffolds, which have anticipated geometries and properties. Among the synthetic strategies based on this concept, coordination-driven supramolecular chemistry uses the robust, reversible, and directional metal-to-ligand coordinative bond to build discrete metallo-supramolecular architectures. Within the last two decades, coordination-driven supramolecular chemistry has proved to be one of the most powerful contemporary synthetic approaches and has provided a significant number of increasingly complex supramolecular assemblies, which have predetermined sizes and geometries. While much focus has been devoted to architectures bearing internal cavities for host-guest chemistry or to generate specific reactivity, particular attention can also be paid to compact supramolecular assemblies given that their specific structures are characterized by peculiar synthetic guiding rules as well as by alternative long-range self-assembling properties. This Account describes how a preassembled Cu I bimetallic clip bearing short intermetallic distances can be used as a U-shaped molecular clip to give general and versatile access to a large variety of original compact supramolecular metallacycles. When this Cu I precursor is reacted with various cyano-capped ditopic linkers that have increasing lengths and complexities, specific effects guiding the selective and straightforward syntheses of such compact supramolecular objects are highlighted. Whereas a subtle compromise between the length of the ditopic linkers and the steric bulk of the molecular clip appears to be a purely stereogeometric preliminary parameter to master, lateral interlinker interactions (π-π stacking interactions or aurophilic interactions depending on the nature of the internal cores of the linkers) can circumvent these constraints regardless of the length of the linkers and allow the selective formation of new compact supramolecular structures. Generally, such derivatives presented a strong tendency to self-assemble in the solid state due to inter-supramolecule interactions. This approach thus opens a new door toward molecular materials having an attractive solid state structure for potential applications related to charge carrier mobility and luminescence properties. These compact supramolecular assemblies can therefore be considered as original secondary binding units directing the predictive preparation of such extended networks. The on-purpose design of original building blocks bearing specific cores allowed the formation of new compact supramolecular metallacycles such as "U-shaped" π-stacked assemblies or "pseudodouble paracyclophanes". Similarly, the control of the secondary structure of one-dimensional coordination polymers alternating π-stacked compact supramolecular metallacycles was also conducted. The results that are discussed in this Account illustrate how the rational design of both preassembled polymetallic precursors bearing short intermetallic distances and ditopic linkers able to induce cumulative lateral weak interactions can implement the general synthetic guiding rules of coordination driven supramolecular chemistry. This opens perspectives to use such compact supramolecular assemblies as secondary building blocks for the design of long-range organized functional molecular materials that have predictable architectures and targeted properties.

Encapsulation of biocides by cyclodextrins: toward synergistic effects against pathogens

PubMed Central

Nardello-Rataj, Véronique

2014-01-01

Summary Host–guest chemistry is useful for the construction of nanosized objects. Some of the widely used hosts are probably the cyclodextrins (CDs). CDs can form water-soluble complexes with numerous hydrophobic compounds. They have been widespread used in medicine, drug delivery and are of interest for the biocides encapsulation. Indeed, this enables the development of more or less complex systems that release antimicrobial agents with time. In this paper, the general features of CDs and their applications in the field of biocides have been reviewed. As the key point is the formation of biocide–CD inclusion complexes, this review deals with this in depth and the advantages of biocide encapsulation are highlighted throughout several examples from the literature. Finally, some future directions of investigation have been proposed. We hope that scientists studying biocide applications receive inspiration from this review to exploit the opportunities offered by CDs in their respective research areas. PMID:25550722

Interactions between cyclodextrins and cellular components: Towards greener medical applications?

PubMed Central

2016-01-01

In the field of host–guest chemistry, some of the most widely used hosts are probably cyclodextrins (CDs). As CDs are able to increase the water solubility of numerous drugs by inclusion into their hydrophobic cavity, they have been widespread used to develop numerous pharmaceutical formulations. Nevertheless, CDs are also able to interact with endogenous substances that originate from an organism, tissue or cell. These interactions can be useful for a vast array of topics including cholesterol manipulation, treatment of Alzheimer’s disease, control of pathogens, etc. In addition, the use of natural CDs offers the great advantage of avoiding or reducing the use of common petroleum-sourced drugs. In this paper, the general features and applications of CDs have been reviewed as well as their interactions with isolated biomolecules leading to the formation of inclusion or exclusion complexes. Finally, some potential medical applications are highlighted throughout several examples. PMID:28144335

Effect of guest drug character encapsulated in the cavity and intermolecular spaces of γ-cyclodextrins on the dissolution property of ternary γ-cyclodextrin complex.

PubMed

Liu, Nan; Higashi, Kenjirou; Ueda, Keisuke; Moribe, Kunikazu

2017-10-15

Various ternary Guest 2/(Guest 1/γ-cyclodextrin (CD)) complexes were prepared using a cogrinding and subsequent heating method, wherein Guest 1 was incorporated in the cavity of γ-CD and Guest 2 was incorporated into the intermolecular spaces between γ-CD columns. Dissolution fluxes of Guest 1 and Guest 2 from all ternary complexes were almost identical. The dissolution flux of flurbiprofen (Guest 1) from the ternary complexes depended on the solubility of Guest 2 drugs (naproxen

Binding of carboxylate and trimethylammonium salts to octa-acid and TEMOA deep-cavity cavitands

NASA Astrophysics Data System (ADS)

Sullivan, Matthew R.; Sokkalingam, Punidha; Nguyen, Thong; Donahue, James P.; Gibb, Bruce C.

2017-01-01

In participation of the fifth statistical assessment of modeling of proteins and ligands (SAMPL5), the strength of association of six guests ( 3- 8) to two hosts ( 1 and 2) were measured by 1H NMR and ITC. Each host possessed a unique and well-defined binding pocket, whilst the wide array of amphiphilic guests possessed binding moieties that included: a terminal alkyne, nitro-arene, alkyl halide and cyano-arene groups. Solubilizing head groups for the guests included both positively charged trimethylammonium and negatively charged carboxylate functionality. Measured association constants ( K a ) covered five orders of magnitude, ranging from 56 M-1 for guest 6 binding with host 2 up to 7.43 × 106 M-1 for guest 6 binding to host 1.

Calculating binding free energies of host-guest systems using the AMOEBA polarizable force field.

PubMed

Bell, David R; Qi, Rui; Jing, Zhifeng; Xiang, Jin Yu; Mejias, Christopher; Schnieders, Michael J; Ponder, Jay W; Ren, Pengyu

2016-11-09

Molecular recognition is of paramount interest in many applications. Here we investigate a series of host-guest systems previously used in the SAMPL4 blind challenge by using molecular simulations and the AMOEBA polarizable force field. The free energy results computed by Bennett's acceptance ratio (BAR) method using the AMOEBA polarizable force field ranked favorably among the entries submitted to the SAMPL4 host-guest competition [Muddana, et al., J. Comput.-Aided Mol. Des., 2014, 28, 305-317]. In this work we conduct an in-depth analysis of the AMOEBA force field host-guest binding thermodynamics by using both BAR and the orthogonal space random walk (OSRW) methods. The binding entropy-enthalpy contributions are analyzed for each host-guest system. For systems of inordinate binding entropy-enthalpy values, we further examine the hydrogen bonding patterns and configurational entropy contribution. The binding mechanism of this series of host-guest systems varies from ligand to ligand, driven by enthalpy and/or entropy changes. Convergence of BAR and OSRW binding free energy methods is discussed. Ultimately, this work illustrates the value of molecular modelling and advanced force fields for the exploration and interpretation of binding thermodynamics.

In situ Low-temperature Pair Distribution Function (PDF) Analysis of CH4 and CO2 Hydrates

NASA Astrophysics Data System (ADS)

Cladek, B.; Everett, M.; McDonnell, M.; Tucker, M.; Keffer, D.; Rawn, C.

2017-12-01

Gas hydrates occur in ocean floor and sub-surface permafrost deposits and are stable at moderate to high pressures and low temperatures. They are a clathrate structure composed of hydrogen bonded water cages that accommodate a wide variety of guest molecules. CO2 and CH4 hydrates both crystallize as the cubic sI hydrate and can form a solid solution. Natural gas hydrates are interesting as a potential methane source and for CO2 sequestration. Long-range diffraction studies on gas hydrates give valuable structural information but do not provide a detailed understanding of the disordered gas molecule interactions with the host lattice. In-situ low temperature total scattering experiments combined with pair distribution function (PDF) analysis are used to investigate the gas molecule motions and guest-cage interactions. CO2 and methane hydrates exhibit different decomposition behavior, and CO2 hydrate has a smaller lattice parameter despite it being a relatively larger molecule. Total scattering studies characterizing both the short- and long-range order simultaneously help to elucidate the structural source of these phenomena. Low temperature neutron total scattering data were collected using the Nanoscale Ordered MAterials Diffractometer (NOMAD) beamline at the Spallation Neutron Source (SNS) on CO2 and CH4 hydrates synthesized with D2O. Guest molecule motion within cages and interactions between gases and cages are investigated through the hydrate stability and decomposition regions. Data were collected from 2-80 K at a pressure of 55 mbar on CO2 and CH4 hydrates, and from 80-270 K at 25 bar on CH4 hydrate. The hydrate systems were modeled with classical molecular dynamic (MD) simulations to provide an analysis of the total energy into guest-guest, guest-host and host-host contributions. Combined Reitveld and Reverse Monte Carlo (RMC) structure refinement were used to fit models of the data. This combined modeling and simulation characterizes the effects of CO2 and CH4 as guest molecules on the structure and decomposition of gas hydrates. Structure and thermodynamic studies will provide a more comprehensive understanding of CO2-CH4 solid solutions, exchange kinetics, and implications on hydrate structure.

Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework

DOE PAGES

Lu, Zhenzhong; Godfrey, Harry G. W.; da Silva, Ivan; ...

2017-02-13

Hydrogen bonds dominate many chemical and biological processes, and chemical modification enables control and modulation of host–guest systems. Here in this paper we report a targeted modification of hydrogen bonding and its effect on guest binding in redox-active materials. MFM-300(V III) {[V III 2(OH) 2(L)], LH 4=biphenyl-3,3',5,5'-tetracarboxylic acid} can be oxidized to isostructural MFM-300(V IV), [V IV 2O 2(L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(V III) shows the second highest CO 2 uptake capacity in metal-organic framework materials at 298 K and 1 bar (6.0 mmol g -1) and involves hydrogen bonding between the OH group of the host and the O-donor of CO 2, which binds in an end-on manner, OH∙∙∙ =1.863(1) Å. In contrast, CO 2-loaded MFM-300(V IV) shows CO 2 bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique O COmore » $$_2$$···c.g.phenyl interaction [3.069(2), 3.146(3) Å]. Lastly, the macroscopic packing of CO 2 in the pores is directly influenced by these primary binding sites.« less

Cellular interactions of a water-soluble supramolecular polymer complex of carbon nanotubes with human epithelial colorectal adenocarcinoma cells.

PubMed

Lee, Yeonju; Geckeler, Kurt E

2012-08-01

Water-soluble, PAX-loaded carbon nanotubes are fabricated by employing a synthetic polyampholyte, PDM. To investigate the suitability of the polyampholyte and the nanotubes as drug carriers, different cellular interactions such as the human epithelial Caco-2 cells viability, their effect on the cell growth, and the change in the transepithelial electrical resistance in Caco-2 cells are studied. The resulting complex is found to exhibit an effective anti-cancer effect against colon cancer cells and an increased the reduction of the electrical resistance in the Caco-2 cells when compared to the precursor PAX. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct patterning of a cyclotriveratrylene derivative for directed self-assembly of C60

NASA Astrophysics Data System (ADS)

Osner, Zachary R.; Nyamjav, Dorjderem; Holz, Richard C.; Becker, Daniel P.

2011-07-01

A novel apex-modified cyclotriveratrylene (CTV) derivative with an attached thiolane-containing lipoic acid linker was directly patterned onto gold substrates via dip-pen nanolithography (DPN). The addition of a dithiolane-containing linker to the apex of CTV provides a molecule that can adhere to a gold surface with its bowl-shaped cavity directed away from the surface, thereby providing a surface-bound CTV host that can be used for the directed assembly of guest molecules. Subsequent exposure of these CTV microarrays to C60 in toluene resulted in the directed assembly of predesigned, spatially controlled, high-density microarrays of C60. The molecular recognition capabilities of this CTV template toward C60 provides proof-of-concept that supramolecular CTV scaffolds can be directly patterned onto surfaces providing a foundation for the development of organic electronic and optoelectronic materials.

Selective C70 encapsulation by a robust octameric nanospheroid held together by 48 cooperative hydrogen bonds

PubMed Central

Markiewicz, Grzegorz; Jenczak, Anna; Kołodziejski, Michał; Holstein, Julian J.; Stefankiewicz, Artur R

2017-01-01

Self-assembly of multiple building blocks via hydrogen bonds into well-defined nanoconstructs with selective binding function remains one of the foremost challenges in supramolecular chemistry. Here, we report the discovery of a enantiopure nanocapsule that is formed through the self-assembly of eight amino acid functionalised molecules in nonpolar solvents through 48 hydrogen bonds. The nanocapsule is remarkably robust, being stable at low and high temperatures, and in the presence of base, presumably due to the co-operative geometry of the hydrogen bonding motif. Thanks to small pore sizes, large internal cavity and sufficient dynamicity, the nanocapsule is able to recognize and encapsulate large aromatic guests such as fullerenes C60 and C70. The structural and electronic complementary between the host and C70 leads to its preferential and selective binding from a mixture of C60 and C70. PMID:28488697

Bio-inspired reversible underwater adhesive.

PubMed

Zhao, Yanhua; Wu, Yang; Wang, Liang; Zhang, Manman; Chen, Xuan; Liu, Minjie; Fan, Jun; Liu, Junqiu; Zhou, Feng; Wang, Zuankai

2017-12-20

The design of smart surfaces with switchable adhesive properties in a wet environment has remained a challenge in adhesion science and materials engineering. Despite intense demands in various industrial applications and exciting progress in mimicking the remarkable wet adhesion through the delicate control of catechol chemistry, polyelectrolyte complex, and supramolecular architectures, the full recapitulation of nature's dynamic function is limited. Here, we show a facile approach to synthesize bioinspired adhesive, which entails the reversible, tunable, and fast regulation of the wet adhesion on diverse surfaces. The smart wet adhesive takes advantage of the host-guest molecular interaction and the adhesive nature of catechol chemistry, as well as the responsive polymer, allowing for screening and activation of the interfacial interaction simply by a local temperature trigger in an on-demand manner. Our work opens up an avenue for the rational design of bioinspired adhesives with performances even beyond nature.

Designing non-native iron-binding site on a protein cage for biological synthesis of nanoparticles.

PubMed

Peng, Tao; Paramelle, David; Sana, Barindra; Lee, Chiu Fan; Lim, Sierin

2014-08-13

In biomineralization processes, a supramolecular organic structure is often used as a template for inorganic nanomaterial synthesis. The E2 protein cage derived from Geobacillus stearothermophilus pyruvate dehydrogenase and formed by the self-assembly of 60 subunits, has been functionalized with non-native iron-mineralization capability by incorporating two types of iron-binding peptides. The non-native peptides introduced at the interior surface do not affect the self-assembly of E2 protein subunits. In contrast to the wild-type, the engineered E2 protein cages can serve as size- and shape-constrained reactors for the synthesis of iron nanoparticles. Electrostatic interactions between anionic amino acids and cationic iron molecules drive the formation of iron oxide nanoparticles within the engineered E2 protein cages. The work expands the investigations on nanomaterial biosynthesis using engineered host-guest encapsulation properties of protein cages. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Construction and DNA condensation of cyclodextrin-coated gold nanoparticles with anthryl grafts.

PubMed

Zhao, Di; Chen, Yong; Liu, Yu

2014-07-01

The condensation of DNA in a controlled manner is one of the key steps in gene delivery and gene therapy. For this purpose, a water-soluble supramolecular nanostructure is constructed by coating 14 β-cyclodextrins onto the surface of a gold nanoparticle, followed by the noncovalent association of different amounts of anthryl-modified adamantanes with coated β-cyclodextrins. The strong binding of β-cyclodextrins with anthryl adamantanes (K(S) =8.61×10(4)  M(-1)) efficiently stabilizes the supramolecular nanostructure. Spectrophotometric fluorescence spectra and microscopic studies demonstrated that, with many anthryl grafts that can intercalate in the outer space of the DNA double helix, this supramolecular nanostructure showed good condensation abilities to calf thymus DNA. Significantly, the condensation efficiency of supramolecular nanostructure towards DNA could be conveniently controlled by adjusting the ratio between gold nanoparticles and anthryl adamantane grafts, leading to the formation of DNA condensates of a size that are suitable for the endocytosis of hepatoma cells, which will make it potentially applicable in many fields of medicinal science and biotechnology. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ferrocene Derivatives Included in a Water-Soluble Cavitand: Are They Electroinactive?

PubMed Central

Podkoscielny, Dagmara; Hooley, Richard J.; Rebek, Julius; Kaifer, Angel E.

2009-01-01

The formation in aqueous solution of kinetically stable inclusion complexes between a deep-cavity cavitand and several redox active ferrocene derivatives was demonstrated using 1H NMR spectroscopy. The electrochemical kinetics of the inclusion complexes was strongly attenuated as compared to that observed with the free guests. PMID:18537255

A structural model of polyglutamine determined from a host-guest method combining experiments and landscape theory.

PubMed

Finke, John M; Cheung, Margaret S; Onuchic, José N

2004-09-01

Modeling the structure of natively disordered peptides has proved difficult due to the lack of structural information on these peptides. In this work, we use a novel application of the host-guest method, combining folding theory with experiments, to model the structure of natively disordered polyglutamine peptides. Initially, a minimalist molecular model (C(alpha)C(beta)) of CI2 is developed with a structurally based potential and captures many of the folding properties of CI2 determined from experiments. Next, polyglutamine "guest" inserts of increasing length are introduced into the CI2 "host" model and the polyglutamine is modeled to match the resultant change in CI2 thermodynamic stability between simulations and experiments. The polyglutamine model that best mimics the experimental changes in CI2 thermodynamic stability has 1), a beta-strand dihedral preference and 2), an attractive energy between polyglutamine atoms 0.75-times the attractive energy between the CI2 host Go-contacts. When free-energy differences in the CI2 host-guest system are correctly modeled at varying lengths of polyglutamine guest inserts, the kinetic folding rates and structural perturbation of these CI2 insert mutants are also correctly captured in simulations without any additional parameter adjustment. In agreement with experiments, the residues showing structural perturbation are located in the immediate vicinity of the loop insert. The simulated polyglutamine loop insert predominantly adopts extended random coil conformations, a structural model consistent with low resolution experimental methods. The agreement between simulation and experimental CI2 folding rates, CI2 structural perturbation, and polyglutamine insert structure show that this host-guest method can select a physically realistic model for inserted polyglutamine. If other amyloid peptides can be inserted into stable protein hosts and the stabilities of these host-guest mutants determined, this novel host-guest method may prove useful to determine structural preferences of these intractable but biologically relevant protein fragments.

Catching TFSI: A Computational-Experimental Approach to β-Cyclodextrin-Based Host-Guest Systems as electrolytes for Li-Ion Batteries.

PubMed

Jeschke, Steffen; Jankowski, Piotr; Best, Adam S; Johansson, Patrik

2018-03-12

Cyclodextrins (CDs) are pyranoside-based macromolecules with a hydrophobic cavity to encapsulate small molecules. They are used as molecular vehicles, for instance in pharmaceutical drug delivery or as solubility enhancer of monomers for their polymerization in aqueous solution. In this context, it was discovered about 10 years ago that the bis(trifluoromethylsulonyl)imide (TFSI) anion forms host-guest complexes with βCD in aqueous media. This sparked interest in using the TFSI anion in lithium-based battery electrolytes open for its encapsulation by βCD as an attractive approach to increase the contribution of the cation to the total ion conductivity. By using semi-empirical quantum mechanical (SQM) methods and the conductor-like screening model for a real solvent (COSMO-RS), a randomly methylated βCD (RMβCD) is here identified as a suitable host for TFSI when using organic solvents often used in battery technology. By combining molecular dynamics (MD) simulations with different NMR and FTIR experiments, the formation of the corresponding RMβCD-TFSI complex was investigated. Finally, the effects of the addition RMβCD to a set of electrolytes on the ion conductivity are measured and explained using three distinct scenarios. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spontaneous Self-Assembly of Polymeric Nanoparticles in Aqueous Media: New Insights From Microfluidics, In Situ Size Measurements, and Individual Particle Tracking.

PubMed

Li, Xue; Salzano, Giuseppina; Zhang, Jiwen; Gref, Ruxandra

2017-01-01

Supramolecular cyclodextrin-based nanoparticles (CD-NPs) mediated by host-guest interactions have gained increased popularity because of their "green" and simple preparation procedure, as well as their versatility in terms of inclusion of active molecules. Herein, we showed that original CD-NPs of around 100 nm are spontaneously formed in water, by mixing 2 aqueous solutions of (1) a CD polymer and (2) dextran grafted with benzophenone moieties. For the first time, CD-NPs were instantaneously produced in a microfluidic interaction chamber by mixing 2 aqueous solutions of neutral polymers, in the absence of organic solvents. Whatever the mixing conditions, CD-NPs with narrow size distributions were immediately formed upon contact of the 2 polymeric solutions. In situ size measurements showed that the CD-NPs were spontaneously formed. Nanoparticle tracking analysis was used to individually follow the CD-NPs in their Brownian motions, to gain insights on their size distribution, concentration, and stability on extreme dilution. Nanoparticle tracking analysis allowed to establish that despite their non-covalent nature, and the CD-NPs were remarkably stable in terms of concentration and size distribution, even on extreme dilution (concentrations as low as 100 ng/mL). Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Analytical techniques for characterization of cyclodextrin complexes in aqueous solution: a review.

PubMed

Mura, Paola

2014-12-01

Cyclodextrins are cyclic oligosaccharides endowed with a hydrophilic outer surface and a hydrophobic inner cavity, able to form inclusion complexes with a wide variety of guest molecules, positively affecting their physicochemical properties. In particular, in the pharmaceutical field, cyclodextrin complexation is mainly used to increase the aqueous solubility and dissolution rate of poorly soluble drugs, and to enhance their bioavailability and stability. Analytical characterization of host-guest interactions is of fundamental importance for fully exploiting the potential benefits of complexation, helping in selection of the most appropriate cyclodextrin. The assessment of the actual formation of a drug-cyclodextrin inclusion complex and its full characterization is not a simple task and often requires the use of different analytical methods, whose results have to be combined and examined together. The purpose of the present review is to give, as much as possible, a general overview of the main analytical tools which can be employed for the characterization of drug-cyclodextrin inclusion complexes in solution, with emphasis on their respective potential merits, disadvantages and limits. Further, the applicability of each examined technique is illustrated and discussed by specific examples from literature. Copyright © 2014 Elsevier B.V. All rights reserved.

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

ERIC Educational Resources Information Center

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…

Tunable Two-color Luminescence and Host-guest Energy Transfer of Fluorescent Chromophores Encapsulated in Metal-Organic Frameworks

NASA Astrophysics Data System (ADS)

Yan, Dongpeng; Tang, Yanqun; Lin, Heyang; Wang, Dan

2014-03-01

Co-assembly of chromophore guests with host matrices can afford materials which have photofunctionalities different from those of individual components. Compared with clay and zeolite materials, the use of metal-organic frameworks (MOFs) as a host structure for fabricating luminescent host-guest materials is still at an early stage. Herein, we report the incorporation of a laser dye, 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), into stilbene-based and naphthalene-based MOF systems. The resulting materials exhibit blue/red two-color emission, and the intensity ratio of blue to red fluorescence varies in different planes within the MOF crystal as detected by 3D confocal fluorescence microscopy. The observed changes in ratiometric fluorescence suggest the occurrence of energy transfer from MOF host to DCM molecules, which can be further confirmed by periodic density functional theoretical (DFT) calculations. Moreover, selective changes in luminescence behavior are observed on treating the guest@MOF samples with volatile organic compounds (methanol, acetone and toluene), indicating that these host-guest systems have potential applications as fluorescence sensors. It can be expected that by rational selection of MOF hosts and guest chromophores with suitable emissive colors and energy levels, a wide variety of multi-color luminescent and energy-transfer systems can readily be prepared in a similar manner.

Preparation, characterization, and thermal stability of β-cyclodextrin/soybean lecithin inclusion complex.

PubMed

Wang, Xinge; Luo, Zhigang; Xiao, Zhigang

2014-01-30

β-Cyclodextrin (β-CD), which is widely used to increase the stability, solubility, and bioavailability of guests, can form host-guest inclusion complexes with a wide variety of organic molecules. In this study the β-CD/soybean lecithin inclusion complex was prepared. The effect of reaction parameters such as reaction temperature, reaction time and the molar ratio of β-CD/soybean lecithin on inclusion ratio were studied. The inclusion ratio of the product prepared under the optimal conditions of β-CD/soybean lecithin molar ratio 2:1, reaction temperature 60°C reaction time 2h was 40.2%. The results of UV-vis, DSC, XRD and FT-IR spectrum indicated the formation of inclusion complex. The thermal stability experiment indicated that the thermal stability of soybean lecithin in inclusion complex was significantly improved compared with free soybean lecithin. Copyright © 2013 Elsevier Ltd. All rights reserved.

Self-Assembled Polysaccharide Nanotubes Generated from β-1,3-Glucan Polysaccharides

NASA Astrophysics Data System (ADS)

Numata, Munenori; Shinkai, Seiji

β-1,3-Glucans act as unique natural nanotubes, the features of which are greatly different from other natural or synthetic helical polymers. The origin mostly stems from their strong helix-forming nature and reversible interconversion between single-strand random coil and triple-strand helix. During this interconversion process, they can accept functional polymers, molecular assemblies and nanoparticles in an induced-fit manner to create water-soluble one-dimensional nanocomposites, where individual conjugated polymers or molecular assemblies can be incorporated into the one-dimensional hollow constructed by the helical superstructure of β-1,3-glucans. The advantageous point of the β-1,3-glucan hosting system is that the selective modification of β-1,3-glucans leads to the creation of various functional one-dimensional nanocomposites in a supramolecular manner, being applicable toward fundamental nanomaterials such as sensors or circuits. Furthermore, the composites with functional surfaces can act as one-dimensional building blocks toward further hierarchical self-assemblies, leading to the creation of two- or three-dimensional nanoarchitectures.

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

PubMed

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.

A pH-responsive carboxylic β-1,3-glucan polysaccharide for complexation with polymeric guests.

PubMed

Lien, Le Thi Ngoc; Shiraki, Tomohiro; Dawn, Arnab; Tsuchiya, Youichi; Tokunaga, Daisuke; Tamaru, Shun-ichi; Enomoto, Naoya; Hojo, Junichi; Shinkai, Seiji

2011-06-07

The helix-forming nature of β-1,3-glucan polysaccharides is a characteristic that has potential for producing gene carriers, bio-nanomaterials and other chiral nanowires. Herein, carboxylic curdlan (CurCOOH) bearing the β-1,3-polyglucuronic acid structure was successfully prepared from β-1,3-glucan polysaccharide curdlan (Cur) by one-step oxidation using a 4-acetamido-TEMPO/NaClO/NaClO(2) system as the oxidant. The resulting high-molecular-weight CurCOOH was proved to bear the 6-COOH group in 100% purity. The optical rotatory dispersion (ORD) spectra indicated that the obtained CurCOOH behaves as a water-soluble single-strand in various pH aqueous media. This advantage has allowed us to use CurCOOH as a polymeric host to form various macromolecular complexes. For example, complexation of CurCOOH with single-walled carbon nanotubes (SWNTs) resulted in a water-soluble one-dimensional architecture, which formed a dispersion in aqueous solution that was stable for several months, and much more stable than SWNTs complexes of the similar negatively-charged polyacrylic acid (PAA) and polymethacrylic acid (PMAA). It was shown that in the complex, SWNTs are effectively wrapped by a small amount of CurCOOH, enabling them to avoid electrostatic repulsion. This pH-responsive CurCOOH formed a very stable complex with cationic water-soluble polythiophenes (PT-1), which was stabilized not only by the hydrophobic interaction but also by the electrostatic attraction between trimethylammonium cations in PT-1 and dissociated anionic COO(-) groups in CurCOOH. The included PT-1 became CD-active only in the neutral to basic pH region, and the positive Cotton effect suggested that the conjugated main chain is twisted in the right-handed direction. We also found that CurCOOH can interact with polycytidylic acid (poly(C)) only under high NaCl concentrations, the binding and release of which could be controlled by a change in the salt concentration. We believe, therefore, that CurCOOH bearing a dissociable COOH group can act as a new potential polymeric host to construct novel polymeric complexes applicable for gene carriers, biosensors, chiral polymer assemblies, etc.

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

NASA Astrophysics Data System (ADS)

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.

What the ultimate polymeric electro-optic materials will be: guest-host, crosslinked, or side-chain?

NASA Astrophysics Data System (ADS)

Zhang, Cheng; Zhang, Hua; Oh, Min-Cheol; Dalton, Larry R.; Steier, William H.

2003-07-01

Material processing and device fabrication of many different electro-optic (EO) polymers developed at USC are reviewed. Detailed discussion is given to guest-host CLD/APCs, crosslinking perfluorocyclobutane (PFCB) polymer CX1, and thermally stable side-chain polymers CX2 and CX3. Excellent EO performance (1.4V at 1.31 μm, 2.1 V at 1.55 μm) was achieved in CLD/APC Mach-Zehnder modulators (2-cm, push-pull). CLD/APCs also possess low optical losses (1.2 dB/cm in slab waveguides and in thick core channel waveguides). However, the guest-host materials only have limited thermal stability (110-132 °C in short term, <60 °C in long term) and require special techniques in device fabrication. The crosslinking polymer CX1 was able to provide long-term stability at 85 oC when fully cured. It also has a low optical loss (comparable to CLD/APCs) before curing and decent EO coefficient when poled at 180 °C. However, after the films were poled at the crosslinking temperatures (200 °C or above), the transmissions of the waveguides and EO activity became very poor due to poling-induced chromophore degradation. By judicial molecular design of both chromophore and monomer structures to suppress thermal motion of polymer segments, we were able to realize the same or even better thermal stability in side-chain polymers CX2 and CX3. Since no curing is needed, devices can be poled at their optimal poling temperatures, and all good properties can be obtained simultaneously. Despite the excellent solubility in chlorinated solvents, these side-chain polymers are resistant to some other organic solvents or solutions such as acetone, photoresist and various UV-curable liquids.

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

PubMed

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.

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

PubMed

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.

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

PubMed

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.

Polymer-free nanofibers from vanillin/cyclodextrin inclusion complexes: high thermal stability, enhanced solubility and antioxidant property.

PubMed

Celebioglu, Asli; Kayaci-Senirmak, Fatma; İpek, Semran; Durgun, Engin; Uyar, Tamer

2016-07-13

Vanillin/cyclodextrin inclusion complex nanofibers (vanillin/CD-IC NFs) were successfully obtained from three modified CD types (HPβCD, HPγCD and MβCD) in three different solvent systems (water, DMF and DMAc) via an electrospinning technique without using a carrier polymeric matrix. Vanillin/CD-IC NFs with uniform and bead-free fiber morphology were successfully produced and their free-standing nanofibrous webs were obtained. The polymer-free CD/vanillin-IC-NFs allow us to accomplish a much higher vanillin loading (∼12%, w/w) when compared to electrospun polymeric nanofibers containing CD/vanillin-IC (∼5%, w/w). Vanillin has a volatile nature yet, after electrospinning, a significant amount of vanillin was preserved due to complex formation depending on the CD types. Maximum preservation of vanillin was observed for vanillin/MβCD-IC NFs which is up to ∼85% w/w, besides, a considerable amount of vanillin (∼75% w/w) was also preserved for vanillin/HPβCD-IC NFs and vanillin/HPγCD-IC NFs. Phase solubility studies suggested a 1 : 1 molar complexation tendency between guest vanillin and host CD molecules. Molecular modelling studies and experimental findings revealed that vanillin : CD complexation was strongest for MβCD when compared to HPβCD and HPγCD in vanillin/CD-IC NFs. For vanillin/CD-IC NFs, water solubility and the antioxidant property of vanillin was improved significantly owing to inclusion complexation. In brief, polymer-free vanillin/CD-IC NFs are capable of incorporating a much higher loading of vanillin and effectively preserve volatile vanillin. Hence, encapsulation of volatile active agents such as flavor, fragrance and essential oils in electrospun polymer-free CD-IC NFs may have potential for food related applications by integrating the particularly large surface area of NFs with the non-toxic nature of CD and inclusion complexation benefits, such as high temperature stability, improved water solubility and an enhanced antioxidant property, etc.

The molecular transport and intercalation of guest molecules into hydrogen-bonded metal-organic frameworks (HMOFs)

NASA Astrophysics Data System (ADS)

Hogan, Greg Anthony

The process of molecular transport and intercalation has been widely studied for many years, resulting in the discovery of molecular frameworks that are capable of hosting guest molecules or ions. Layered and porous metal-organic frameworks (MOFs) have been found to have applications in the field of catalysis, storage, separations, and ion-exchange. More recently, molecular components with peripheral hydrogen-bonding moieties have been used to affect the synthesis of hydrogen-bonded metal-organic frameworks (HMOFs) as an alternative to MOFs, which are interconnected via coordinate-covalent bonds. While MOFs are perhaps stronger materials, HMOFs have the advantage of being easily modifiable and more flexible. Because HMOFs have not been extensively studied for their ability to host molecules, and because their ability to withstand guest loss and guest exchange is essentially unknown, here we report the synthesis and molecular transport properties of both close-packed and porous HMOFs. Layered materials can mimic the behavior of naturally occurring clays, where guest molecules are absorbed and the layer will expand to accommodate the entering guest molecule. We have created a clay mimic composed of a metal pyridine-dicarboxylates and ammonium counterions (a layered HMOF), which is suitable for studying the ability of such materials to absorb guest molecules. We can control the distance of the interlayer region, as well as the chemical nature (hydrophobic or hydrophilic) by varying the organic amine. The metal complex contains axial water ligands that are replaceable, and such ligand exchange has precedence in coordination polymer (MOF) systems, and has been termed "coordinative intercalation". Using the synthesized layered material we examined the process of intercalation, having chosen a variety of guest molecules ranging from alkyl to aryl molecules, each of which have substituents varying in size, shape and electronics. The first set of guest molecules are non-coordinating and are theoretically capable of entering the layer and anchoring freely through the use of non-covalent interactions. The second set of guest molecules contain a pyridine moiety that can exchange with the coordinated water ligand through coordinative-intercalation. The products have been characterized by TGA, DSC, UV-Vis, and powder XRD. Further work was dedicated to examining porous materials, which were created using organic diamines, rather than simple primary amines, as starting materials. The resulting diammonium cations act as pillars, forming open channels. The predefined channel dimensions allow the insertion of specific sized guest molecules. The walls of the channel are close-packed, so that in theory guest molecules can travel in one direction through the solid. Using the synthesized pillared structure we investigated guest inclusion and selectivity through the process of co-crystallization. The stability of the pillared structure in the absence of guests is also reported, as well as the potential for the empty pillared structure to withstand guest re-insertion and removal.

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

PubMed

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sreedhar, Sreeja, E-mail: sreejasreedhar83@gmail.com; Muneera, C. I., E-mail: drcimuneera@hotmail.com; Illyaskutty, Navas

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 themore » 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.« less

2D-1D structural phase transformation of Co(II) 3,5-pyridinedicarboxylate frameworks with chromotropism.

PubMed

Cheansirisomboon, Achareeya; Pakawatchai, Chaveng; Youngme, Sujittra

2012-09-21

Two new metal-organic frameworks [Co(pydc)(H(2)O)(2)](n) (1) and [Co(pydc)(H(2)O)(4)](n)(H(2)O)(n) (2), (pydc = 3,5-pyridinedicarboxylate) have been synthesized by a diffusion method and characterized by single-crystal X-ray diffraction. The structure of 1 reveals an infinite 2D layer with honeycomb-like cavities in which each pydc ligand bridges three Co(II) ions. The adjacent 2D layers are orderly packed in an ABAB-type array via intermolecular interactions of the combined π-π stacking and hydrogen bonds to form a 3D supramolecular architecture. Interestingly, compound 1 exhibits a water induced crystal-to-amorphous transformation with chromotropism confirmed by spectroscopic techniques, elemental analysis, TGA and XRPD. When this amorphous phase (1A) was exposed to water vapor, it was readily converted into the second crystalline phase 1B with a color change. Moreover, a reversible process between 1A and 1B was performed. In the case of compound 2, pydc acts as didentate bridging ligand connecting two Co(II) ions, leading to a 1D zig-zag chain. Guest water molecules fill the gaps in between chains and form hydrogen bonds with the host chains stabilizing the 3D network of 2. Additionally, compound 2 also exhibits a water induced crystal-to-amorphous transformation with chromotropism and the reversible process was also performed between the dehydrated (2A) and rehydrated (2') forms. Surprisingly, the IR and UV-vis spectra, elemental analysis, TGA curve and XRPD pattern of the rehydrated second phase 1B are found to be identical to that of 2 and 2', these results confirm that 2, 2' and 1B are the same compound.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang Hui; Zou Kang; Guo Shaohuan

A nanostructural drug-inorganic clay composite involving a pharmaceutically active compound captopril (Cpl) intercalated Mg-Al-layered double hydroxides (Cpl-LDHs) with Mg/Al molar ratio of 2.06 has been assembled by coprecipitation method. Powder X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR) and Raman spectra analysis indicate a successful intercalation of Cpl between the layers with a vertical orientation of Cpl disulphide-containing S-S linkage. SEM photo indicates that as-synthesized Cpl-LDHs possess compact and non-porous structure with approximately and linked elliptical shape particles of ca. 50 nm. TG-DTA analyses suggest that the thermal stability of intercalated organic species is largely enhanced due to host-guest interactionmore » involving the hydrogen bond compared to pure form before intercalation. The in vitro release studies show that both the release rate and release percentages markedly decrease with increasing pH from 4.60 to 7.45 due to possible change of release mechanism during the release process. The kinetic simulation for the release data, and XRD and FT-IR analyses for samples recovered from release media indicate that the dissolution mechanism is mainly responsible for the release behaviour of Cpl-LDHs at pH 4.60, while the ion-exchange one is responsible for that at pH 7.45. - Graphical abstract: Based on XRD, FT-IR and Raman spectra analyses, it is suggested that captopril (Cpl) exists as its disulphide metabolites in the interlayer of Mg-Al-LDHs via hydrogen bonding between guest carboxylate function and hydroxyl group of the host layers. A schematic supramolecular structure of Cpl intercalates involving a vertical orientation of Cpl disulphide-containing S-S bond between the layers with carboxylate anions pointing to both hydroxide layers is presented.« less

Complexation of polyoxometalates with cyclodextrins.

PubMed

Wu, Yilei; Shi, Rufei; Wu, Yi-Lin; Holcroft, James M; Liu, Zhichang; Frasconi, Marco; Wasielewski, Michael R; Li, Hui; Stoddart, J Fraser

2015-04-01

Although complexation of hydrophilic guests inside the cavities of hydrophobic hosts is considered to be unlikely, we demonstrate herein the complexation between γ- and β-cyclodextrins (γ- and β-CDs) with an archetypal polyoxometalate (POM)--namely, the [PMo12O40](3-) trianion--which has led to the formation of two organic-inorganic hybrid 2:1 complexes, namely [La(H2O)9]{[PMo12O40]⊂[γ-CD]2} (CD-POM-1) and [La(H2O)9] {[PMo12O40]⊂[β-CD]2} (CD-POM-2), in the solid state. The extent to which these complexes assemble in solution has been investigated by (i) (1)H, (13)C, and (31)P NMR spectroscopies and (ii) small- and wide-angle X-ray scattering, as well as (iii) mass spectrometry. Single-crystal X-ray diffraction reveals that both complexes have a sandwich-like structure, wherein one [PMo12O40](3-) trianion is encapsulated by the primary faces of two CD tori through intermolecular [C-H···O═Mo] interactions. X-ray crystal superstructures of CD-POM-1 and CD-POM-2 show also that both of these 2:1 complexes are lined up longitudinally in a one-dimensional columnar fashion by means of [O-H···O] interactions. A beneficial nanoconfinement-induced stabilizing effect is supported by the observation of slow color changes for these supermolecules in aqueous solution phase. Electrochemical studies show that the redox properties of [PMo12O40](3-) trianions encapsulated by CDs in the complexes are largely preserved in solution. The supramolecular complementarity between the CDs and the [PMo12O40](3-) trianion provides yet another opportunity for the functionalization of POMs under mild conditions by using host-guest chemistry.

Mechanised nanoparticles for drug delivery

NASA Astrophysics Data System (ADS)

Cotí, Karla K.; Belowich, Matthew E.; Liong, Monty; Ambrogio, Michael W.; Lau, Yuen A.; Khatib, Hussam A.; Zink, Jeffrey I.; Khashab, Niveen M.; Stoddart, J. Fraser

2009-09-01

Time and time again humanity is faced with a unifying global crisis that crosses the many great divides in different societies and serves to bring once segregated communities back together as a collective whole. This global community instinctively turns to science to develop the means of addressing its most pressing problems. More often than not, these forces dictate the direction that scientific research takes. This influence is no more apparent than in the field of supramolecular chemistry where, for decades now, its responsibility to tackle such issues has been put on the back burner as a consequence of a lack of platforms with which to deliver this contemporary brand of chemistry to meaningful applications. However, the tide is slowly turning as new materials emerge from the field of nanotechnology that are poised to host the many attractive attributes that are inherent in the chemistry of these supermolecules and also in the mechanostereochemistry of mechanically interlocked molecules (MIMs), which can be reused as a sequel to supramolecular chemistry. Mesoporous silica nanoparticles (SNPs) have proven to be supremely effective solid supports as their surfaces are easily functionalised with either supermolecules or MIMs. In turn, the blending of supramolecular chemistry and mechanostereochemistry with mesoporous SNPs has led to a new class of materials - namely, mechanised SNPs that are effectively biological nanoscale `bombs' that have the potential to infiltrate cells and then, upon the pulling of a chemical trigger, explode! The development of these materials has been driven by the need to devise new therapies for the treatment of cancer. Recent progress in research promises not only to control the acuteness of this widespread and insidious disease, but also to make the harsh treatment less debilitating to patients. This global scourge is the unifying force that has brought together supramolecular chemistry, mechanostereochemistry and nanotechnology, uniting these three communities for the common good. At the nanoscale level, the mechanism for the release of cargos from the confines of the nanopores in the SNPs is accomplished by way of mechanical modifications made on the surface of these functionalised supports. These mechanical motions rely on both supramolecular, i.e., host-guest complexes, and mechanostereochemical phenomena (e.g., bistable rotaxanes), which are often stimulated by changes in pH, light and redox potentials, in addition to enzymatic catalysis. The future of this field lies in the development of `smart bombs' wherein the loaded mechanised SNPs are endocytosed selectively by cancer cells, whereupon an intracellular trigger causes release of a cytotoxin, effectively leading to apoptosis. This review serves to highlight (1) the evolution of surface-functionalisation of SNPs with supermolecules and also with MIMs, (2) the mechanisms through which controlled-release of cargo from mechanised SNPs occurs, and (3) results from the in vitro application of these mechanised SNPs.

Electronegative Guests in CoSb 3

DOE PAGES

Duan, Bo; Yang, Jiong; Salvador, James R.; ...

2016-04-19

Introducing guests into a host framework to form a so called inclusion compound can be used to design materials with new and fascinating functionalities. The vast majority of inclusion compounds have electropositive guests with neutral or negatively charged frameworks. Here, we show a series of electronegative guest filled skutterudites with inverse polarity. The strong covalent guest-host interactions observed for the electronegative group VIA guests, i.e., S and Se, feature a unique localized cluster vibration which significantly influences the lattice dynamics, together with the point-defect scattering caused by element substitutions, resulting in very low lattice thermal conductivity values. The findings ofmore » electronegative guests provide a new perspective for guest-filling in skutterudites, and the covalent filler/lattice interactions lead to an unusual lattice dynamics phenomenon which can be used for designing high-efficiency thermoelectric materials and novel functional inclusion compounds with open structures.« less

A spectroscopic study of the structure and occupancies of clathrate hydrates incorporating hydrogen

NASA Astrophysics Data System (ADS)

Grim, R. Gary

With the ability to store and concentrate gases inside a clean and abundant water framework, clathrate hydrates are considered to be a promising material for many applications related to gas storage, separation, and sequestration. Hydrates of hydrogen are particularly interesting, for in addition to these potential applications, the small molecular size provides an opportunity for use as a model guest in many fundamental studies such as guest diffusion, multiple guest occupancy, and quantum mechanical effects upon confinement. In attempt to study these effects and the viability of H 2 hydrates as an energy storage material, a combined experimental and theoretical approach incorporating Raman spectroscopy, X-ray and neutron diffraction, nuclear magnetic resonance, ab-initio calculations, and molecular dynamic simulations was performed. One of the most significant challenges in the application of H2 clathrate hydrates is the demanding thermodynamic requirements needed for stability. In recent years, a mechanism known as the `tuning' effect had reportedly solved this issue where thermodynamic requirements could be reduced while simultaneously maintaining high storage capacities. In this work, the viability and validity of this technique is explored and alternative explanations in the form of epitaxial hydrate growth under high driving force conditions are discussed. A second, and equally important challenge facing clathrate hydrates as a future storage material is the overall storage capacity of H2. In previous work, H2 has only been experimentally verified to occupy the small 512 and 43566 3 cages and also in the large 51264 cages of the type II clathrate, often with an energy deficient promoter. In order to achieve more robust energy densities, other hydrate cages must be accessible. Herein a new method for increasing overall hydrate energy densities is presented involving the incorporation of H2 in the large cages of the type I clathrate with CH4 as a co-guest molecule. Finally, for all of the collective research on gas hydrates since their discovery in 1810 by Sir Humphrey Davy, the one common theme that unites them is the assumption that guest molecules are trapped at the center (or near center) of the host water cages that makes up the respective crystal structure. For the first time, this work provides evidence suggesting that this definition of clathrate hydrate guest occupancy is possibly incomplete, and should include the addition of interstitial sites within the water crystal lattice. Specifically, H2 is found within the shared heptagonal faces of the large (4 3596273) cage and in cavities formed from the disruption of smaller (445 4) water cages in structure VI hydrates. The ability of H2 to occupy these interstitial sites and fluctuate position in the crystal lattice demonstrates the dynamic behavior of H2 in solids and reveals new insight into guest-guest and guest-host interactions in clathrate hydrates with potential implications in increasing overall energy storage properties.

The Design of Molecular Hosts, Guests, and Their Complexes.

ERIC Educational Resources Information Center

Cram, Donald J.

1988-01-01

Describes the origins, definitions, tools, and principles of host-guest chemistry. Gives examples of chiral recognition in complexation, of partial transacylase mimics, of caviplexes, and of a synthetic molecular cell. (Author/RT)

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

NASA Astrophysics Data System (ADS)

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.

Self-assembled Nanofibrils for Immunomodulation

NASA Astrophysics Data System (ADS)

Zhao, Fan

This thesis has been mainly focused on applying self-assembled nanofibrils as unique depots for controlled release to modulate immune system, with two major chapters on modulation of innate immunity in chapter 2 and adaptive immunity in chapter 3, respectively. There are 5 chapters in the thesis. Chapter 1 gives a detailed review on the discovery, synthesis and application of self-assembled nanofibrils of therapeutic agents (termed as "self-delivery drugs"), including bioactive molecules; Chapter 2 demonstrates the supramolecular hydrogel of chemotactic peptides as a prolonged inflammation model through proper molecular engineering; Chapter 3 reports a suppressive antibody response achieved by encapsulation of antigens by supramolecular hydrogel of glycopeptide; Chapter 4 illustrates an example of supramolecular hydrogel formation of molecules with extremely low solubility, based on the fact that many small organic drugs have poor solubility. Chapter 5 used beta-galatosidase as a model to study glycosidase-instructed supramolecular hydrogel formation, with potential to target cancer cells due to their distinct metabolic profile.

Use of cyclodextrins as a cosmetic delivery system for fragrance materials: linalool and benzyl acetate.

PubMed

Numanoğlu, Ulya; Sen, Tangül; Tarimci, Nilüfer; Kartal, Murat; Koo, Otilia M Y; Onyüksel, Hayat

2007-10-19

The aim of this study was to increase the stability and water solubility of fragrance materials, to provide controlled release of these compounds, and to convert these substances from liquid to powder form by preparing their inclusion complexes with cyclodextrins (CDs). For this purpose, linalool and benzyl acetate were chosen as the fragrance materials. The use of beta-cyclodextrin (beta CD) and 2-hydroxypropyl-beta-cyclodextrin (2-HP beta CD) for increasing the solubility of these 2 fragrance materials was studied. Linalool and benzyl acetate gave a B-type diagram with beta CD, whereas they gave an A(L)-type diagram with 2-HP beta CD. Therefore, complexes of fragrance materials with 2-HP beta CD at 1:1 and 1:2 molar ratios (guest:host) were prepared. The formation of inclusion complexes was confirmed using proton nuclear magnetic resonance ((1)H-NMR) spectroscopy and circular dichroism spectroscopy. The results of the solubility studies showed that preparing the inclusion complex with 2-HP beta CD at a 1:1 molar ratio increased the solubility of linalool 5.9-fold and that of benzyl acetate 4.2-fold, whereas the complexes at a 1:2 molar ratio increased the solubility 6.4- and 4.5-fold for linalool and benzyl acetate, respectively. The stability and in vitro release studies were performed on the gel formulations prepared using uncomplexed fragrance materials or inclusion complexes of fragrance materials at a 1:1 molar ratio. It was observed that the volatility of both fragrance materials was decreased by preparing the inclusion complexes with 2-HP beta CD. Also, in vitro release data indicated that controlled release of fragrances could be possible if inclusion complexes were prepared.

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

PubMed

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.

DNA-based nonlinear photonic materials

NASA Astrophysics Data System (ADS)

Heckman, Emily M.; Grote, James G.; Yaney, Perry P.; Hopkins, F. K.

2004-10-01

Deoxyribonucleic acid (DNA), extracted from salmon sperm through an enzyme isolation process, is a by-product of Japan"s fishing industry. To make DNA a suitable material for nonlinear optic (NLO) applications, it is precipitated with a surfactant complex, hexadecyltrimethlammonium chloride (CTMA). Preliminary characterization studies suggest DNA-CTMA may be a suitable host material for guest-host NLO polymer based electro-optic (EO) waveguide devices. The optical and electromagnetic properties of DNA-CTMA, as well as the development and EO measurement of a disperse red 1 (DR1) guest / DNA/CTMA host NLO material, are reported. Comparisons to a DR1 guest / poly(methyl methacrylate) (PMMA) host NLO material are made.

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

PubMed

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.

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

PubMed Central

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

2017-01-01

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. PMID:28246642

Probing the inner space of resorcinarene molecular capsules with nitroxide guests.

PubMed

Mileo, Elisabetta; Yi, Song; Bhattacharya, Papri; Kaifer, Angel E

2009-01-01

In quarantine: Nitroxide spin probes are encapsulated by hexameric resorcinarene molecular capsules in dichloromethane solutions (see picture). A substantial reduction in the tumbling rates occurs upon encapsulation of two cationic probes and one neutral probe. As the molecular volume of the probe increases, the tumbling rate of the probe reflects the overall tumbling rate of the entire supramolecular assembly.

Effects of multiple pathways on excited-state energy flow in self-assembled wheel-and-spoke light-harvesting architectures.

PubMed

Song, Hee-eun; Kirmaier, Christine; Schwartz, Jennifer K; Hindin, Eve; Yu, Lianhe; Bocian, David F; Lindsey, Jonathan S; Holten, Dewey

2006-10-05

Static and time-resolved optical measurements are reported for three cyclic hexameric porphyrin arrays and their self-assembled complexes with guest chromophores. The hexameric hosts contain zinc porphyrins and 0, 1, or 2 free base (Fb) porphyrins (denoted Zn(6), Zn(5)Fb, or Zn(4)Fb(2), respectively). The guest is a core-modified (O replacing one of the four N atoms) dipyridyl-substituted Fb porphyrin (DPFbO) that coordinates to zinc porphyrins of a host via pyridyl-zinc dative bonding. Each architecture is designed to have a gradient of excited-state energies for excitation funneling among the weakly coupled constituents of the host to the guest. Energy transfer to the lowest-energy chromophore(s) (coordinated zinc porphyrins or Fb porphyrins) within a hexameric host occurs primarily via a through-bond (TB) mechanism, is rapid ( approximately 40 ps), and is essentially quantitative (>or=98%). Energy transfer from a pyridyl-coordinated zinc porphyrin of the host to the guest in the Zn(6)*DPFbO complex has a yield of approximately 75%, a rate constant of approximately (0.7 ns)(-1), and significant Förster through-space (TS) character. In the case of Zn(5)Fb*DPFbO, which has an additional TS route via the Fb porphyrin with a rate constant of approximately (20 ns)(-1), the yield of energy transfer to the guest is somewhat lower ( approximately 50%) than that for Zn(6)*DPFbO. Complex Zn(4)Fb(2)*DPFbO has an identical TS pathway via the Fb porphyrin plus an additional TS pathway involving the second Fb porphyrin (closer to the guest) with a rate constant of approximately (0.5 ns)(-1). This complex exhibits an energy-transfer yield to the guest that is significantly enhanced over that for Zn(5)Fb*DPFbO and comparable to that for Zn(6)*DPFbO. Collectively, the results for the various arrays suggest designs for similar host-guest complexes that are expected to exhibit much more efficient light harvesting and excitation trapping at the central guest chromophore.

Energy transfer in a mechanically trapped exciplex.

PubMed

Klosterman, Jeremy K; Iwamura, Munetaka; Tahara, Tahei; Fujita, Makoto

2009-07-15

Host-guest complexes involving M(6)L(4) coordination cages can display unusual photoreactivity, and enclathration of the very large fluorophore bisanthracene resulted in an emissive, mechanically trapped intramolecular exciplex. Mechanically linked intramolecular exciplexes are important for understanding the dependence of energy transfer on donor-acceptor distance, orientation, and electronic coupling but are relatively unexplored. Steady-state and picosecond time-resolved fluorescence measurements have revealed that selective excitation of the encapsulated guest fluorophore results in efficient energy transfer from the excited guest to an emissive host-guest exciplex state.

Supramolecular regulation of bioorthogonal catalysis in cells using nanoparticle-embedded transition metal catalysts

NASA Astrophysics Data System (ADS)

Tonga, Gulen Yesilbag; Jeong, Youngdo; Duncan, Bradley; Mizuhara, Tsukasa; Mout, Rubul; Das, Riddha; Kim, Sung Tae; Yeh, Yi-Cheun; Yan, Bo; Hou, Singyuk; Rotello, Vincent M.

2015-07-01

Bioorthogonal catalysis broadens the functional possibilities of intracellular chemistry. Effective delivery and regulation of synthetic catalytic systems in cells are challenging due to the complex intracellular environment and catalyst instability. Here, we report the fabrication of protein-sized bioorthogonal nanozymes through the encapsulation of hydrophobic transition metal catalysts into the monolayer of water-soluble gold nanoparticles. The activity of these catalysts can be reversibly controlled by binding a supramolecular cucurbit[7]uril ‘gate-keeper’ onto the monolayer surface, providing a biomimetic control mechanism that mimics the allosteric regulation of enzymes. The potential of this gated nanozyme for use in imaging and therapeutic applications was demonstrated through triggered cleavage of allylcarbamates for pro-fluorophore activation and propargyl groups for prodrug activation inside living cells.

Probing the intracellular fate of supramolecular nanocarriers and their cargo with FRET schemes

NASA Astrophysics Data System (ADS)

Thapaliya, Ek Raj; Fowley, Colin; Callan, Bridgeen; Tang, Sicheng; Zhang, Yang; Callan, John F.; Raymo, Françisco M.

2017-02-01

We designed a strategy to monitor self-assembling supramolecular nanocarriers and their cargo simultaneously in the intracellular space with fluorescence measurements. It is based on Förster resonance energy transfer (FRET) between complementary chromophores covalently integrated in the macromolecular backbone of amphiphilic polymers and/or noncovalently encapsulated in supramolecular assemblies of the amphiphilic components. Indeed, these polymers assemble into a micelles in aqueous phase to bring energy donors and acceptors in close proximity and allow energy transfer. The resulting supramolecular assemblies maintain their integrity after travelling into the intracellular space and do not lose their molecular guests in the process. Furthermore, this mechanism can also be exploited to probe the fate of complementary nanoparticles introduced within cells in consecutive incubation steps. Efficient energy transfer occurs in the intracellular space after the sequential incubation of nanocarriers incorporating donors first and then nanoparticles containing acceptors or vice versa. The two sets of nanostructured assemblies ultimately co-localize in the cell interior to bring donors and acceptors together and enable energy transfer. Thus, this protocol is particularly valuable to monitor the transport properties of supramolecular nanocarriers inside living cells and can eventually contribute to the fundamental understating of the ability of these promising vehicles to deliver contrast agents and/or drugs intracellularly in view of possible diagnostics and/or therapeutic applications.

Highly Efficient Chirality Transfer from Diamines Encapsulated within a Self-Assembled Calixarene-Salen Host.

PubMed

Martínez-Rodríguez, Luis; Bandeira, Nuno A G; Bo, Carles; Kleij, Arjan W

2015-05-04

A calix[4]arene host equipped with two bis-[Zn(salphen)] complexes self-assembles into a capsular complex in the presence of a chiral diamine guest with an unexpected 2:1 ratio between the host and the guest. Effective chirality transfer from the diamine to the calix-salen hybrid host is observed by circular dichroism (CD) spectroscopy, and a high stability constant K2,1 of 1.59×10(11)  M(-2) for the assembled host-guest ensemble has been determined with a substantial cooperativity factor α of 6.4. Density functional calculations are used to investigate the origin of the stability of the host-guest system and the experimental CD spectrum compared with those calculated for both possible diastereoisomers showing that the M,M isomer is the one that is preferentially formed. The current system holds promise for the chirality determination of diamines, as evidenced by the investigated substrate scope and the linear relationship between the ee of the diamine and the amplitude of the observed Cotton effects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

How the Dynamics of a Supramolecular Polymer Determines Its Dynamic Adaptivity and Stimuli-Responsiveness: Structure-Dynamics-Property Relationships From Coarse-Grained Simulations.

PubMed

Torchi, Andrea; Bochicchio, Davide; Pavan, Giovanni M

2018-04-12

The rational design of supramolecular polymers that can adapt or respond in time to specific stimuli in a controlled way is interesting for many applications, but this requires understanding the molecular factors that make the material faster or slower in responding to the stimulus. To this end, it is necessary to study the dynamic adaptive properties at submolecular resolution, which is difficult at an experimental level. Here we show coarse-grained molecular dynamics simulations (<5 Å resolution) demonstrating how the dynamic adaptivity and stimuli responsiveness of a supramolecular polymer is controlled by the intrinsic dynamics of the assembly, which is in turn determined by the structure of the monomers. As a representative case, we focus on a water-soluble 1,3,5-benzenetricarboxamide (BTA) supramolecular polymer incorporating (charged) receptor monomers, experimentally seen to undergo dynamic clustering following the superselective binding to a multivalent recruiter. Our simulations show that the dynamic reorganization of the supramolecular structure proceeds via monomer diffusion on the dynamic fiber surface (exchange within the fiber). Rationally changing the structure of the monomers to make the fiber surface more or less dynamic allows tuning the rate of response to the stimulus and of supramolecular reconfiguration. Simple in silico experiments draw a structure-dynamics-property relationship revealing the key factors underpinning the dynamic adaptivity and stimuli-responsiveness of these supramolecular polymers. We come out with clear evidence that to master the bioinspired properties of these fibers, it is necessary to control their intrinsic dynamics, while the high-resolution of our molecular models permits us to show how.

Self-reproduction of supramolecular giant vesicles combined with the amplification of encapsulated DNA.

PubMed

Kurihara, Kensuke; Tamura, Mieko; Shohda, Koh-Ichiroh; Toyota, Taro; Suzuki, Kentaro; Sugawara, Tadashi

2011-09-04

The construction of a protocell from a materials point of view is important in understanding the origin of life. Both self-reproduction of a compartment and self-replication of an informational substance have been studied extensively, but these processes have typically been carried out independently, rather than linked to one another. Here, we demonstrate the amplification of DNA (encapsulated guest) within a self-reproducible cationic giant vesicle (host). With the addition of a vesicular membrane precursor, we observe the growth and spontaneous division of the giant vesicles, accompanied by distribution of the DNA to the daughter giant vesicles. In particular, amplification of the DNA accelerated the division of the giant vesicles. This means that self-replication of an informational substance has been linked to self-reproduction of a compartment through the interplay between polyanionic DNA and the cationic vesicular membrane. Our self-reproducing giant vesicle system therefore represents a step forward in the construction of an advanced model protocell.

The bright future of unconventional σ/π-hole interactions.

PubMed

Bauzá, Antonio; Mooibroek, Tiddo J; Frontera, Antonio

2015-08-24

Non-covalent interactions play a crucial role in (supramolecular) chemistry and much of biology. Supramolecular forces can indeed determine the structure and function of a host-guest system. Many sensors, for example, rely on reversible bonding with the analyte. Natural machineries also often have a significant non-covalent component (e.g. protein folding, recognition) and rational interference in such 'living' devices can have pharmacological implications. For the rational design/tweaking of supramolecular systems it is helpful to know what supramolecular synthons are available and to understand the forces that make these synthons stick to one another. In this review we focus on σ-hole and π-hole interactions. A σ- or π-hole can be seen as positive electrostatic potential on unpopulated σ* or π(() *()) orbitals, which are thus capable of interacting with some electron dense region. A σ-hole is typically located along the vector of a covalent bond such as XH or XHlg (X=any atom, Hlg=halogen), which are respectively known as hydrogen and halogen bond donors. Only recently it has become clear that σ-holes can also be found along a covalent bond with chalcogen (XCh), pnictogen (XPn) and tetrel (XTr) atoms. Interactions with these synthons are named chalcogen, pnigtogen and tetrel interactions. A π-hole is typically located perpendicular to the molecular framework of diatomic π-systems such as carbonyls, or conjugated π-systems such as hexafluorobenzene. Anion-π and lone-pair-π interactions are examples of named π-hole interactions between conjugated π-systems and anions or lone-pair electrons respectively. While the above nomenclature indicates the distinct chemical identity of the supramolecular synthon acting as Lewis acid, it is worth stressing that the underlying physics is very similar. This implies that interactions that are now not so well-established might turn out to be equally useful as conventional hydrogen and halogen bonds. In summary, we describe the physical nature of σ- and π-hole interactions, present a selection of inquiries that utilise σ- and π-holes, and give an overview of analyses of structural databases (CSD/PDB) that demonstrate how prevalent these interactions already are in solid-state structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electroluminescence Properties of IrQ(ppy)2 Dual-Emitter Organometallic Compound in Organic Light-Emitting Devices

NASA Astrophysics Data System (ADS)

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.

Development of a salt drug with improved solubility: Ethionamide nitrate

NASA Astrophysics Data System (ADS)

Diniz, Luan F.; Carvalho, Paulo S.; de Melo, Cristiane C.; Ellena, Javier

2017-06-01

To avoid drug resistance, an adequate tuberculosis treatment should include not only a first-line drug but also at least one second-line drug such as, for example, Ethionamide (ETH). However, the dissolution rate and oral absorption of ETH is highly limited by its low aqueous solubility. Considering that a salt is in general more soluble than its parent compound, herein we depicted a new supramolecular modification of ETH, an Ethionamide nitrate salt (ETHNO3). This salt is the first ETH structure that has been crystallized with four independent ionic pairs (ETH+NO3-) in the asymmetric unit. In addition to the structural study, the salt formation was also identified on the FT-IR and FT-Raman spectra. The thermal behavior of ETHNO3 was also investigated here together with its solubility profile in three dissolution media (purified water, pH 4.0 and 7.0).

Cage Occupation of Light Hydrocarbons in Gas Hydrate Crystals

NASA Astrophysics Data System (ADS)

Kida, M.; Watanabe, M.; Konno, Y.; Yoneda, J.; Jin, Y.; Nagao, J.

2016-12-01

Naturally occurring gas hydrates in marine or permafrost environments can trap methane and heavier hydrocarbons within its host lattice structure built up with hydrogen-bonded water molecules. Naturally occurring gas hydrates have been expected as new natural gas resources. It is important to reveal the distribution of guest hydrocarbons in host hydrate framework from viewpoint of assessment of gas capacity. In this study, we assessed cage occupancies of guest hydrocarbons in host hydrate framework of synthetic and natural gas hydrates using solid-state 13C NMR technique. As synthetic samples, gas hydrates formed from gas mixtures including C1 to C5 were investigated. As a natural sample, the pore-space gas hydrate sample recovered from the eastern Nankai Trough area during the 2012 JOGMEC/JAPEX Pressure coring operation was studied. As a result, it revealed that all heavier hydrocarbons than ethane are preferentially incorporated into the larger cage cavities in hydrate frameworks. We performed this study as a part of a Japanese National hydrate research program (MH21, funded by METI).

Giant Negative Area Compressibility Tunable in a Soft Porous Framework Material.

PubMed

Cai, Weizhao; Gładysiak, Andrzej; Anioła, Michalina; Smith, Vincent J; Barbour, Leonard J; Katrusiak, Andrzej

2015-07-29

A soft porous material [Zn(L)2(OH)2]n·Guest (where L is 4-(1H-naphtho[2,3-d]imidazol-1-yl)benzoate, and Guest is water or methanol) exhibits the strongest ever observed negative area compressibility (NAC), an extremely rare property, as at hydrostatic pressure most materials shrink in all directions and few expand in one direction. This is the first NAC reported in metal-organic frameworks (MOFs), and its magnitude, clearly visible and by far the highest of all known materials, can be reversibly tuned by exchanging guests adsorbed from hydrostatic fluids. This counterintuitive strong NAC of [Zn(L)2(OH)2]n·Guest arises from the interplay of flexible [-Zn-O(H)-]n helices with layers of [-Zn-L-]4 quadrangular puckered rings comprising large channel voids. The compression of helices and flattening of puckered rings combine to give a giant piezo-mechanical response, applicable in ultrasensitive sensors and actuators. The extrinsic NAC response to different hydrostatic fluids is due to varied host-guest interactions affecting the mechanical strain within the range permitted by exceptionally high flexibility of the framework.

Application Driven Self-Assembly of Discrete, Three-Dimensional Architectures in Water.

PubMed

Taylor, Lauren; Riddell, Imogen; Smulders, Maarten M J

2018-06-25

In this review we discuss the recent advances in the construction of discrete, self-assembled architectures in water, a field that has gained significant interest in recent years because of the wide range of applications that arises from their well-defined 3D structure. We jointly discuss the efforts undertaken by supramolecular chemists and biotechnologists who previously worked independently to overcome discipline-specific challenges associated with construction of assemblies from synthetic and bio-derived components, respectively. We propose that going forward a more interdisciplinary research approach will expedite development of both synthetic and bio-derived complexes with real-world applications that exploit the benefits of compartmentalisation. In support of this, we summarise advances made in the development of discrete, water-soluble architectures, paying particular attention to their current and prospective applications. We also highlight keys areas where understanding and methodologies developed in the field of synthetic supramolecular chemistry can be integrated into the field of biotechnology and vice versa, in anticipation this will yield advances not possible from either field alone. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrical conductivity behavior of Gum Arabic biopolymer-Fe3O4 nanocomposites

NASA Astrophysics Data System (ADS)

Bhakat, D.; Barik, P.; Bhattacharjee, A.

2018-01-01

Present work reports a study on the electrical conduction properties of some composites of Gum Arabic biopolymer and magnetite nanoparticles as host and guest, respectively, synthesized in different weight percentages. The nanocomposites are found to be non-extrinsic type of semiconductors with guest content dependent trap distribution of charge carriers. Conductivity of these materials increases with increasing guest content along with a concomitant decrease in the activation energy. Percolation theory has been employed for the analysis of the electrical conductivity results to explore the effect of the guest on the electrical conductivity of the host.

Switch-peptides: design and characterization of controllable super-amyloid-forming host-guest peptides as tools for identifying anti-amyloid agents.

PubMed

Camus, Marie-Stéphanie; Dos Santos, Sonia; Chandravarkar, Arunan; Mandal, Bhubaneswar; Schmid, Adrian W; Tuchscherer, Gabriele; Mutter, Manfred; Lashuel, Hilal A

2008-09-01

Several amyloid-forming proteins are characterized by the presence of hydrophobic and highly amyloidogenic core sequences that play critical roles in the initiation and progression of amyloid fibril formation. Therefore targeting these sequences represents a viable strategy for identifying candidate molecules that could interfere with amyloid formation and toxicity of the parent proteins. However, the highly amyloidogenic and insoluble nature of these sequences has hampered efforts to develop high-throughput fibrillization assays. Here we describe the design and characterization of host-guest switch peptides that can be used for in vitro mechanistic and screening studies that are aimed at discovering aggregation inhibitors that target highly amyloidogenic sequences. These model systems are based on a host-guest system where the amyloidogenic sequence (guest peptide) is flanked by two beta-sheet-promoting (Leu-Ser)(n) oligomers as host sequences. Two host-guest peptides were prepared by using the hydrophobic core of Abeta comprising residues 14-24 (HQKLVFFAEDV) as the guest peptide with switch elements inserted within (peptide 1) or at the N and C termini of the guest peptide (peptide 2). Both model peptides can be triggered to undergo rapid self-assembly and amyloid formation in a highly controllable manner and their fibrillization kinetics is tuneable by manipulating solution conditions (for example, peptide concentration and pH). The fibrillization of both peptides reproduces many features of the full-length Abeta peptides and can be inhibited by known inhibitors of Abeta fibril formation. Our results suggest that this approach can be extended to other amyloid proteins and should facilitate the discovery of small-molecule aggregation inhibitors and the development of more efficacious anti-amyloid agents to treat and/or reverse the pathogenesis of neurodegenerative and systemic amyloid diseases.

The amorphous solid dispersion of the poorly soluble ABT-102 forms nano/microparticulate structures in aqueous medium: impact on solubility.

PubMed

Frank, Kerstin J; Westedt, Ulrich; Rosenblatt, Karin M; Hölig, Peter; Rosenberg, Jörg; Mägerlein, Markus; Fricker, Gert; Brandl, Martin

2012-01-01

Amorphous solid dispersions (ASDs) are a promising formulation approach for poorly soluble active pharmaceutical ingredients (APIs), because they ideally enhance both dissolution rate and solubility. However, the mechanism behind this is not understood in detail. In the present study, we investigated the supramolecular and the nano/microparticulate structures that emerge spontaneously upon dispersion of an ASD in aqueous medium and elucidated their influence on solubility. The ASD, prepared by hot melt extrusion, contained the poorly soluble ABT-102 (solubility in buffer, 0.05 μg/mL), a hydrophilic polymer, and three surfactants. The apparent solubility of ABT-102 from the ASD-formulation was enhanced up to 200 times in comparison to crystalline ABT-102. At the same time, the molecular solubility, as assessed by inverse equilibrium dialysis, was enhanced two times. Asymmetrical flow field-flow fractionation in combination with a multiangle light-scattering detector, an ultraviolet detector, and a refractometer enabled us to separate and identify the various supramolecular assemblies that were present in the aqueous dispersions of the API-free ASD (placebo) and of binary/ternary blends of the ingredients. Thus, the supramolecular assemblies with a molar mass between 20,000 and 90,000 could be assigned to the polyvinylpyrrolidone/vinyl acetate 64, while two other kinds of assemblies were assigned to different surfactant assemblies (micelles). The amount of ABT-102 remaining associated with each of the assemblies upon fractionation was quantified offline with high-performance liquid chromatography-ultraviolet-visible. The polymeric and the micellar fraction contributed to the substantial increase in apparent solubility of ABT-102. Furthermore, a microparticulate fraction was isolated by centrifugation and analyzed by scanning electron microscopy, X-ray scattering, and infrared spectroscopy. The microparticles were found to be amorphous and to contain two of the surfactants besides ABT-102 as the main component. The amorphous microparticles are assumed to be the origin of the observed increase in molecular solubility ("true" supersaturation).

Diffusion of vaporous guests into a seemingly non-porous organic crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herbert, Simon A.; Janiak, Agnieszka; Thallapally, Praveen K.

2014-10-07

In this research, the tetragonal apohost phase of p-tert-butyltetramethoxythiacalix[4]arene absorbs hydrochloric acid and iodine. These guest molecules occupy different sites in the solid-state structure -- either within the small intrinsic voids of the macrocycle or within the interstitial spaces between the host molecules. This study illustrates the dynamic deformation of the host, providing strong mechanistic insight into the diffusion of guests into this seemingly non-porous material.

Exploring the oxidation and iron binding profile of a cyclodextrin encapsulated quercetin complex unveiled a controlled complex dissociation through a chemical stimulus.

PubMed

Diamantis, Dimitrios A; Ramesova, Sarka; Chatzigiannis, Christos M; Degano, Ilaria; Gerogianni, Paraskevi S; Karadima, Constantina; Perikleous, Sonia; Rekkas, Dimitrios; Gerothanassis, Ioannis P; Galaris, Dimitrios; Mavromoustakos, Thomas; Valsami, Georgia; Sokolova, Romana; Tzakos, Andreas G

2018-06-07

Flavonoids possess a rich polypharmacological profile and their biological role is linked to their oxidation state protecting DNA from oxidative stress damage. However, their bioavailability is hampered due to their poor aqueous solubility. This can be surpassed through encapsulation to supramolecular carriers as cyclodextrin (CD). A quercetin- 2HP-β-CD complex has been formerly reported by us. However, once the flavonoid is in its 2HP-β-CD encapsulated state its oxidation potential, its decomplexation mechanism, its potential to protect DNA damage from oxidative stress remained elusive. To unveil this, an array of biophysical techniques was used. The quercetin-2HP-β-CD complex was evaluated through solubility and dissolution experiments, electrochemical and spectroelectrochemical studies (Cyclic Voltammetry) UV-Vis spectroscopy, HPLC-ESI-MS/MS and HPLC-DAD, fluorescence spectroscopy, NMR Spectroscopy, theoretical calculations (density functional theory (DFT)) and biological evaluation of the protection offered against H 2 O 2 -induced DNA damage. Encapsulation of quercetin inside the supramolecule's cavity enhanced its solubility and oxidation profile is retained in its encapsulated state. Although the protective ability of the quercetin-2HP-β-CD complex against H 2 O 2 was diminished, iron serves as a chemical stimulus to dissociate the complex and release quercetin. We found that in a quercetin-2HP-β-CD inclusion complex quercetin retains its oxidation profile similarly to its native state, while iron can operate as a chemical stimulus to release quercetin from its host cavity. The oxidation profile of a natural product once it is encapsulated in a supramolecular cyclodextrin carrier as also it was discovered that decomplexation can be triggered by a chemical stimulus. Copyright © 2018. Published by Elsevier B.V.

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

PubMed

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.

Force-field and quantum-mechanical binding study of selected SAMPL3 host-guest complexes

NASA Astrophysics Data System (ADS)

Hamaguchi, Nobuko; Fusti-Molnar, Laszlo; Wlodek, Stanislaw

2012-05-01

A Merck molecular force field classical potential combined with Poisson-Boltzmann electrostatics (MMFF/PB) has been used to estimate the binding free energy of seven guest molecules (six tertiary amines and one primary amine) into a synthetic receptor (acyclic cucurbit[4]uril congener) and two benzimidazoles into cyclic cucurbit[7]uril (CB[7]) and cucurbit[8]uril (CB[8]) hosts. In addition, binding enthalpies for the benzimidazoles were calculated with density functional theory (DFT) using the B3LYP functional and a polarizable continuum model (PCM). Although in most cases the MMFF/PB approach returned reasonable agreements with the experiment (±2 kcal/mol), significant, much larger deviations were reported in the case of three host-guest pairs. All four binding enthalpy predictions with the DFT/PCM method suffered 70% or larger deviations from the calorimetry data. Results are discussed in terms of the molecular models used for guest-host complexation and the quality of the intermolecular potentials.

Calixarene-Mediated Liquid-Membrane Transport of Choline Conjugates.

PubMed

Adhikari, Birendra Babu; Fujii, Ayu; Schramm, Michael P

2014-05-01

A series of supramolecular calixarenes efficiently transport distinct molecular species through a liquid membrane when attached to a receptor-complementary choline handle. Calix-[6]arene hexacarboxylic acid was highly effective at transporting different target molecules against a pH gradient. Both carboxylic- and phosphonic-acid-functionalized calix[4]arenes effect transport without requiring a pH or ion gradient. NMR binding studies, two-phase solvent extraction, and three-phase transport experiments reveal the necessary and subtle parameters to effect the transport of molecules attached to a choline "handle". On the other hand, rescorin[4]arene cavitands, which have similar guest recognition profiles, did not transport guest molecules. These developments reveal new approaches towards attempting synthetic-receptor-mediated selective small-molecule transport in vesicular and cellular systems.

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

PubMed

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.

Chemically bonded stationary phases that use synthetic hosts containing aromatic binding clefts: HPLC analysis of nitro-substituted polycyclic aromatic hydrocarbons.

PubMed Central

Zimmerman, S C; Saionz, K W; Zeng, Z

1993-01-01

The synthesis of hosts with improved binding affinities for nitroaromatic guests is described. Association constants for several host-guest complexes were measured in chloroform solution and ranged over three orders of magnitude. Two hosts were covalently linked to silica gel to produce chemically bonded stationary phases for HPLC. The use of these phases for HPLC analysis of nitro-substituted polycyclic aromatic hydrocarbons is discussed. PMID:8433981

Towards the fluorogenic detection of peroxide explosives through host-guest chemistry.

PubMed

Almenar, Estefanía; Costero, Ana M; Gaviña, Pablo; Gil, Salvador; Parra, Margarita

2018-04-01

Two dansyl-modified β-cyclodextrin derivatives ( 1 and 2 ) have been synthesized as host-guest sensory systems for the direct fluorescent detection of the peroxide explosives diacetone diperoxide (DADP) and triacetone triperoxide (TATP) in aqueous media. The sensing is based on the displacement of the dansyl moiety from the cavity of the cyclodextrin by the peroxide guest resulting in a decrease of the intensity of the fluorescence of the dye. Both systems showed similar fluorescent responses and were more sensitive towards TATP than DADP.

Molecular recognition on a cavitand-functionalized silicon surface.

PubMed

Biavardi, Elisa; Favazza, Maria; Motta, Alessandro; Fragalà, Ignazio L; Massera, Chiara; Prodi, Luca; Montalti, Marco; Melegari, Monica; Condorelli, Guglielmo G; Dalcanale, Enrico

2009-06-03

A Si(100) surface featuring molecular recognition properties was obtained by covalent functionalization with a tetraphosphonate cavitand (Tiiii), able to complex positively charged species. Tiiii cavitand was grafted onto the Si by photochemical hydrosilylation together with 1-octene as a spatial spectator. The recognition properties of the Si-Tiiii surface were demonstrated through two independent analytical techniques, namely XPS and fluorescence spectroscopy, during the course of reversible complexation-guest exchange-decomplexation cycles with specifically designed ammonium and pyridinium salts. Control experiments employing a Si(100) surface functionalized with a structurally similar, but complexation inactive, tetrathiophosphonate cavitand (TSiiii) demonstrated no recognition events. This provides evidence for the complexation properties of the Si-Tiiii surface, ruling out the possibility of nonspecific interactions between the substrate and the guests. The residual Si-O(-) terminations on the surface replace the guests' original counterions, thus stabilizing the complex ion pairs. These results represent a further step toward the control of self-assembly of complex supramolecular architectures on surfaces.

Hexahomotrioxacalix[3]arene derivatives as ionophores for molecular recognition of dopamine, serotonin and phenylethylamine.

PubMed

Ni, Xin-Long; Rahman, Shofiur; Wang, Shi; Jin, Cheng-Cheng; Zeng, Xi; Hughes, David L; Redshaw, Carl; Yamato, Takehiko

2012-06-21

The lower rim functionalized hexahomotrioxacalix[3]arene derivatives cone-3 and cone-5 bearing three benzyl and three N,N-diethyl-2-aminoethoxy groups, respectively, were synthesized from triol 1. Their complexation with 2-(3,4-dihydroxyphenyl)ethylamine (dopamine), 5-hydroxytryptamine (serotonin), and 2-phenylethylamine (phenethylamine), which have biologically important activities, has been studied by (1)H-NMR spectroscopy. The chemical shifts of the aromatic protons of the host and guest molecules and the up-field shifts of the ethyl protons of the guest molecules strongly suggest the formation of inclusion complexes in solution. The formation of the host-guest complexes is assisted by a hydrogen bond and/or an electrostatic interaction between the host and ammonium ion (RNH(3)(+)) of the guest. The structures of receptors cone-3 and cone-5 have been determined by X-ray crystallography.

Free-volume characterization of nanostructurized substances by positron annihilation lifetime spectroscopy

NASA Astrophysics Data System (ADS)

Shpotyuk, O.; Ingram, A.; Shpotyuk, Ya.

2018-02-01

Methodological possibilities of positron annihilation lifetime (PAL) spectroscopy are examined to parameterize free-volume structural evolution processes in some nanostructurized substances obeying conversion from positronium (Ps) decaying to positron trapping. Unlike conventional x3-term fitting analysis based on admixed positron trapping and Ps decaying, the effect of nanostructurization is considered as occurring due to conversion from preferential Ps decaying in initial host matrix to positron trapping in modified (nanostructurized) host-guest matrix. The developed approach referred to as x3-x2-CDA (coupling decomposition algorithm) allows estimation defect-free bulk and defect-specific positron lifetimes of free-volume elements responsible for nanostructurization. The applicability of this approach is proved for some nanostructurized materials allowing free-volume changes through Ps-to-positron trapping conversion, such as (i) metallic Ag nanoparticles embedded in polymer matrix, (ii) structure-modification processes caused by swift heavy ions irradiation in polystyrene, and (iii) host-guest chemistry problems like water immersion in alumomagnesium spinel ceramics. This approach is considered to be used as test-indicator, separating processes of host-matrix nanostructurization due to embedded nanoparticles from uncorrelated changes in positron-trapping and Ps-decaying channels.

Novel inclusion complex of ibuprofen tromethamine with cyclodextrins: physico-chemical characterization.

PubMed

Al Omari, Mahmoud M; Daraghmeh, Nidal H; El-Barghouthi, Musa I; Zughul, Mohammad B; Chowdhry, Babur Z; Leharne, Stephen A; Badwan, Adnan A

2009-10-15

Guest-host interactions of ibuprofen tromethamine salt (Ibu.T) with native and modified cyclodextrins (CyDs) have been investigated using several techniques, namely phase solubility diagrams (PSDs), proton nuclear magnetic resonance ((1)H NMR), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffractometry (XRPD), scanning-electron microscopy (SEM) and molecular mechanics (MM). From the analysis of PSD data (A(L)-type) it is concluded that the anionic tromethamine salt of ibuprofen (pK(a)=4.55) forms 1:1 soluble complexes with all CyDs investigated in buffered water at pH 7.0, while the neutral form of Ibu forms an insoluble complex with beta-CyD (B(S)-type) in buffered water at pH 2.0. Ibu.T has a lower tendency to complex with beta-CyD (K(11)=58 M(-1) at pH 7.0) compared with the neutral Ibu (K(11)=4200 M(-1)) in water. Complex formation of Ibu.T with beta-CyD (DeltaG(o)=-20.4 kJ/mol) is enthalpy driven (DeltaH(o)=-22.9 kJ/mol) and is accompanied by a small unfavorable entropy (DeltaS(o)=-8.4 J/mol K) change. (1)H NMR studies and MM computations revealed that, on complexation, the hydrophobic central benzene ring of Ibu.T and part of the isobutyl group reside within the beta-CyD cavity leaving the peripheral groups (carboxylate, tromethamine and methyl groups) located near the hydroxyl group networks at either rim of beta-CyD. PSD, (1)H NMR, DSC, FT-IR, XRPD, SEM and MM studies confirmed the formation of Ibu.T/beta-CyD inclusion complex in solution and the solid state.

High-brightness blue organic light emitting diodes with different types of guest-host systems

NASA Astrophysics Data System (ADS)

Wang, Xiao; Zhang, Jing-shuang; Peng, Cui-yun; Guo, Kun-ping; Wei, Bin; Zhang, Hao

2016-03-01

We demonstrate high-brightness blue organic light emitting diodes (OLEDs) using two types of guest-host systems. A series of blue OLEDs were fabricated using three organic emitters of dibenz anthracene (perylene), di(4-fluorophenyl) amino-di (styryl) biphenyl (DSB) and 4,4'-bis[2-(9-ethyl-3-carbazolyl)vinyl]biphenyl (BCzVBi) doped into two hosting materials of 4,4'-bis(9-carbazolyl) biphenyl (CBP) and 2-(4-biphenylyl)-5(4-tert-butyl-phenyl)-1,3,4-oxadiazole (PBD) as blue emitting layers, respectively. We achieve three kinds of devices with colors of deep-blue, pure-blue and sky-blue with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.16, 0.10), (0.15, 0.15) and (0.17, 0.24), respectively, by employing PBD as host material. In addition, we present a microcavity device using the PBD guest-host system and achieve high-purity blue devices with narrowed spectrum.

Redesigning Channel-Forming Peptides: Amino Acid Substitutions that Enhance Rates of Supramolecular Self-Assembly and Raise Ion Transport Activity

PubMed Central

Shank, Lalida P.; Broughman, James R.; Takeguchi, Wade; Cook, Gabriel; Robbins, Ashley S.; Hahn, Lindsey; Radke, Gary; Iwamoto, Takeo; Schultz, Bruce D.; Tomich, John M.

2006-01-01

Three series of 22-residue peptides derived from the transmembrane M2 segment of the glycine receptor α1-subunit (M2GlyR) have been designed, synthesized, and tested to determine the plasticity of a channel-forming sequence and to define whether channel pores with enhanced conductive properties could be created. Sixteen sequences were examined for aqueous solubility, solution-association tendency, secondary structure, and half-maximal concentration for supramolecular assembly, channel activity, and ion transport properties across epithelial monolayers. All peptides interact strongly with membranes: associating with, inserting across, and assembling to form homooligomeric bundles when in micromolar concentrations. Single and double amino acid replacements involving arginine and/or aromatic amino acids within the final five C-terminal residues of the peptide cause dramatic effects on the concentration dependence, yielding a range of K1/2 values from 36 ± 5 to 390 ± 220 μM for transport activity. New water/lipid interfacial boundaries were established for the transmembrane segment using charged or aromatic amino acids, thus limiting the peptides' ability to move perpendicularly to the plane of the bilayer. Formation of discrete water/lipid interfacial boundaries appears to be necessary for efficient supramolecular assembly and high anion transport activity. A peptide sequence is identified that may show efficacy in channel replacement therapy for channelopathies such as cystic fibrosis. PMID:16387776

Defined Host–Guest Chemistry on Nanocarbon for Sustained Inhibition of Cancer

PubMed Central

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

2017-01-01

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 IC50 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. PMID:27545321

Self-assembling graphene-anthraquinone-2-sulphonate supramolecular nanostructures with enhanced energy density for supercapacitors

NASA Astrophysics Data System (ADS)

Gao, Lifang; Gan, Shiyu; Li, Hongyan; Han, Dongxue; Li, Fenghua; Bao, Yu; Niu, Li

2017-07-01

Boosting the energy density of capacitive energy storage devices remains a crucial issue for facilitating applications. Herein, we report a graphene-anthraquinone supramolecular nanostructure by self-assembly for supercapacitors. The sulfonated anthraquinone exhibits high water solubility, a π-conjugated structure and redox active features, which not only serve as a spacer to interact with and stabilize graphene but also introduce extra pseudocapacitance contributions. The formed nest-like three-dimensional (3D) nanostructure with further hydrothermal treatment enhances the accessibility of ion transfer and exposes the redox-active quinone groups in the electrolytes. A fabricated all-solid-state flexible symmetric device delivers a high specific capacitance of 398.5 F g-1 at 1 A g-1 (1.5 times higher than graphene), superior energy density (52.24 Wh kg-1 at about 1 kW kg-1) and good stability (82% capacitance retention after 10 000 cycles).

Ultrasonic assisted synthesis of adenosine triphosphate capped manganese-doped ZnS quantum dots for selective room temperature phosphorescence detection of arginine and methylated arginine in urine based on supramolecular Mg(2+)-adenosine triphosphate-arginine ternary system.

PubMed

Ren, Hu-Bo; Yan, Xiu-Ping

2012-08-15

An ultrasonic assisted approach was developed for rapid synthesis of highly water soluble phosphorescent adenosine triphosphate (ATP)-capped Mn-doped ZnS QDs. The prepared ATP-capped Mn-doped ZnS QDs allow selective phosphorescent detection of arginine and methylated arginine based on the specific recognition nature of supramolecular Mg(2+)-ATP-arginine ternary system in combination with the phosphorescence property of Mn-doped ZnS QDs. The developed QD based probe gives excellent selectivity and reproducibility (1.7% relative standard deviation for 11 replicate detections of 10 μM arginine) and low detection limit (3 s, 0.23 μM), and favors biological applications due to the effective elimination of interference from scattering light and autofluorescence. Copyright © 2012 Elsevier B.V. All rights reserved.

Supramolecular Complex Antioxidant Consisting of Vitamins C, E and Hydrophilic-Hydrophobic Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Laguta, I. V.; Kuzema, P. O.; Stavinskaya, O. N.; Kazakova, O. A.

Samples with varied amount of surface trimethylsilyl groups were obtained via gas-phase chemical modification of silica nanoparticles. The biocompatibility tests conducted in erythrocyte suspension have shown that hydrophobization of silica decreases its damaging effect to the cells. Being wettable in aqueous media, partially silylated silicas have higher affinity to hydrophobic bioactive molecules in comparison with the initial silica. Novel antioxidant consisting of vitamins C and E and silica with 40% of surface trimethylsilyl groups was formulated. It was found that supramolecular complexes are formed on the silica surface due to the affinity of water- and fat-soluble antioxidants to hydrophilic silanol and hydrophobic trimethylsilyl groups, respectively. Test reactions (total phenolic index determination, DPPH test) and in vitro studies (spectral analysis of erythrocyte suspensions undergoing UV irradiation) revealed the correlation between antioxidant activity of the complex antioxidant and the vitamins’ content. The antioxidant remained active during long-term storage under standard conditions.

Supramolecular Complex Antioxidant Consisting of Vitamins C, E and Hydrophilic-Hydrophobic Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Laguta, I. V.; Kuzema, P. O.; Stavinskaya, O. N.; Kazakova, O. A.

Samples with varied amount of surface trimethylsilyl groups were obtained via gas-phase chemical modification of silica nanoparticles. The biocompatibility tests conducted in erythrocyte suspension have shown that hydrophobization of silica decreases its damaging effect to the cells. Being wettable in aqueous media, partially silylated silicas have higher affinity to hydrophobic bioactive molecules in comparison with the initial silica. Novel antioxidant consisting of vitamins C and E and silica with 40% of surface trimethylsilyl groups was formulated. It was found that supramolecular complexes are formed on the silica surface due to the affinity of water- and fat-soluble antioxidants to hydrophilic silanol and hydrophobic trimethylsilyl groups, respectively. Test reactions (total phenolic index determination, DPPH test) and in vitro studies (spectral analysis of erythrocyte suspensions undergoing UV irradiation) revealed the correlation between antioxidant activity of the complex antioxidant and the vitamins' content. The antioxidant remained active during long-term storage under standard conditions.

Tadalafil inclusion in microporous silica as effective dissolution enhancer: optimization of loading procedure and molecular state characterization.

PubMed

Mehanna, Mohammed M; Motawaa, Adel M; Samaha, Magda W

2011-05-01

Tadalafil is an efficient drug used to treat erectile dysfunction characterized by poor water solubility, which has a negative influence on its bioavailability. Utilization of microporous silica represents an effective and facile technology to increase the dissolution rate of poorly soluble drugs. Our strategy involved directly introducing tadalafil as guest molecule into microporous silica as host material by incipient wetness impregnation method. To optimize tadalafil inclusion, response surface methodology (RSM) using 3(3) factorial design was utilized. Furthermore, to investigate the molecular state of tadalafil, Fourier-transform infrared spectroscopy, differential scanning calorimetery, thermal gravimetrical analysis, nitrogen adsorption, and powder X-ray diffraction (PXRD) were carried out. The results obtained pointed out that the quantity of microporous silica was the predominant factor that increased the loading efficiency. For the optimized formula, the loading efficiency was 42.50 wt %. Adsorption-desorption experiments indicated that tadalafil has been introduced into the micropores. Powder XRD and differential scanning calorimetry analyses revealed that tadalafil is arranged in amorphous form. In addition, the dissolution rate of tadalafil from the microporous silica was faster than that of free drug. Amorphous tadalafil occluded in microporous silica did not crystallize over 3 months. These findings contributed in opening a new strategy concerning the utilization of porous silica for the dissolution rate enhancement. Copyright © 2010 Wiley-Liss, Inc.

Theory of gas hydrates: effect of the approximation of rigid water lattice.

PubMed

Pimpalgaonkar, Hrushikesh; Veesam, Shivanand K; Punnathanam, Sudeep N

2011-08-25

One of the assumptions of the van der Waals and Platteeuw theory for gas hydrates is that the host water lattice is rigid and not distorted by the presence of guest molecules. In this work, we study the effect of this approximation on the triple-point lines of the gas hydrates. We calculate the triple-point lines of methane and ethane hydrates via Monte Carlo molecular simulations and compare the simulation results with the predictions of van der Waals and Platteeuw theory. Our study shows that even if the exact intermolecular potential between the guest molecules and water is known, the dissociation temperatures predicted by the theory are significantly higher. This has serious implications to the modeling of gas hydrate thermodynamics, and in spite of the several impressive efforts made toward obtaining an accurate description of intermolecular interactions in gas hydrates, the theory will suffer from the problem of robustness if the issue of movement of water molecules is not adequately addressed. © 2011 American Chemical Society

Host-Guest Complexes with Protein-Ligand-Like Affinities: Computational Analysis and Design

PubMed Central

Moghaddam, Sarvin; Inoue, Yoshihisa

2009-01-01

It has recently been discovered that guests combining a nonpolar core with cationic substituents bind cucurbit[7]uril (CB[7]) in water with ultra-high affinities. The present study uses the Mining Minima algorithm to study the physics of these extraordinary associations and to computationally test a new series of CB[7] ligands designed to bind with similarly high affinity. The calculations reproduce key experimental observations regarding the affinities of ferrocene-based guests with CB[7] and β-cyclodextrin and provide a coherent view of the roles of electrostatics and configurational entropy as determinants of affinity in these systems. The newly designed series of compounds is based on a bicyclo[2.2.2]octane core, which is similar in size and polarity to the ferrocene core of the existing series. Mining Minima predicts that these new compounds will, like the ferrocenes, bind CB[7] with extremely high affinities. PMID:19133781

Synthesis and Small Molecule Exchange Studies of a Magnesium Bisformate Metal-Organic Framework: An Experiment in Host-Guest Chemistry for the Undergraduate Laboratory

ERIC Educational Resources Information Center

Rood, Jeffrey A.; Henderson, Kenneth W.

2013-01-01

concepts of host-guest chemistry and size exclusion in porous metal-organic frameworks (MOFs). The experiment has been successfully carried out in both introductory and advanced-level inorganic chemistry laboratories. Students synthesized the porous MOF, alpha-Mg[subscript…

Vibrational Dynamics and Guest-Host Coupling in Clathrate Hydrates

NASA Astrophysics Data System (ADS)

Koza, Michael M.; Schober, Helmut

Clathrate hydrates may turn out either a blessing or a curse for mankind. On one hand, they constitute a huge reservoir of fossil fuel. On the other hand, their decomposition may liberate large amounts of green house gas and have disastrous consequences on sea floor stability. It is thus of paramount importance to understand the formation and stability of these guest-host compounds. Neutron diffraction has successfully occupied a prominent place on the stage of these scientific investigations. Complete understanding, however, is not achieved without an explanation for the thermal properties of clathrates. In particular, the thermal conductivity has a large influence on clathrate formation and conservation. Neutron spectroscopy allows probing the microscopic dynamics of clathrate hydrates. We will show how comparative studies of vibrations in clathrate hydrates give insight into the coupling of the guest to the host lattice. This coupling together with the anharmonicity of the vibrational modes is shown to lay the foundations for the peculiar thermodynamic properties of clathrate hydrates. The results obtained reach far beyond the specific clathrate system. Similar mechanisms are expected to be at work in any guest-host complex.

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

PubMed Central

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

2016-01-01

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. PMID:26874280

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

PubMed

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

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

PubMed

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.

Nano-aggregates: emerging delivery tools for tumor therapy.

PubMed

Sharma, Vinod Kumar; Jain, Ankit; Soni, Vandana

2013-01-01

A plethora of formulation techniques have been reported in the literature for site-specific targeting of water-soluble and -insoluble anticancer drugs. Along with other vesicular and particulate carrier systems, nano-aggregates have recently emerged as a novel supramolecular colloidal carrier with promise for using poorly water-soluble drugs in molecular targeted therapies. Nano-aggregates possess some inherent properties such as size in the nanometers, high loading efficiency, and in vivo stability. Nano-aggregates can provide site-specific drug delivery via either a passive or active targeting mechanism. Nano-aggregates are formed from a polymer-drug conjugated amphiphilic block copolymer. They are suitable for encapsulation of poorly water-soluble drugs by covalent conjugation as well as physical encapsulation. Because of physical encapsulation, a maximum amount of drug can be loaded in nano-aggregates, which helps to achieve a sufficiently high drug concentration at the target site. Active transport can be achieved by conjugating a drug with vectors or ligands that bind specifically to receptors being overexpressed in the tumor cells. In this review, we explore synthesis and tumor targeting potential of nano-aggregates with active and passive mechanisms, and we discuss various characterization parameters, ex vivo studies, biodistribution studies, clinical trials, and patents.

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

PubMed

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.

Host–guest complexes between cryptophane-C and chloromethanes revisited

PubMed Central

Takacs, Z; Soltesova, M; Kowalewski, J; Lang, J; Brotin, T; Dutasta, J-P

2013-01-01

Cryptophane-C is composed of two nonequivalent cyclotribenzylene caps, one of which contains methoxy group substituents on the phenyl rings. The two caps are connected by three OCH2CH2O linkers in an anti arrangement. Host–guest complexes of cryptophane-C with dichloromethane and chloroform in solution were investigated in detail by nuclear magnetic resonance techniques and density functional theory (DFT) calculations. Variable temperature proton and carbon-13 spectra show a variety of dynamic processes, such as guest exchange and host conformational transitions. The guest exchange was studied quantitatively by exchange spectroscopy measurements or by line-shape analysis. The conformational preferences of the guest-containing host were interpreted through cross-relaxation measurements, providing evidence of the gauche+2 and gauche−2 conformations of the linkers. In addition, the mobility of the chloroform guest inside the cavity was studied by carbon-13 relaxation experiments. Combining different types of evidence led to a detailed picture of molecular recognition, interpreted in terms of conformational selection. Copyright © 2012 John Wiley & Sons, Ltd. PMID:23132654

Guest Chain ``Melting'' in Incommensurate Host-Guest Potassium

NASA Astrophysics Data System (ADS)

McBride, Emma; Munro, Keith; McMahon, Malcolm

2013-06-01

Upon increasing pressure the group-I elements transform from close-packed structures (bcc and fcc) to a series of low-symmetry complex structures. Residing in the middle of the group, potassium (K) has numerous structures in common with its neighbours, and, in fact, is remarkably structurally similar to sodium (Na) and rubidium (Rb). For example, the post-fcc transition in K is to a composite incommensurate host-guest structure (tI19), and the host structure of this phase is isostructural with that found in Na and Rb. Previously we have reported that below 16.7GPa, the Bragg peaks from the guest component of tI19-Rb broaden considerably, signalling a loss of the inter-chain correlation, or a ``melting'' of the chains. Furthermore, in tI19-Na above 125 GPa, the Bragg peaks from the guest component are also broadened, suggesting that the guest chains are also nearly ``melted.'' During studies of the melting curve of K, we observed that the guest peaks from tI19-K broaden dramatically on heating. Here we report single-crystal, quasi-single-crystal, and powder synchrotron x-ray diffraction measurements of tI19-K to 50 GPa and 800 K, which allowed a detailed study of this chain ``melting'' transition. The order-disorder transition is clearly visible over a 30 GPa pressure range, and there are significant changes in the gradient of the phase boundary, which may be influenced by the nature of the guest structure. Furthermore, data extending the melting curve will also be presented.

Calixarene-Mediated Liquid-Membrane Transport of Choline Conjugates

PubMed Central

Adhikari, Birendra Babu; Fujii, Ayu

2015-01-01

A series of supramolecular calixarenes efficiently transport distinct molecular species through a liquid membrane when attached to a receptor-complementary choline handle. Calix-[6]arene hexacarboxylic acid was highly effective at transporting different target molecules against a pH gradient. Both carboxylic- and phosphonic-acid-functionalized calix[4]arenes effect transport without requiring a pH or ion gradient. NMR binding studies, two-phase solvent extraction, and three-phase transport experiments reveal the necessary and subtle parameters to effect the transport of molecules attached to a choline “handle”. On the other hand, rescorin[4]arene cavitands, which have similar guest recognition profiles, did not transport guest molecules. These developments reveal new approaches towards attempting synthetic-receptor-mediated selective small-molecule transport in vesicular and cellular systems. PMID:26161034

Unusual nanosized associates of carboxy-calix[4]resorcinarene and cetylpyridinium chloride: the macrocycle as a glue for surfactant micelles.

PubMed

Morozova, Ju E; Syakaev, V V; Shalaeva, Ya V; Ermakova, A M; Nizameev, I R; Kadirov, M K; Voloshina, A D; Zobov, V V; Antipin, I S; Konovalov, A I

2017-03-08

The association of cetylpyridinium chloride (CPC) micelles in the presence of octaacetated tetraphenyleneoxymethylcalix[4]resorcinarene (CR) leads to the formation of unusual spherical supramolecular nanoparticles (SNPs). Within the range of CR/CPC molar ratios from 10/1 to 1/10 (except for 1/8), CR, acting as a counterion, decreases the critical micelle concentration of CPC by one order of magnitude and leads to the formation of SNPs with an average hydrodynamic radius of 164 nm and an average zeta potential of -60 mV. The formation of SNPs was studied by NMR FT-PGSE and 2D NOESY, DLS, TEM, fluorimetry, and UV-Vis methods. The stability of SNPs at different temperatures and pH values and in the presence of electrolytes was investigated. The specificity of the interactions of the SNPs with substrates that were preferentially bound by a macrocycle or CPC micelle was studied. The enhancement of cation dye binding in the presence of SNPs is shown. The presented supramolecular system may serve as a nanocapsule for water-soluble and water-insoluble compounds.

[Synthesis of a supermolecular nanoparticle γ-hy-PC/Ada-Dox and its antitumor activity].

PubMed

Li, Yong-bin; Wang, Kai; Hu, Tian-nan; Wang, Qi-wen; Hu, Qi-da; Zhou, Jun; Hu, Xiu-rong; Tang, Gu-ping

2012-11-01

To synthesize a (2-Hydroxypropyl)-γ-cyclodextrin-polyethylenimine/adamantane-conjugated doxorubicin (γ-hy-PC/Ada-Dox) based supramolecular nanoparticle with host-guest interaction and to identify its physicochemical characterizations and antitumor effect. A novel non-viral gene delivery vector γ-hy-PC/Ada-Dox was synthesized based on host-guest interaction. 1H-NMR, NOESY, UV-Vis, XRD and TGA were used to confirm the structure of the vector. The DNA condensing ability of complexes was investigated by particle size, zeta potential and gel retardation assay. Cytotoxicity of complexes was determined by MTT assay in BEL-7402 and SMMC-7721 cells. Cell wound healing assay was performed in HEK293 and BEL-7404 cells. The transfection efficiency was investigated in HEK293 cells. H/E staining and cell uptake assay was performed in BEL-7402 cells. The structure of γ-hy-PC/Ada-Dox was characterized by 1H-NMR, NOESY, UV-Vis, XRD, TGA. The drug loading was 0.5% and 5.5%. Gel retardation assay showed that γ-hy-PC was able to completely condense DNA at N/P ratio of 2; 0.5% and 5.5% γ-hy-PC/Ada-Dox was able to completely condense DNA at N/P ratio of 3 and 4,respectively. The cytotoxicity of polymers was lower than that of PEI25KDa. The transfection efficiency of γ-hy-PC was higher than that of γ-hy-PC/Ada-Dox at N/P ratio of 30 in HEK293 cells; and the transfection efficiency was decreasing when Ada-Dox loading was increasing. Cell uptake assay showed that γ-hy-PC/Ada-Dox was able to carry drug and FAM-siRNA into cells. The novel vector γ-hy-PC/Ada-Dox has been developed successfully, which has certain transfection efficiency and antitumor activity.

3D FTO/FTO-Nanocrystal/TiO2 Composite Inverse Opal Photoanode for Efficient Photoelectrochemical Water Splitting.

PubMed

Wang, Zhiwei; Li, Xianglin; Ling, Han; Tan, Chiew Kei; Yeo, Loo Pin; Grimsdale, Andrew Clive; Tok, Alfred Iing Yoong

2018-05-01

A 3D fluorine-doped SnO 2 (FTO)/FTO-nanocrystal (NC)/TiO 2 inverse opal (IO) structure is designed and fabricated as a new "host and guest" type of composite photoanode for efficient photoelectrochemical (PEC) water splitting. In this novel photoanode design, the highly conductive and porous FTO/FTO-NC IO acts as the "host" skeleton, which provides direct pathways for faster electron transport, while the conformally coated TiO 2 layer acts as the "guest" absorber layer. The unique composite IO structure is fabricated through self-assembly of colloidal spheres template, a hydrothermal method and atomic layer deposition (ALD). Owing to its large surface area and efficient charge collection, the FTO/FTO-NC/TiO 2 composite IO photoanode shows excellent photocatalytic properties for PEC water splitting. With optimized dimensions of the SnO 2 nanocrystals and the thickness of the ALD TiO 2 absorber layers, the 3D FTO/FTO-NC/TiO 2 composite IO photoanode yields a photocurrent density of 1.0 mA cm -2 at 1.23 V versus reversible hydrogen electrode (RHE) under AM 1.5 illumination, which is four times higher than that of the FTO/TiO 2 IO reference photoanode. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

Host-guest capability of a three-dimensional heterometallic macrocycle.

PubMed

Fan, Qi-Jia; Lin, Yue-Jian; Hahn, F Ekkehardt; Jin, Guo-Xin

2018-02-13

A three-dimensional heterometallic coordination macrocycle is found to be capable of encapsulating planar pyrene (G1), coronene (G4) and non-planar corannulene (G2) guest molecules in high yields, giving rise to 1 : 1 host-guest complexes. The bowl-shaped guest corannulene is found to be significantly flattened upon inclusion within the cavity. However, macrocyclic compounds with larger cavity sizes, which form 1 : 1 stoichiometry assemblies with a naphthalene bisimide planar molecule (G3), are more inclined to form infinite sandwich structures. Furthermore, these heterometallic coordination macrocycles can be destroyed in the presence of a soft base to form hexanuclear triangular prism complexes. These structures are unambiguously revealed by single-crystal X-ray analysis.

Supramolecular structures on silica surfaces and their adsorptive properties.

PubMed

Belyakov, Vladimir N; Belyakova, Lyudmila A; Varvarin, Anatoly M; Khora, Olexandra V; Vasilyuk, Sergei L; Kazdobin, Konstantin A; Maltseva, Tetyana V; Kotvitskyy, Alexey G; Danil de Namor, Angela F

2005-05-01

The study of adsorptive and chemical immobilization of beta-cyclodextrin on a surface of hydroxylated silicas with various porous structure is described. Using IR spectroscopy, thermal gravimetrical analysis with a programmed heating, and chemical analysis of the silica surface, it is shown that the process of adsorption-desorption of beta-cyclodextrin depends on the porous structure of the silica. The reaction of esterification was used for chemical grafting of beta-cyclodextrin on the surface of hydroxylated silicas. Hydrolytic stability of silicas chemically modified by beta-cyclodextrin apparently is explained by simultaneous formation of chemical and hydrogen bonds between surface silanol groups and hydroxyl groups of beta-cyclodextrin. The uptake of the cations Cu(II), Cd(II), and Pb(II) and the anions Cr(VI) and As(V) by silicas modified with beta-cyclodextrin is investigated as a function of equilibrium ion concentrations. The increase of ion uptake and selectivity of ion extraction in comparison with starting silicas is established. It is due to the formation of surface inclusion complexes of the "host-guest" type in which one molecule of beta-cyclodextrin interacts simultaneously with several ions.

Spectrofluorimetric study on the inclusion interaction between vitamin K 3 with p-( p-sulfonated benzeneazo)calix[6]arene and determination of VK 3

NASA Astrophysics Data System (ADS)

Zhou, Yunyou; Xu, Hongwei; Wu, Lian; Liu, Chun; Lu, Qin; Wang, Lun

2008-11-01

The characteristics of host-guest complexation between p-( p-sulfonated benzeneazo) calix[6]arene (SBC6A) and vitamin K 3 (VK 3) were investigated by fluorescence spectrometry. A 1:1 stoichiometry for the complexation was established and was verified by Job's plot. An association constant of 4.95 × 10 3 L mol -1 at 20 °C was calculated by applying a deduced equation. The interaction mechanism of the inclusion complex was discussed. It was found that the fluorescence of SBC6A could be remarkably quenched by an appropriate amount of VK 3 especially when non-ionic surfactant Triton X-100 existed. According to the obtained results, a novel sensitive spectrofluorimetric method for the determination of VK 3 based on supramolecular complex was developed with a linear range of 5.0 × 10 -7-3.0 × 10 -5 mol L -1 and a detection limit of 2.0 × 10 -7 mol L -1. The proposed method was used to determine VK 3 in commercial preparations with satisfactory results.

Spectrofluorimetric study on the inclusion interaction between vitamin K3 with p-(p-sulfonated benzeneazo)calix[6]arene and determination of VK3.

PubMed

Zhou, Yunyou; Xu, Hongwei; Wu, Lian; Liu, Chun; Lu, Qin; Wang, Lun

2008-11-15

The characteristics of host-guest complexation between p-(p-sulfonated benzeneazo) calix[6]arene (SBC6A) and vitamin K3 (VK3) were investigated by fluorescence spectrometry. A 1:1 stoichiometry for the complexation was established and was verified by Job's plot. An association constant of 4.95 x 10(3)L mol(-1) at 20 degrees C was calculated by applying a deduced equation. The interaction mechanism of the inclusion complex was discussed. It was found that the fluorescence of SBC6A could be remarkably quenched by an appropriate amount of VK3 especially when non-ionic surfactant Triton X-100 existed. According to the obtained results, a novel sensitive spectrofluorimetric method for the determination of VK3 based on supramolecular complex was developed with a linear range of 5.0 x 10(-7) -3.0 x 10(-5)mol L(-1) and a detection limit of 2.0 x 10(-7)mol L(-1). The proposed method was used to determine VK3 in commercial preparations with satisfactory results.

Reversible and oriented immobilization of ferrocene-modified proteins.

PubMed

Yang, Lanti; Gomez-Casado, Alberto; Young, Jacqui F; Nguyen, Hoang D; Cabanas-Danés, Jordi; Huskens, Jurriaan; Brunsveld, Luc; Jonkheijm, Pascal

2012-11-21

Adopting supramolecular chemistry for immobilization of proteins is an attractive strategy that entails reversibility and responsiveness to stimuli. The reversible and oriented immobilization and micropatterning of ferrocene-tagged yellow fluorescent proteins (Fc-YFPs) onto β-cyclodextrin (βCD) molecular printboards was characterized using surface plasmon resonance (SPR) spectroscopy and fluorescence microscopy in combination with electrochemistry. The proteins were assembled on the surface through the specific supramolecular host-guest interaction between βCD and ferrocene. Application of a dynamic covalent disulfide lock between two YFP proteins resulted in a switch from monovalent to divalent ferrocene interactions with the βCD surface, yielding a more stable protein immobilization. The SPR titration data for the protein immobilization were fitted to a 1:1 Langmuir-type model, yielding K(LM) = 2.5 × 10(5) M(-1) and K(i,s) = 1.2 × 10(3) M(-1), which compares favorably to the intrinsic binding constant presented in the literature for the monovalent interaction of ferrocene with βCD self-assembled monolayers. In addition, the SPR binding experiments were qualitatively simulated, confirming the binding of Fc-YFP in both divalent and monovalent fashion to the βCD monolayers. The Fc-YFPs could be patterned on βCD surfaces in uniform monolayers, as revealed using fluorescence microscopy and atomic force microscopy measurements. Both fluorescence microscopy imaging and SPR measurements were carried out with the in situ capability to perform cyclic voltammetry and chronoamperometry. These studies emphasize the repetitive desorption and adsorption of the ferrocene-tagged proteins from the βCD surface upon electrochemical oxidation and reduction, respectively.

Electrostatically Driven Guest Binding in a Self-Assembled Porous Network at the Liquid/Solid Interface.

PubMed

Iritani, Kohei; Ikeda, Motoki; Yang, Anna; Tahara, Kazukuni; Anzai, Masaru; Hirose, Keiji; De Feyter, Steven; Moore, Jeffrey S; Tobe, Yoshito

2018-05-29

We present here the construction of a self-assembled two-dimensional (2D) porous monolayer bearing a highly polar 2D space to study guest co-adsorption through electrostatic interactions at the liquid/solid interface. For this purpose, a dehydrobenzo[12]annulene (DBA) derivative, DBA-TeEG, having tetraethylene glycol (TeEG) groups at the end of the three alternating alkoxy chains connected by p-phenylene linkers was synthesized. As a reference host molecule, DBA-C10, having nonpolar C 10 alkyl chains at three alternating terminals, was employed. As guest molecules, hexagonal phenylene-ethynylene macrocycles (PEMs) attached by triethylene glycol (TEG) ester and hexyl ester groups, PEM-TEG and PEM-C6, respectively, at each vertex of the macrocyclic periphery were used. Scanning tunneling microscopy observations at the 1,2,4-trichlorobenzene/highly oriented pyrolytic graphite interface revealed that PEM-TEG was immobilized in the pores formed by DBA-TeEG at higher probability because of electrostatic interactions such as dipole-dipole and hydrogen bonding interactions between oligoether units of the host and guest, in comparison to PEM-C6 with nonpolar groups. These observations are discussed based on molecular mechanics simulations to investigate the role of the polar functional groups. When a nonpolar host matrix formed by DBA-C10 was used, however, only phase separation and preferential adsorption were observed; virtually no host-guest complexation was discernible. This is ascribed to the strong affinity between the guest molecules which form by themselves densely packed van der Waals networks on the surface.

Subcutaneous injection of water-soluble multi-walled carbon nanotubes in tumor-bearing mice boosts the host immune activity

NASA Astrophysics Data System (ADS)

Meng, Jie; Yang, Man; Jia, Fumin; Kong, Hua; Zhang, Weiqi; Wang, Chaoying; Xing, Jianmin; Xie, Sishen; Xu, Haiyan

2010-04-01

The immunological responses induced by oxidized water-soluble multi-walled carbon nanotubes on a hepatocarcinoma tumor-bearing mice model via a local administration of subcutaneous injection were investigated. Experimental results show that the subcutaneously injected carbon nanotubes induced significant activation of the complement system, promoted inflammatory cytokines' production and stimulated macrophages' phagocytosis and activation. All of these responses increased the general activity of the host immune system and inhibited the progression of tumor growth.

Mechanisms, pathways, and dynamics of excited-state energy flow in self-assembled wheel-and-spoke light-harvesting architectures.

PubMed

Song, Hee-eun; Kirmaier, Christine; Schwartz, Jennifer K; Hindin, Eve; Yu, Lianhe; Bocian, David F; Lindsey, Jonathan S; Holten, Dewey

2006-10-05

Static and time-resolved optical measurements are reported for two cyclic hexameric porphyrin arrays and their self-assembled complexes with guest chromophores. The hexameric hosts contain zinc porphyrins and 0 or 3 free base (Fb) porphyrins (denoted Zn(6) or Zn(3)Fb(3), respectively). The guests are a tripyridyl arene (TP) and a dipyridyl-substituted free base porphyrin (DPFb), each of which coordinates to zinc porphyrins of a host via pyridyl-zinc dative bonding. Each architecture is designed to have an overall gradient of excited-state energies that affords excitation funneling within the host and ultimately to the guest. Collectively, the studies delineate the various pathways, mechanisms, and rate constants of energy flow among the weakly coupled constituents of the host-guest complexes. The pathways include downhill unidirectional energy transfer between adjacent chromophores, bidirectional energy migration between identical chromophores, and energy transfer between nonadjacent chromophores. The energy transfer to the lowest-energy chromophore(s) within the backbone of a hexameric host (Fb porphyrins in Zn(3)Fb(3) or pyridyl-coordinated zinc porphyrins in Zn(6)*TP and Zn(6)*DPFb) proceeds primarily via a through-bond mechanism; the transfer is rapid (approximately 40 ps depending on the array) and essentially quantitative (>or=98%). The energy transfer from a pyridyl-coordinated zinc porphyrin of the host to the Fb porphyrin guest in the Zn(6)*DPFb complex is almost exclusively Förster through-space in nature; this process is much slower ( approximately 1 ns) and has a lower yield (65%). These studies highlight the utility of cyclic architectures for efficient light harvesting and energy transfer to a designated trapping site.

Design, synthesis, and characterization of new phosphazene related materials, and study the structure property correlations

NASA Astrophysics Data System (ADS)

Tian, Zhicheng

The work described in this thesis is divided into three major parts, and all of which involve the exploration of the chemistry of polyphosphazenes. The first part (chapters 2 and 3) of my research is synthesis and study polyphoshazenes for biomedical applications, including polymer drug conjugates and injectable hydrogels for drug or biomolecule delivery. The second part (chapters 4 and 5) focuses on the synthesis of several organic/inorganic hybrid polymeric structures, such as diblock, star, brush and palm tree copolymers using living cationic polymerization and atom transfer radical polymerization techniques. The last part (chapters 6 and 7) is about exploratory synthesis of new polymeric structures with fluorinated side groups or cycloaliphatic side groups, and the study of new structure property relationships. Chapter 1 is an outline of the fundamental concepts for polymeric materials, as such the history, important definitions, and some introductory material for to polymer chemistry and physics. The chemistry and applications of phopshazenes is also briefly described. Chapter 2 is a description of the design, synthesis, and characterization of development of a new class of polymer drug conjugate materials based on biodegradable polyphosphazenes and antibiotics. Poly(dichlorophosphazene), synthesized by a thermal ring opening polymerization, was reacted with up to 25 mol% of ciprofloxacin or norfloxacin and three different amino acid esters (glycine, alanine, or phenylalanine) as cosubstituents via macromolecular substitutions. Nano/microfibers of several selected polymers were prepared by an electrospinning technique. Chapter 3 is concerned with the development of a class of injectable and biodegradable hydrogels based on water-soluble poly(organophosphazenes) containing oligo(ethylene glycol) methyl ethers and glycine ethyl esters. The hydrogels can be obtained by mixing alpha-cyclodextrin aqueous solution and poly(organophosphazenes) aqueous solution in various gelation rates depending on the polymer structures and the concentrations. The rheological measurements of the supramolecular hydrogels indicate a fast gelation process and flowable character under a large stain. Chapter 4 outlines the preparation of a number of amphiphilic diblock copolymers based on poly[bis(trifluoroethoxy)phosphazene] (TFE) as the hydrophobic block and poly(dimethylaminoethylmethacrylate) (PDMAEMA) as the hydrophilic block. The TFE block was synthesized first by the controlled living cationic polymerization of a phosphoranimine, followed by replacement of all the chlorine atoms using sodium trifluoroethoxide. To allow for the growth of the PDMAEMA block, 3-azidopropyl-2-bromo-2-methylpropanoate, an atom transfer radical polymerization (ATRP) initiator, was grafted onto the endcap of the TFE block via the 'click' reaction followed by the ATRP of 2-(dimethylamino)ethyl methacrylate (DMAEMA). Chapter 5 is a report on the design and assembly of polyphosphazene materials based on the non-covalent "host--guest" interactions either at the terminus of the polymeric main-chains or the pendant side-chains. The supramolecular interaction at the main chain terminus was used to produce amphiphilic palm-tree like pseudo-block copolymers via host-guest interactions between an adamantane end-functionalized polyphosphazene and a 4-armed beta-cyclodextrin (beta-CD) initiated poly[poly(ethylene glycol) methyl ether methacylate] branched-star type polymer. The formation of micelles of the obtained amphiphiles was analyzed by fluorescence technique, dynamic light scattering, transmission electron microscopy, and atomic force microscopy. Chapter 6 is an investigation of the influence of bulky fluoroalkoxy side groups on the properties of polyphosphazenes. A new series of mixed-substituent high polymeric poly(fluoroalkoxyphosphazenes) containing trifluoroethoxy and branched fluoroalkoxy side groups was synthesized and characterized by NMR and GPC methods. These polymers contained 19--29 mol% of di-branched hexafluoropropoxy groups or 4mol% of tri-branched tert-perfluorobutoxy groups, which serve as regio-irregularities to reduce the macromolecular microcrystallinity. The structure--property correlations of the polymers were then analyzed and interpreted by several techniques: specifically by the thermal behavior by DSC and TGA methods, the crystallinity by wide-angle X-ray diffraction, and the surface hydrophobicity/oleophobicity by contact angle measurements. (Abstract shortened by UMI.). Chapter 7 is an outline of the exploratory synthesis of a new series of phosphazene model cyclic trimers and single- and mixed- substituent high polymers containing cyclic aliphatic rings, --CnH2n-1 (where n = 4--8). The cylco-aliphatic side group containing phosphazenes expand the structural and property boundaries of phosphazene chemistry, and suggest additional approaches for studying slow macromolecular substitution reactions and substituent exchange reactions.

Paramagnetic NMR Investigation of Dendrimer-Based Host-Guest Interactions

PubMed Central

Wang, Fei; Shao, Naimin; Cheng, Yiyun

2013-01-01

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. PMID:23762249

Chemical Sensors Based on Cyclodextrin Derivatives.

PubMed

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.

Chirality Differentiation by Diffusion in Chiral Nematic Liquid Crystals

NASA Astrophysics Data System (ADS)

Jiang, Jinghua; Yang, Deng-Ke

2017-01-01

Chirality is of great importance in the living world. It helps differentiate biochemical reactions such as those that take place during digestion. It may also help differentiate physical processes such as diffusion. Aiming to study the latter effect, we investigate the diffusion of guest chiral molecules in chiral nematic (cholesteric) liquid-crystal hosts. We discover that the diffusion dramatically depends on the handedness of the guest and host molecules and the chiral differentiation is greatly enhanced by the proper alignment of the liquid-crystal host. The diffusion of a guest chiral molecule in a chiral host with the same handedness is much faster than in a chiral host with opposite handedness. We also observe that the differentiation of chirality depends on the diffusion direction with respect to the twisting direction (helical axis). These results might be important in understanding effects of chirality on physical processes that take place in biological organisms. In addition, this effect could be utilized for enantiomer separation.

Crystallographic and theoretical studies of an inclusion complex of β-cyclodextrin with fentanyl.

PubMed

Ogawa, Noriko; Nagase, Hiromasa; Loftsson, Thorsteinn; Endo, Tomohiro; Takahashi, Chisato; Kawashima, Yoshiaki; Ueda, Haruhisa; Yamamoto, Hiromitsu

2017-10-15

The crystal structure of an inclusion complex of β-cyclodextrin (β-CD) with fentanyl was determined by single crystal X-ray diffraction analysis. The crystal belongs to the triclinic space group P1 and the complex comprises one fentanyl, two β-CD, and several water molecules. β-CD and fentanyl form a host-guest inclusion complex at a ratio of 2:1 and the asymmetric unit of the complex contains two host molecules (β-CDs) in a head-to-head arrangement that form dimers through hydrogen bonds between the secondary hydroxyl groups of β-CD and one guest molecule. Fentanyl is totally contained within the β-CD cavity and the structure of the phenylethyl part of fentanyl inside the dimeric cavity of the complex is disordered. Furthermore, theoretical molecular conformational calculations were conducted to clarify the mobility of the guest molecule in the β-CD cavity using CONFLEX software. Crystal optimization and crystal energy calculations were also conducted. The results of the theoretical calculations confirmed that the conformation of disorder part 1, which was high in occupancy by crystal structure analysis, was more stable. The phenylethyl part of fentanyl existed in several stable conformations. Copyright © 2017 Elsevier B.V. All rights reserved.

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).

PubMed

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.

Heterostructured layered aluminosilicate-itraconazole nanohybrid for drug delivery system.

PubMed

Yang, Jae-Hun; Jung, Hyun; Kim, Su Yeon; Yo, Chul Hyun; Choy, Jin-Ho

2013-11-01

A nanohybrid, consisting of layered aluminosilicate as a host material and itraconazole as a guest molecule, was successfully synthesized through the interfacial intercalation reaction across the boundary between water and water-immiscible liquid at the various pH. According to the powder X-ray diffraction pattern, the basal spacing of the intraconazole-layered aluminosilicate nanohybrid increased from 14.7 to 22.7 A depending on the pH of the aqueous suspension. The total amounts of itraconazole in the hybrids were determined to be 2.3-25.4 wt% by HPLC analysis. The in vivo pharmacokinetics study was performed in rats in order to compare the absorptions of itraconazole for the itraconazole-layered aluminosilicate nanohybrid and a commercial product, Sporanox. The pharmacokinetic data for the nanohybrid and Sporanox showed that the mean area under the plasma concentration-time curve (AUC, 2477 +/- 898 ng x hr/mL and 2630 +/- 953 ng x hr/mL, respectively) and maximum concentration (Cmax, 225.4 +/- 77.4 ng x hr/mL and 223.6 +/- 51.9 ng x hr/mL, respectively), were within the bioequivalence (BE) range. Therefore, we concluded that this drug-layered aluminosilicate nanohybrid system has a great potential for its application in formulation of poorly soluble drugs.

Host-Guest Interaction between Herbicide Oxadiargyl and Hydroxypropyl-β-Cyclodextrin

PubMed Central

Benfeito, Sofia; Borges, Fernanda; Garrido, E. Manuela

2013-01-01

In the face of a growing human population and increased urbanization, the demand for pesticides will simply rise. Farmers must escalate yields on increasingly fewer farm acres. However, the risks of pesticides, whether real or perceived, may force changes in the way these chemicals are used. Scientists are working toward pest control plans that are environmentally sound, effective, and profitable. In this context the development of new pesticide formulations which may improve application effectiveness, safety, handling, and storage can be pointed out as a solution. As a contribution to the area, the microencapsulation of the herbicide oxadiargyl (OXA) in (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD) was performed. The study was conducted in different aqueous media (ultrapure water and in different pH buffer solutions). In all cases an increment of the oxadiargyl solubility as a function of the HP-β-CD concentration that has been related to the formation of an inclusion complex was verified. UV-Vis and NMR experiments allowed concluding that the stoichiometry of the OXA/HP-β-CD complex formed is 1 : 1. The gathered results can be regarded as an important step for its removal from industrial effluents and/or to increase the stabilizing action, encapsulation, and adsorption in water treatment plants. PMID:24396310

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

NASA Astrophysics Data System (ADS)

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

2011-11-01

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 regime the charge carrier density dependent mobility can be described consistently with the extended Gaussian disorder model, with a density of hopping sites which is proportional to the TAD concentration and comparable to the molecular density.

Structural and electronic properties of the alkali metal incommensurate phases

NASA Astrophysics Data System (ADS)

Woolman, Gavin; Naden Robinson, Victor; Marqués, Miriam; Loa, Ingo; Ackland, Graeme J.; Hermann, Andreas

2018-05-01

Under pressure, the alkali elements sodium, potassium, and rubidium adopt nonperiodic structures based on two incommensurate interpenetrating lattices. While all elements form the same "host" lattice, their "guest" lattices are all distinct. The physical mechanism that stabilizes these phases is not known, and detailed calculations are challenging due to the incommensurability of the lattices. Using a series of commensurate approximant structures, we tackle this issue using density functional theory calculations. In Na and K, the calculations prove accurate enough to reproduce not only the stability of the host-guest phases, but also the complicated pressure dependence of the host-guest ratio and the two guest-lattice transitions. We find Rb-IV to be metastable at all pressures, and suggest it is a high-temperature phase. The electronic structure of these materials is unique: they exhibit two distinct, coexisting types of electride behavior, with both fully localized pseudoanions and electrons localized in 1D wells in the host lattice, leading to low conductivity. While all phases feature pseudogaps in the electronic density of states, the perturbative free-electron picture applies to Na, but not to K and Rb, due to significant d -orbital population in the latter.

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

PubMed

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.

Amphiphilic inclusion spaces for various guests and regulation of fluorescence intensity of 1,8-bis(4-aminophenyl)anthracene crystals.

PubMed

Sugino, Misa; Hatanaka, Keisuke; Araki, Yusuke; Hisaki, Ichiro; Miyata, Mikiji; Tohnai, Norimitsu

2014-03-10

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

Investigation of the interactions of silibinin with 2-hydroxypropyl-β-cyclodextrin through biophysical techniques and computational methods.

PubMed

Kellici, Tahsin F; Ntountaniotis, Dimitrios; Leonis, Georgios; Chatziathanasiadou, Maria; Chatzikonstantinou, Alexandra V; Becker-Baldus, Johanna; Glaubitz, Clemens; Tzakos, Andreas G; Viras, Kyriakos; Chatzigeorgiou, Petros; Tzimas, Stavros; Kefala, Evangelia; Valsami, Georgia; Archontaki, Helen; Papadopoulos, Manthos G; Mavromoustakos, Thomas

2015-03-02

Cyclodextrins (CDs) are a well-known class of supermolecules that have been widely used to protect drugs against conjugation and metabolic inactivation as well as to enhance the aqueous solubility and hence to ameliorate the oral bioavailability of sparingly soluble drug molecules. The hepatoprotectant drug silibinin can be incorporated into CDs, and here we elucidate the interaction between the drug and the host at the molecular level. The complexation product of silibinin with 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) is characterized by Differential Scanning Calorimetry, mass spectrometry, solid and liquid high-resolution NMR spectroscopy. The chemical shift changes using (13)C CP/MAS on the complexing of the guest with the host provided significant information on the molecular interactions, and they were in agreement with the 2D NOESY results. These results point out that in both solid and liquid forms, the drug is engulfed and interacts with HP-β-CD in identical manner. Molecular dynamics calculations have been performed to examine the thermodynamic characteristics associated with the silibinin-HP-β-CD interactions and to study the stability of the complex. To approximate the physiological conditions, the aqueous solubility and dissolution characteristics of the complex at pH states simulating those of the upper gastrointestinal tract have been applied. To evaluate the antiproliferative activity of silibinin-HP-β-CD complex comparatively to silibinin in MCF-7 human cancer cells, MTT assays have been performed.

para-Sulfonatocalix[6]arene-modified silver nanoparticles electrodeposited on glassy carbon electrode: preparation and electrochemical sensing of methyl parathion.

PubMed

Bian, Yinghui; Li, Chunya; Li, Haibing

2010-05-15

In this paper, a new electrochemical sensor, based on modified silver nanoparticles, was fabricated using one-step electrodeposition approach. The para-sulfonatocalix[6]arene-modified silver nanoparticles coated on glassy carbon electrode (pSC(6)-Ag NPs/GCE) was characterized by attenuated total reflection IR spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), etc. The pSC(6) as the host are highly efficient to capture organophosphates (OPs), which dramatically facilitates the enrichment of nitroaromatic OPs onto the electrochemical sensor surface. The combination of the host-guest supramolecular structure and the excellent electrochemical catalytic activities of the pSC(6)-Ag NPs/GCE provides a fast, simple, and sensitive electrochemical method for detecting nitroaromatic OPs. In this work, methyl parathion (MP) was used as a nitroaromatic OP model for testing the proposed sensor. In comparison with Ag NPs-modified electrode, the cathodic peak current of MP was amplified significantly. Differential pulse voltammetry was used for the simultaneous determination of MP. Under optimum conditions, the current increased linearly with the increasing concentration of MP in the range of 0.01-80microM, with a detection limit of 4.0nM (S/N=3). The fabrication reproducibility and stability of the sensor is better than that of enzyme-based electrodes. The possible underlying mechanism is discussed.

Characterization of supramolecular (H2O)18 water morphology and water-methanol (H2O)15(CH3OH)3 clusters in a novel phosphorus functionalized trimeric amino acid host.

PubMed

Raghuraman, Kannan; Katti, Kavita K; Barbour, Leonard J; Pillarsetty, Nagavarakishore; Barnes, Charles L; Katti, Kattesh V

2003-06-11

Phosphorus functionalized trimeric alanine compounds (l)- and (d)-P(CH(2)NHCH(CH(3))COOH)(3) 2 are prepared in 90% yields by the Mannich reaction of Tris(hydroxymethyl)phosphine 1 with (l)- or (d)- Alanine in aqueous media. The hydration properties of (l)-2 and (d)-2 in water and water-methanol mixtures are described. The crystal structure analysis of (l)-2.4H(2)O, reveals that the alanine molecules pack to form two-dimensional bilayers running parallel to (001). The layered structural motif depicts two closely packed monolayers of 2 each oriented with its phosphorus atoms projected at the center of the bilayer and adjacent monolayers are held together by hydrogen bonds between amine and carboxylate groups. The water bilayers are juxtaposed with the H-bonded alanine trimers leading to 18-membered (H(2)O)(18) water rings. Exposure of aqueous solution of (l)-2 and (d)-2 to methanol vapors resulted in closely packed (l)-2 and (d)-2 solvated with mixed water-methanol (H(2)O)(15)(CH(3)OH)(3) clusters. The O-O distances in the mixed methanol-water clusters of (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH (O-O(average) = 2.857 A) are nearly identical to the O-O distance observed in the supramolecular (H(2)O)(18) water structure (O-O(average) = 2.859 A) implying the retention of the hydrogen bonded structure in water despite the accommodation of hydrophobic methanol groups within the supramolecular (H(2)O)(15)(CH(3)OH)(3) framework. The O-O distances in (l)-2.3H(2)O.CH(3)OH and (d)-2.3H(2)O.CH(3)OH and in (H(2)O)(18) are very close to the O-O distance reported for liquid water (2.85 A).

A molecular dynamics study of model SI clathrate hydrates: the effect of guest size and guest-water interaction on decomposition kinetics.

PubMed

Das, Subhadip; Baghel, Vikesh Singh; Roy, Sudip; Kumar, Rajnish

2015-04-14

One of the options suggested for methane recovery from natural gas hydrates is molecular replacement of methane by suitable guests like CO2 and N2. This approach has been found to be feasible through many experimental and molecular dynamics simulation studies. However, the long term stability of the resultant hydrate needs to be evaluated; the decomposition rate of these hydrates is expected to depend on the interaction between these guest and water molecules. In this work, molecular dynamics simulation has been performed to illustrate the effect of guest molecules with different sizes and interaction strengths with water on structure I (SI) hydrate decomposition and hence the stability. The van der Waals interaction between water of hydrate cages and guest molecules is defined by Lennard Jones potential parameters. A wide range of parameter spaces has been scanned by changing the guest molecules in the SI hydrate, which acts as a model gas for occupying the small and large cages of the SI hydrate. All atomistic simulation results show that the stability of the hydrate is sensitive to the size and interaction of the guest molecules with hydrate water. The increase in the interaction of guest molecules with water stabilizes the hydrate, which in turn shows a slower rate of hydrate decomposition. Similarly guest molecules with a reasonably small (similar to Helium) or large size increase the decomposition rate. The results were also analyzed by calculating the structural order parameter to understand the dynamics of crystal structure and correlated with the release rate of guest molecules from the solid hydrate phase. The results have been explained based on the calculation of potential energies felt by guest molecules in amorphous water, hydrate bulk and hydrate-water interface regions.

Large refractive index variations induced by accumulating triplet excitons under photoexcitation at low power

NASA Astrophysics Data System (ADS)

Hori, Tomoe; Totani, Kenro; Hirata, Shuzo; Watanabe, Toshiyuki

2018-07-01

Herein, we present a method for the modification of the refractive index (n), based on employing an organic molecule with a long triplet excited-state lifetime. A host-guest material composed of a cyclic aromatic as the guest and an amorphous steroidal compound as the host was used to modulate n. The guest material exhibited a triplet lifetime longer than 1 s, and a high-density triplet excited-state population was obtained upon excitation with blue-violet light. The refractive index could be changed by 0.002, even when using a relatively low excitation power level of 100 mW cm-2.

Electrospun Lipid Binding Proteins Composite Nanofibers with Antibacterial Properties.

PubMed

Tomaselli, Simona; Ramirez, Diego Omar Sanchez; Carletto, Riccardo Andrea; Varesano, Alessio; Vineis, Claudia; Zanzoni, Serena; Molinari, Henriette; Ragona, Laura

2017-04-01

Electrospinning is here used for the first time to prepare nanofibers including a host/guest complex in a keratin/poly(ethylene oxide) matrix. The host is a lipid binding protein and the guest is an insoluble bactericidal molecule, irgasan, bound within the protein internal cavity. The obtained nanofibers, characterized by scanning electron microscopy, exhibit excellent antibacterial activity toward Gram positive and negative bacteria, even with a moderate protein/irgasan cargo. Solution NMR studies, employed to provide molecular information on the cargo system, points to a micromolar affinity, compatible with both the electrospinning process and slow guest release. The versatility of the carrier protein, capable of interacting with a variety of druggable hydrophobic molecules, is exploitable for the development of innovative biomedical devices, whose properties can be tuned by the selected guest. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Triplet exciton confinement for enhanced fluorescent organic light-emitting diodes using a co-host system

NASA Astrophysics Data System (ADS)

Yoo, Han Kyu; Lee, Ho Won; Lee, Song Eun; Kim, Young Kwan; Kim, Se Hyun; Yoon, Seung Soo; Park, Jaehoon

2016-05-01

In this work, the co-host system within an emitting layer (EML) consists of the host and triplet managing (TM) host materials. A set of EML structures was fabricated with various concentrations of the TM host (0, 10, 30, 50, and 70%). The TM host triplet energy level is lower than the energy levels of the host and the guest, which leads to a reduction in the triplet exciton density and the singlet-triplet annihilation of the guest. Blue fluorescent organic light-emitting diodes exhibit a maximum luminous efficiency (LE) and an external quantum efficiency (EQE) of 9.74 cd/A and 4.92%, respectively. In addition, the efficiency roll-off ratios of the LE and the EQE are 14.25 and 13.16%, respectively.

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

PubMed Central

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

Multiheteromacrocycles that Complex Metal Ions. Ninth Progress Report (includes results of last three years), 1 May 1980 -- 30 April 1983

DOE R&D Accomplishments Database

Cram, D. J.

1982-09-15

The overall objective of this research is to design, synthesize, and evaluate cyclic and polycyclic host organic compounds for the abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions, or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; numbers of binding sites; characters of binding sites; and valences. The hope is to synthesize new classes of compounds useful in the separation of metal ions, their complexes, and their clusters.

Electrospinning bioactive supramolecular polymers from water.

PubMed

Tayi, Alok S; Pashuck, E Thomas; Newcomb, Christina J; McClendon, Mark T; Stupp, Samuel I

2014-04-14

Electrospinning is a high-throughput, low-cost technique for manufacturing long fibers from solution. Conventionally, this technique is used with covalent polymers with large molecular weights. We report here the electrospinning of functional peptide-based supramolecular polymers from water at very low concentrations (<4 wt %). Molecules with low molecular weights (<1 kDa) could be electrospun because they self-assembled into one-dimensional supramolecular polymers upon solvation and the critical parameters of viscosity, solution conductivity, and surface tension were optimized for this technique. The supramolecular structure of the electrospun fibers could ensure that certain residues, like bioepitopes, are displayed on the surface even after processing. This system provides an opportunity to electrospin bioactive supramolecular materials from water for biomedical applications.

Seeking Ways to Break Energy Storage Limits

DTIC Science & Technology

2016-05-02

system sizes that we simulated. 15. SUBJECT TERMS density functional theory, guest-host structures, carbon nanotubes , free atom limit, geometry...unlimited. iii Contents List of Figures iv 1. Introduction 1 2. Xenon-Buckminsterfullerene (Xe-C60) 3 3. Xe-C980 4 4. Xe-Carbon Nanotube (CNT) 4 5...calculations. 4. Xe-Carbon Nanotube (CNT) Because of our inability to attain guest-host complexes that would achieve energies in excess of the

Self-assembling graphene-anthraquinone-2-sulphonate supramolecular nanostructures with enhanced energy density for supercapacitors.

PubMed

Gao, Lifang; Gan, Shiyu; Li, Hongyan; Han, Dongxue; Li, Fenghua; Bao, Yu; Niu, Li

2017-07-07

Boosting the energy density of capacitive energy storage devices remains a crucial issue for facilitating applications. Herein, we report a graphene-anthraquinone supramolecular nanostructure by self-assembly for supercapacitors. The sulfonated anthraquinone exhibits high water solubility, a π-conjugated structure and redox active features, which not only serve as a spacer to interact with and stabilize graphene but also introduce extra pseudocapacitance contributions. The formed nest-like three-dimensional (3D) nanostructure with further hydrothermal treatment enhances the accessibility of ion transfer and exposes the redox-active quinone groups in the electrolytes. A fabricated all-solid-state flexible symmetric device delivers a high specific capacitance of 398.5 F g -1 at 1 A g -1 (1.5 times higher than graphene), superior energy density (52.24 Wh kg -1 at about 1 kW kg -1 ) and good stability (82% capacitance retention after 10 000 cycles).

Supramolecular PEGylation of biopharmaceuticals

PubMed Central

Webber, Matthew J.; Vinciguerra, Brittany; Cortinas, Abel B.; Thapa, Lavanya S.; Jhunjhunwala, Siddharth; Isaacs, Lyle; Langer, Robert; Anderson, Daniel G.

2016-01-01

The covalent modification of therapeutic biomolecules has been broadly explored, leading to a number of clinically approved modified protein drugs. These modifications are typically intended to address challenges arising in biopharmaceutical practice by promoting improved stability and shelf life of therapeutic proteins in formulation, or modifying pharmacokinetics in the body. Toward these objectives, covalent modification with poly(ethylene glycol) (PEG) has been a common direction. Here, a platform approach to biopharmaceutical modification is described that relies on noncovalent, supramolecular host–guest interactions to endow proteins with prosthetic functionality. Specifically, a series of cucurbit[7]uril (CB[7])–PEG conjugates are shown to substantially increase the stability of three distinct protein drugs in formulation. Leveraging the known and high-affinity interaction between CB[7] and an N-terminal aromatic residue on one specific protein drug, insulin, further results in altering of its pharmacological properties in vivo by extending activity in a manner dependent on molecular weight of the attached PEG chain. Supramolecular modification of therapeutic proteins affords a noncovalent route to modify its properties, improving protein stability and activity as a formulation excipient. Furthermore, this offers a modular approach to append functionality to biopharmaceuticals by noncovalent modification with other molecules or polymers, for applications in formulation or therapy. PMID:27911829

The supramolecular chemistry of lipid oxidation and antioxidation in bulk oils

PubMed Central

Budilarto, Elizabeth S; Kamal-Eldin, Afaf

2015-01-01

The microenvironment formed by surface active compounds is being recognized as the active site of lipid oxidation. Trace amounts of water occupy the core of micro micelles and several amphiphilic minor components (e.g., phospholipids, monoacylglycerols, free fatty acids, etc.) act as surfactants and affect lipid oxidation in a complex fashion dependent on the structure and stability of the microemulsions in a continuous lipid phase such as bulk oil. The structures of the triacylglycerols and other lipid-soluble molecules affect their organization and play important roles during the course of the oxidation reactions. Antioxidant head groups, variably located near the water-oil colloidal interfaces, trap and scavenge radicals according to their location and concentration. According to this scenario, antioxidants inhibit lipid oxidation not only by scavenging radicals via hydrogen donation but also by physically stabilizing the micelles at the microenvironments of the reaction sites. There is a cut-off effect (optimum value) governing the inhibitory effects of antioxidants depending inter alias on their hydrophilic/lipophilic balance and their concentrations. These complex effects, previously considered as paradoxes in antioxidants research, are now better explained by the supramolecular chemistry of lipid oxidation and antioxidants, which is discussed in this review. PMID:26448722

Formation of Supramolecular Nanotubes by Self-assembly of a Phosphate-linked Dimeric Anthracene in Water.

PubMed

Yu, Hao; Sabetti, Mattia; Häner, Robert

2018-04-16

The assembly of supramolecular polymers from a phosphodiester-linked dimeric anthracene is described. AFM and TEM imaging reveals that the supramolecular polymers self-assemble into nanotubes in water. Subsequent photodimerization experiments indicate that the supramolecular polymerization occurs via end-to-end stacking rather than an interdigitation arrangement of the building blocks. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Non-covalent interactions across organic and biological subsets of chemical space: Physics-based potentials parametrized from machine learning

NASA Astrophysics Data System (ADS)

Bereau, Tristan; DiStasio, Robert A.; Tkatchenko, Alexandre; von Lilienfeld, O. Anatole

2018-06-01

Classical intermolecular potentials typically require an extensive parametrization procedure for any new compound considered. To do away with prior parametrization, we propose a combination of physics-based potentials with machine learning (ML), coined IPML, which is transferable across small neutral organic and biologically relevant molecules. ML models provide on-the-fly predictions for environment-dependent local atomic properties: electrostatic multipole coefficients (significant error reduction compared to previously reported), the population and decay rate of valence atomic densities, and polarizabilities across conformations and chemical compositions of H, C, N, and O atoms. These parameters enable accurate calculations of intermolecular contributions—electrostatics, charge penetration, repulsion, induction/polarization, and many-body dispersion. Unlike other potentials, this model is transferable in its ability to handle new molecules and conformations without explicit prior parametrization: All local atomic properties are predicted from ML, leaving only eight global parameters—optimized once and for all across compounds. We validate IPML on various gas-phase dimers at and away from equilibrium separation, where we obtain mean absolute errors between 0.4 and 0.7 kcal/mol for several chemically and conformationally diverse datasets representative of non-covalent interactions in biologically relevant molecules. We further focus on hydrogen-bonded complexes—essential but challenging due to their directional nature—where datasets of DNA base pairs and amino acids yield an extremely encouraging 1.4 kcal/mol error. Finally, and as a first look, we consider IPML for denser systems: water clusters, supramolecular host-guest complexes, and the benzene crystal.

Macroscopic ordering of helical pores for arraying guest molecules noncentrosymmetrically

PubMed Central

Li, Chunji; Cho, Joonil; Yamada, Kuniyo; Hashizume, Daisuke; Araoka, Fumito; Takezoe, Hideo; Aida, Takuzo; Ishida, Yasuhiro

2015-01-01

Helical nanostructures have attracted continuous attention, not only as media for chiral recognition and synthesis, but also as motifs for studying intriguing physical phenomena that never occur in centrosymmetric systems. To improve the quality of signals from these phenomena, which is a key issue for their further exploration, the most straightforward is the macroscopic orientation of helices. Here as a versatile scaffold to rationally construct this hardly accessible structure, we report a polymer framework with helical pores that unidirectionally orient over a large area (∼10 cm2). The framework, prepared by crosslinking a supramolecular liquid crystal preorganized in a magnetic field, is chemically robust, functionalized with carboxyl groups and capable of incorporating various basic or cationic guest molecules. When a nonlinear optical chromophore is incorporated in the framework, the resultant complex displays a markedly efficient nonlinear optical output, owing to the coherence of signals ensured by the macroscopically oriented helical structure. PMID:26416086

Peptide π-Electron Conjugates: Organic Electronics for Biology?

PubMed

Ardoña, Herdeline Ann M; Tovar, John D

2015-12-16

Highly ordered arrays of π-conjugated molecules are often viewed as a prerequisite for effective charge-transporting materials. Studies involving these materials have traditionally focused on organic electronic devices, with more recent emphasis on biological systems. In order to facilitate the transition to biological environments, biomolecules that can promote hierarchical ordering and water solubility are often covalently appended to the π-electron unit. This review highlights recent work on π-conjugated systems bound to peptide moieties that exhibit self-assembly and aims to provide an overview on the development and emerging applications of peptide-based supramolecular π-electron systems.

Functionalization of Cyclodextrins with N-Hydroxyphthalimide Moiety: A New Class of Supramolecular Pro-Oxidant Organocatalysts.

PubMed

Melone, Lucio; Petroselli, Manuel; Pastori, Nadia; Punta, Carlo

2015-08-31

N-hydroxyphthalimide (NHPI) is an organocatalyst for free-radical processes able to promote the aerobic oxidation of a wide range of organic substrates. In particular, NHPI can catalyze the hydroperoxidation of polyunsaturated fatty acids (PUFA). This property could be of interest for biological applications. This work reports the synthesis of two β-cyclodextrin derivatives (CD5 and CD6) having a different degree of methylation and bearing a NHPI moiety. These compounds, having different solubility in water, have been successfully tested for the hydroperoxidation of methyl linoleate, chosen as the PUFA model molecule.

Superstructure based on β-CD self-assembly induced by a small guest molecule†

PubMed Central

De Sousa, Frederico B.; Lima, Ana C.; Denadai, Ângelo M. L.; Anconi, Cleber P. A.; De Almeida, Wagner B.; Novato, Willian T. G.; Dos Santos, Hélio F.; Drum, Chester L.; Langer, Robert

2014-01-01

The size, shape and surface chemistry of nanoparticles play an important role in cellular interaction. Thus, the main objective of the present study was the determination of the β-cyclodextrin (β-CD) self-assembly thermodynamic parameters and its structure, aiming to use these assemblies as a possible controlled drug release system. Light scattering measurements led us to obtain the β-CD’s critical aggregation concentration (cac) values, and consequently the thermodynamic parameters of the β-CD spontaneous self-assembly in aqueous solution: ΔaggGo = − 16.31 kJ mol−1, ΔaggHo = − 26.48 kJ mol−1 and TΔaggSo = − 10.53 kJ mol−1 at 298.15 K. Size distribution of the self-assembled nanoparticles below and above cac was 1.5 nm and 60–120 nm, respectively. The number of β-CD molecules per cluster and the second virial coefficient were identified through Debye’s plot and molecular dynamic simulations proposed the three-fold assembly for this system below cac. Ampicillin (AMP) was used as a drug model in order to investigate the key role of the guest molecule in the self-assembly process and the β-CD:AMP supramolecular system was studied in solution, aiming to determine the structure of the supramolecular aggregate. Results obtained in solution indicated that the β-CD’s cac was not affected by adding AMP. Moreover, different complex stoichiometries were identified by nuclear magnetic resonance and isothermal titration calorimetry experiments. PMID:22234498

Multiheteromacrocycles that Complex Metal Ions. Sixth Progress Report, 1 May 1979-30 April 1980

DOE R&D Accomplishments Database

Cram, D. J.

1980-01-15

Objective is to design synthesize, and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; number of binding sites; character of binding sites; and valences. During this period, hemispherands based on an aryloxy or cyclic urea unit, spherands based on aryloxyl units only, and their complexes with alkali metals and alkaline earths were investigated. An attempt to separate {sup 6}Li and {sup 7}Li by gel permeation chromatography of lithiospherium chloride failed. (DLC)

Optical Sensing of Aromatic Amino Acids and Dipeptides by a Crown-Ether-Functionalized Perylene Bisimide Fluorophore.

PubMed

Weißenstein, Annike; Saha-Möller, Chantu R; Würthner, Frank

2018-06-04

The host-guest binding properties of a fluorescent perylene bisimide (PBI) receptor equipped with crown ether were studied in detail with a series of aromatic amino acids and dipeptides by UV/Vis, fluorescence and NMR spectroscopy. Fluorescence titration experiments showed that electron-rich aromatic amino acids and dipeptides strongly quench the fluorescence of the electron-poor PBI host molecule. Benesi-Hildebrand plots of fluorescence titration data confirmed the formation of host-guest complexes with 1:2 stoichiometry. Binding constants determined by global analysis of UV/Vis and fluorescence titration experiments revealed values between 10 3  m -1 and 10 5  m -1 in acetonitrile/methanol (9:1) at 23 °C. These data showed that amino acid l-Trp having an indole group and dipeptides containing this amino acid bind to the PBI receptor more strongly than other amino acids and dipeptides investigated here. For dipeptides containing l-Trp or l-Tyr, the binding strength is dependent on the distance between the ammonium group and the aromatic unit of the amino acids and dipeptides leading to a strong sensitivity for Ala-Trp dipeptide. 1D and 2D NMR experiments also corroborated 1:2 host-guest complexation and indicated formation of two diastereomeric species of host-guest complexes. The studies have shown that a properly functionalized PBI fluorophore functions as a molecular probe for the optical sensing of aromatic amino acids and dipeptides. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chitosan and β-Cyclodextrin-epichlorohydrin Polymer Composite Film as a Plant Healthcare Material for Carbendazim-Controlled Release to Protect Rape against Sclerotinia sclerotiorum (Lib.) de Bary.

PubMed

Wang, Delong; Jia, Mingchen; Wang, Lanying; Song, Shuang; Feng, Juntao; Zhang, Xing

2017-03-26

The influence of β-cyclodextrin-epichlorohydrin (β-CD-EP) polymers on the improvement of the solubility and antifungal activity of carbendazim has been investigated. Meanwhile, the potential of the chitosan and β-CD-EP composite film used as a plant healthcare material for carbendazim-controlled release to protect rape against Sclerotinia sclerotiorum (Lib.) de Bary has been evaluated. β-CD-EP-1 and 2 (β-CD content, 750 mg/g and 440 mg/g, respectively) were found to significantly improve the solubility of the guest molecule carbendazim (17.9 and 18.5 times, respectively) and the 1:1 stoichiometry of the host-guest was confirmed by the Job's plot. A slight synergism was observed for the β-CD-EP/carbendazim complex against S. sclerotiorum (Lib.) de Bary, indicating an enhancement to the bioavailability of carbendazim. The in vitro release studies revealed that β-CD-EP polymers could efficiently modulate carbendazim release behaviors, such as the release retard and rate. The in vivo efficacy experiments demonstrated that the β-CD-EP/carbendazim and chitosan composite film could significantly prolong the effective duration of carbendazim at a concentration of 100 μg/mL compared with spraying carbendazim at 500 μg/mL. Thereby, a highly useful and strategic concept in plant disease control by a plant healthcare material-the chitosan and polymeric β-CD-EP composite film-is provided, which could also serve as a concept for related plant diseases.

The Thermodynamics of Anion Complexation to Nonpolar Pockets.

PubMed

Sullivan, Matthew R; Yao, Wei; Tang, Du; Ashbaugh, Henry S; Gibb, Bruce C

2018-02-08

The interactions between nonpolar surfaces and polarizable anions lie in a gray area between the hydrophobic and Hofmeister effects. To assess the affinity of these interactions, NMR and ITC were used to probe the thermodynamics of eight anions binding to four different hosts whose pockets each consist primarily of hydrocarbon. Two classes of host were examined: cavitands and cyclodextrins. For all hosts, anion affinity was found to follow the Hofmeister series, with associations ranging from 1.6-5.7 kcal mol -1 . Despite the fact that cavitand hosts 1 and 2 possess intrinsic negative electrostatic fields, it was determined that these more enveloping hosts generally bound anions more strongly. The observation that the four hosts each possess specific anion affinities that cannot be readily explained by their structures, points to the importance of counter cations and the solvation of the "empty" hosts, free guests, and host-guest complexes, in defining the affinity.

Cucurbituril mediated single molecule detection and identification via recognition tunneling.

PubMed

Xiao, Bohuai; Liang, Feng; Liu, Simin; Im, JongOne; Li, Yunchuan; Liu, Jing; Zhang, Bintian; Zhou, Jianghao; He, Jin; Chang, Shuai

2018-06-08

Recognition tunneling (RT) is an emerging technique for investigating single molecules in a tunnel junction. We have previously demonstrated its capability of single molecule detection and identification, as well as probing the dynamics of intermolecular bonding at the single molecule level. Here by introducing cucurbituril as a new class of recognition molecule, we demonstrate a powerful platform for electronically investigating the host-guest chemistry at single molecule level. In this report, we first investigated the single molecule electrical properties of cucurbituril in a tunnel junction. Then we studied two model guest molecules, aminoferrocene and amantadine, which were encapsulated by cucurbituril. Small differences in conductance and lifetime can be recognized between the host-guest complexes with the inclusion of different guest molecules. By using a machine learning algorithm to classify the RT signals in a hyper dimensional space, the accuracy of guest molecule recognition can be significantly improved, suggesting the possibility of using cucurbituril molecule for single molecule identification. This work enables a new class of recognition molecule for RT technique and opens the door for detecting a vast variety of small molecules by electrical measurements.

Catalytic control over supramolecular gel formation

NASA Astrophysics Data System (ADS)

Boekhoven, Job; Poolman, Jos M.; Maity, Chandan; Li, Feng; van der Mee, Lars; Minkenberg, Christophe B.; Mendes, Eduardo; van Esch, Jan H.; Eelkema, Rienk

2013-05-01

Low-molecular-weight gels show great potential for application in fields ranging from the petrochemical industry to healthcare and tissue engineering. These supramolecular gels are often metastable materials, which implies that their properties are, at least partially, kinetically controlled. Here we show how the mechanical properties and structure of these materials can be controlled directly by catalytic action. We show how in situ catalysis of the formation of gelator molecules can be used to accelerate the formation of supramolecular hydrogels, which drastically enhances their resulting mechanical properties. Using acid or nucleophilic aniline catalysis, it is possible to make supramolecular hydrogels with tunable gel-strength in a matter of minutes, under ambient conditions, starting from simple soluble building blocks. By changing the rate of formation of the gelator molecules using a catalyst, the overall rate of gelation and the resulting gel morphology are affected, which provides access to metastable gel states with improved mechanical strength and appearance despite an identical gelator composition.

Host-Guest Assembly of a Molecular Reporter with Chiral Cyanohydrins for Assignment of Absolute Stereochemistry.

PubMed

Gholami, Hadi; Anyika, Mercy; Zhang, Jun; Vasileiou, Chrysoula; Borhan, Babak

2016-06-27

The absolute stereochemistry of cyanohydrins, derived from ketones and aldehydes, is obtained routinely, in a microscale and derivatization-free manner, upon their complexation with Zn-MAPOL, a zincated porphyrin host with a binding pocket comprised of a biphenol core. The host-guest complex leads to observable exciton-coupled circular dichroism (ECCD), the sign of which is easily correlated to the absolute stereochemistry of the bound cyanohydrin. A working model, based on the ECCD signal of cyanohydrins with known configuration, is proposed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective inclusion of PO4(3-) within persistent dimeric capsules of a tris(thiourea) receptor and evidence of cation/solvent sealed unimolecular capsules.

PubMed

Dey, Sandeep Kumar; Das, Gopal

2012-08-07

A tren-based tris(thiourea) receptor, L with electron-withdrawing p-nitrophenyl terminals has been established as a competent hydrogen-bonding scaffold that can selectively encapsulate PO(4)(3-) within persistent and rigid dimeric capsules, assembled by aromatic π-stacking interactions between the receptor side-arms. A quaternary ammonium salt of PO(4)(3-) capsules (complexes 1 and 1b, 2:1 host-guest) can reproducibly be obtained in quantitative yields by a solution-state deprotonation of [HL](+) moieties and a bound HPO(4)(2-) anion of complex 1a (HPO(4)(2-) complex of protonated L, 2:1 host-guest), induced by the presence of a large excess of anions such as HCO(3)(-), CH(3)CO(2)(-), and F(-). Qualitative as well as quantitative (1)H and (31)P NMR experiments (DMSO-d(6)) have been carried out in detail to demonstrate the selective and preferential inclusion of PO(4)(3-) by L in solution-states. Competitive crystallization experiments performed in the presence of an excess of anions such as HCO(3)(-), HSO(4)(-), CH(3)CO(2)(-), NO(3)(-) and halides (F(-) and Cl(-)) further establish the phenomenon of selective PO(4)(3-) encapsulation as confirmed by (1)H NMR, (31)P NMR, FT-IR and powder X-ray diffraction patterns of the isolated crystals. X-ray structural analyses and (31)P NMR studies of the isolated crystals of phosphate complexes (1, 1a and 1b) provide evidence of the binding discrepancy of inorganic phosphates with protonated and neutral form of L. Furthermore, extensive studies have been carried out with other anions of different sizes and dimensions in solid- and solution-states (complexes 2a, 3, 4 and 5). Crystal structure elucidation revealed the formation of a solvent (DMSO) sealed unimolecular capsule in the F(-) encapsulated complex, 2a (1:1 host-guest), a CO(3)(2-) encapsulated centrosymmetric molecular capsule in 3 (2:1 host-guest) and a cation (tetrabutylammonium) sealed SO(4)(2-) encapsulated unimolecular capsule in 4 (1:1 host-guest). 2D-NOESY NMR experiments carried out on these capsule complexes further confirm the relevant binding stoichiometry of complexes (2a-4) except for the PO(4)(3-)-encapsulated complex (1b) which showed a 1:1 host-guest stoichiometry in solution.

Host-Guest Chemistry in Integrated Porous Space Formed by Molecular Self-Assembly at Liquid-Solid Interfaces.

PubMed

Iritani, Kohei; Tahara, Kazukuni; De Feyter, Steven; Tobe, Yoshito

2017-05-16

Host-guest chemistry in two-dimensional (2D) space, that is, physisorbed monolayers of a single atom or a single molecular thickness on surfaces, has become a subject of intense current interest because of perspectives for various applications in molecular-scale electronics, selective sensors, and tailored catalysis. Scanning tunneling microscopy has been used as a powerful tool for the visualization of molecules in real space on a conducting substrate surface. For more than a decade, we have been investigating the self-assembly of a series of triangle-shaped phenylene-ethynylene macrocycles called dehydrobenzo[12]annulenes (DBAs). These molecules are substituted with six alkyl chains and are capable of forming hexagonal porous 2D molecular networks via van der Waals interactions between interdigitated alkyl chains at the interface of organic solvents and graphite. The dimension of the nanoporous space or nanowell formed by the self-assembly of DBAs can be controlled from 1.6 to 4.7 nm by simply changing the alkyl chain length from C 6 to C 20 . Single molecules as well as homoclusters and heteroclusters are capable of coadsorbing within the host matrix using shape- and size-complementarity principles. Moreover, on the basis of the versatility of the DBA molecules that allows chemical modification of the alkyl chain terminals, we were able to decorate the interior space of the nanoporous networks with functional groups such as azobenzenedicarboxylic acid for photoresponsive guest adsorption/desorption or fluoroalkanes and tetraethylene glycol groups for selective guest binding by electrostatic interactions and zinc-porphyrin units for complexation with a guest by charge-transfer interactions. In this Feature Article, we describe the general aspects of molecular self-assembly at liquid/solid interfaces, followed by the formation of programmed porous molecular networks using rationally designed molecular building blocks. We focus on our own work involving host-guest chemistry in integrated nanoporous space that is modified for specific purposes.

Facile and efficient electrochemical enantiomer recognition of phenylalanine using β-Cyclodextrin immobilized on reduced graphene oxide.

PubMed

Zaidi, Shabi Abbas

2017-08-15

This work demonstrates the facile and efficient preparation protocol of β-Cyclodextrin-reduced graphene oxide modified glassy carbon electrode (β-CD/RGO/GCE) sensor for an impressive chiral selectivity analysis for phenylalanine enantiomers. In this work, the immobilization of β-CD over graphene sheets allows the excellent enantiomer recognition due to the large surface area and high conductivity of graphene sheets and extraordinary supramolecular (host-guest interaction) property of β-CD. The proposed sensor was well characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and electrochemical impedance spectroscopy (EIS) techniques. The analytical studies demonstrated that the β-CD/RGO/GCE exhibit superior chiral recognition toward L-phenylalanine as compared to D-phenylalanine. Under optimum conditions, the developed sensor displayed a good linear range from 0.4 to 40µM with the limit of detection (LOD) values of 0.10µM and 0.15µM for l- and D-phenylalanine, respectively. Furthermore, the proposed sensor exhibits good stability and regeneration capacity. Thus, the as-synthesized material can be exploited for electrochemical enantiomer recognition successfully. Copyright © 2017 Elsevier B.V. All rights reserved.

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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.

Bulky melamine-based Zn-porphyrin tweezer as a CD probe of molecular chirality.

PubMed

Petrovic, Ana G; Vantomme, Ghislaine; Negrón-Abril, Yashira L; Lubian, Elisa; Saielli, Giacomo; Menegazzo, Ileana; Cordero, Roselynn; Proni, Gloria; Nakanishi, Koji; Carofiglio, Tommaso; Berova, Nina

2011-10-01

The transfer of chirality from a guest molecule to an achiral host is the subject of significant interest especially when, upon chiral induction, the chiroptical response of the host/guest complex can effectively report the absolute configuration (AC) of the guest. For more than a decade, dimeric metalloporphyrin hosts (tweezers) have been successfully applied as chirality probes for determination of the AC for a wide variety of chiral synthetic compounds and natural products. The objective of this study is to investigate the utility of a new class of melamine-bridged Zn-porphyrin tweezers as sensitive AC reporters. A combined approach based on an experimental CD analysis and a theoretical prediction of the prevailing interporphyrin helicity demonstrates that these tweezers display favorable properties for chiral recognition. Herein, we discuss the application of the melamine-bridged tweezer to the chiral recognition of a diverse set of chiral guests, such as 1,2-diamines, α-amino-esters and amides, secondary alcohols, and 1,2-amino-alcohols. The bulky periphery and the presence of a rigid porphyrin linkage lead, in some cases, to a more enhanced CD sensitivity than that reported earlier with other tweezers. Copyright © 2011 Wiley-Liss, Inc.

Assembly and property research on seven 0D-3D complexes derived from imidazole dicarboxylate and 1,2-bi(pyridin-4-yl)ethene

NASA Astrophysics Data System (ADS)

Mu, Bao; Li, Qian; Lv, Lei; Yang, Dan-Dan; Wang, Qing; Huang, Ru-Dan

2015-03-01

The hydrothermal reaction of transition metals, 1H-imidazole-4,5-dicarboxylic acid (H3ImDC) and 1,2-bi(pyridin-4-yl)ethene (bpe) affords a series of new complexes, namely, [Mn(HImDC)(bpe)(H2O)] (1), [M(H2ImDC)2(H2O)2]·(bpe) (M=Fe(2), Co(3), Zn(4), Cd(6)), [Zn3(ImDC)2(bpe)(H2O)]·3H2O (5) and [Cd(H2ImDC)(bpe)] (7), which are characterized by elemental analyses, IR, TG, XRPD and single crystal X-ray diffraction. Complex 1 exhibits a one dimensional (1D) zigzag chain with two types of irregular rings, and the 1D chains are linked to form a three dimensional (3D) supramolecular framework by the hydrogen bonding interactions (O-H•••O and O-H•••N). Complexes 2-4 and 6 are isomorphous, and they display the mononuclear structures. In these complexes, the O-H•••O and O-H•••N hydrogen bonds play an important role in sustaining the whole 3D supramolecular frameworks. Complex 5 shows a (3,3)-connected 3D framework with (103) topology, and the lattice water molecules as guest molecules exist in the 3D framework. Complex 7 is a wave-like two dimensional (2D) structure, in which the adjacent 1D chains point at the opposite directions. Moreover, the fluorescent properties of complexes 1-7 and the magnetic property of 1 have been investigated. The water vapor adsorption for complex 5 has been researched at 298 K.

Electrochemiluminescence aptasensor for adenosine triphosphate detection using host-guest recognition between metallocyclodextrin complex and aptamer.

PubMed

Chen, Hong; Chen, Qiong; Zhao, Yingying; Zhang, Fan; Yang, Fan; Tang, Jie; He, Pingang

2014-04-01

A sensitive and label-free electrochemiluminescence (ECL) aptasensor for the detection of adenosine triphosphate (ATP) was successfully designed using host-guest recognition between a metallocyclodextrin complex, i.e., tris(bipyridine)ruthenium(II)-β-cyclodextrin [tris(bpyRu)-β-CD], and an ATP-binding aptamer. In the protocol, the NH2-terminated aptamer was immobilized on a glassy carbon electrode (GCE) by a coupling interaction. After host-guest recognition between tris(bpyRu)-β-CD and aptamer, the tris(bpyRu)-β-CD/aptamer/GCE produced a strong ECL signal as a result of the photoactive properties of tris(bpyRu)-β-CD. However, in the presence of ATP, the ATP/aptamer complex was formed preferentially, which restricted host-guest recognition, and therefore less tris(bpyRu)-β-CD was attached to the GCE surface, resulting in an obvious decrease in the ECL intensity. Under optimal determination conditions, an excellent logarithmic linear relationship between the ECL decrease and ATP concentration was obtained in the range 10.0-0.05 nM, with a detection limit of 0.01 nM at the S/N ratio of 3. The proposed ECL-based ATP aptasensor exhibited high sensitivity and selectivity, without time-consuming signal-labeling procedures, and is considered to be a promising model for detection of aptamer-specific targets. Copyright © 2014. Published by Elsevier B.V.

Multifunctional guest-host particles engineered by reversal nanoimprint lithography

NASA Astrophysics Data System (ADS)

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.

Removal or storage of environmental pollutants and alternative fuel sources with inorganic adsorbents via host–guest encapsulation

DOE PAGES

Cramer, Alisha J.; Cole, Jacqueline M.

2017-05-08

The ever-increasing demands of the modern world continue to place substantial strain on the environment. To help alleviate the damage done to the natural world, the encapsulation of small molecules or ions (guests) into porous inorganic structural frameworks (hosts) provides a potential remedy for some of the environmental concerns facing us today. These concerns include the removal of harmful pollutants from water or air, the safe entrapment of nuclear waste materials, or the purification and storage of small molecules that act as alternative fuel sources. For this study, we review the trends in using inorganic materials as hostmedia for themore » removal or storage of various wastes and alternative fuels. In conclusion, we cover the treatment of water contaminated with dyes or heavy metals, air pollution alleviation via CO 2, SO x, NO x, and volatile organic compound containment, nuclear waste immobilization, and storage for H 2 and methane as alternative fuels.« less

Optically Tunable Chiral Plasmonic Guest-Host Cellulose Films Weaved with Long-range Ordered Silver Nanowires.

PubMed

Chu, Guang; Wang, Xuesi; Chen, Tianrui; Gao, Jianxiong; Gai, Fangyuan; Wang, Yu; Xu, Yan

2015-06-10

Plasmonic materials with large chiroptical activity at visible wavelength have attracted considerable attention due to their potential applications in metamaterials. Here we demonstrate a novel guest-host chiral nematic liquid crystal film composed of bulk self-co-assembly of the dispersed plasmonic silver nanowires (AgNWs) and cellulose nanocrystals (CNCs). The AgNWs-CNCs composite films show strong plasmonic optical activities, that are dependent on the chiral photonic properties of the CNCs host medium and orientation of the guest AgNWs. Tunable chiral distribution of the aligned anisotropic AgNWs with long-range order is obtained through the CNCs liquid crystal mediated realignment. The chiral plasmonic optical activity of the AgNWs-CNCs composite films can be tuned by changing the interparticle electrostatic repulsion between the CNCs nanorods and AgNWs. We also observe an electromagnetic energy transfer phenomena among the plasmonic bands of AgNWs, due to the modulation of the photonic band gap of the CNCs host matrix. This facile approach for fabricating chiral macrostructured plasmonic materials with optically tunable property is of interest for a variety of advanced optics applications.

Circularly polarized luminescence of syndiotactic polystyrene

NASA Astrophysics Data System (ADS)

Rizzo, Paola; Abbate, Sergio; Longhi, Giovanna; Guerra, Gaetano

2017-11-01

Syndiotactic polystyrene (s-PS) films, when crystallized from the amorphous state by temporary sorption of non-racemic guest molecules (like carvone) not only exhibit unusually high optical activity, both in the UV-Visible and Infrared ranges, but also present circularly polarized luminescence (CPL) with high dissymmetry ratios (g = ΔI/I values in the range 0.02-0.03). Experimental evidences provide support, rather than to the usual molecular circular dichroism, to a supramolecular chiral optical response being extrinsic to the site of photon absorption and emission, possibly associated with a helical morphology of s-PS crystallites.

Encapsulation of a [Dy(OH2)8](3+) cation: magneto-optical and theoretical studies of a caged, emissive SMM.

PubMed

Al Hareri, M; Gavey, E L; Regier, J; Ras Ali, Z; Carlos, L D; Ferreira, R A S; Pilkington, M

2016-10-15

The first supramolecular cage formed by three benzo-15-crown-5 macrocycles encapsulating a [Dy(OH2)8](3+) guest cation is reported, with the Dy(iii) centre exhibiting local pseudo square antiprismatic D4d symmetry. The anisotropy barrier extracted from ac susceptibility studies, emission spectroscopy and ab initio calculations reveals that the second excited state Kramers doublet plays a key role in the magnetization dynamics due to the Ising character and near coparallel nature of the ground and first excited Kramers doublets.

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

NASA Astrophysics Data System (ADS)

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 possible ways for detecting PTMs and may find use in the development of new assays for enzymes that lack robust methods for measuring their activity. The third section explores the development of new small molecule receptors capable of selectively binding hydrophilic guests in water, such as the lower methylation states of lysine. We identified a receptor, A2I, that has improved binding affinity and selectivity for dimethyllysine (Kme2). The receptor was discovered and synthesized by using dynamic combinatorial chemistry (DCC) to redesign a small molecule receptor (A2B ) that preferentially binds trimethyllysine (Kme3). Incorporating a biphenyl monomer with ortho-di-substituted carboxylates into the receptor lead to the formation of a salt bridge interaction with Kme2. These favorable electrostatic and hydrogen bonding interactions produced a receptor with 32-fold tighter binding to Kme2, which is the highest affinity synthetic receptor for Kme2 in the context of a peptide that has been reported. This work provides insight into effective strategies for binding hydrophilic, cationic guests in water and is an encouraging result toward a synthetic receptor that selectively binds Kme2 over other methylation states of lysine. In the final section, a small molecule receptor for Kme3 (A 2B) was redesigned using DCC to incorporate either aromatic or acidic amino acids into the receptor. We proposed that the incorporation of amino acids could introduce additional non-covalent interactions (such as cation-pi, electrostatic, and hydrogen bonding) with a guest bound inside the pocket of the receptor. However, selective non-covalent interactions between the amino acid side chain on the modified receptor and the bound methylated lysine guest could not be achieved. This is most likely due to the conformational flexibility of the amino acid-functionalized receptors. Furthermore, attaching amino acids to the receptor seemed to increase non-specific electrostatic interactions, resulting in tighter binding to the unmethylated lysine peptide (compared to A2B). Ultimately, this highlights the importance of incorporating monomers with less conformational flexibility that can rigidly place functional groups into the binding pocket.

Overview of the SAMPL5 host-guest challenge: Are we doing better?

PubMed

Yin, Jian; Henriksen, Niel M; Slochower, David R; Shirts, Michael R; Chiu, Michael W; Mobley, David L; Gilson, Michael K

2017-01-01

The ability to computationally predict protein-small molecule binding affinities with high accuracy would accelerate drug discovery and reduce its cost by eliminating rounds of trial-and-error synthesis and experimental evaluation of candidate ligands. As academic and industrial groups work toward this capability, there is an ongoing need for datasets that can be used to rigorously test new computational methods. Although protein-ligand data are clearly important for this purpose, their size and complexity make it difficult to obtain well-converged results and to troubleshoot computational methods. Host-guest systems offer a valuable alternative class of test cases, as they exemplify noncovalent molecular recognition but are far smaller and simpler. As a consequence, host-guest systems have been part of the prior two rounds of SAMPL prediction exercises, and they also figure in the present SAMPL5 round. In addition to being blinded, and thus avoiding biases that may arise in retrospective studies, the SAMPL challenges have the merit of focusing multiple researchers on a common set of molecular systems, so that methods may be compared and ideas exchanged. The present paper provides an overview of the host-guest component of SAMPL5, which centers on three different hosts, two octa-acids and a glycoluril-based molecular clip, and two different sets of guest molecules, in aqueous solution. A range of methods were applied, including electronic structure calculations with implicit solvent models; methods that combine empirical force fields with implicit solvent models; and explicit solvent free energy simulations. The most reliable methods tend to fall in the latter class, consistent with results in prior SAMPL rounds, but the level of accuracy is still below that sought for reliable computer-aided drug design. Advances in force field accuracy, modeling of protonation equilibria, electronic structure methods, and solvent models, hold promise for future improvements.

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

PubMed

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 light. Published by Elsevier B.V.

Contrasting guest binding interaction of cucurbit[7-8]urils with neutral red dye: controlled exchange of multiple guests.

PubMed

Shaikh, Mhejabeen; Choudhury, Sharmistha Dutta; Mohanty, Jyotirmayee; Bhasikuttan, Achikanath C; Pal, Haridas

2010-07-14

Interactions among macrocyclic hosts and dyes/drugs have been explored extensively for their direct usage in controlled uptake and release of large number of potential drug molecules. In this paper we report the non-covalent interaction of cucurbit[8]uril macrocycle (CB8) with a biologically important dye, neutral red, by absorption and fluorescence spectroscopy. A comparative analysis with the complexation behaviour of the dye with CB7, the lower homologue of CB8, indicates contrasting guest binding behaviour with significant changes in the photophysical characteristics of the dye. While CB7 interaction leads to a 1 ratio 1 stoichiometry resulting in approximately 6 fold enhancement in the fluorescence emission of the dye, CB8 displays signatures for a 1 ratio 2 host-guest stoichiometry with drastic reduction in the fluorescence emission. Apart from the evaluation of approximately 2 unit shift in the protolytic equilibrium on complexation (pK(a) shift), the measurements with tryptophan established a selective guest exchange to favour a co-localized dimer inside the CB8 cavity. In a protein medium (BSA), the 1 ratio 2 complex was converted to a 1 ratio 1 ratio 1 CB8-NRH(+)-BSA complex. The finding that NRH(+) can be transferred from CB8 to BSA, even though the binding constant for NRH(+)-CB8 is much higher than NRH(+)-BSA, is projected for a controlled slow release of NRH(+) towards BSA. Since the release and activity of drugs can be controlled by regulating the protolytic equilibrium, the macromolecular encapsulation and release of NRH(+) demonstrated here provide information relevant to host-guest based drug delivery systems and its applications.

Electrochemically driven host-guest interactions on patterned donor/acceptor self-assembled monolayers.

PubMed

Maglione, Maria Serena; Casado-Montenegro, Javier; Fritz, Eva-Corinna; Crivillers, Núria; Ravoo, Bart Jan; Rovira, Concepció; Mas-Torrent, Marta

2018-03-25

Here, on ITO//Au patterned substrates SAMs of ferrocene (Fc) on the Au regions and of anthraquinone (AQ) on the ITO areas are prepared, exhibiting three stable redox states. Furthermore, by selectively oxidizing or reducing the Fc or AQ units, respectively, the surface properties are locally modified. As a proof-of-concept, such a confinement of the properties is exploited to locally form host-guest complexes with β-cyclodextrin on specific surface regions depending on the applied voltage.

Structural investigation of the β-cyclodextrin complexes with chiral bicyclic monoterpenes - Influence of the functionality group on the host-guest stoichiometry

NASA Astrophysics Data System (ADS)

Ceborska, Magdalena

2017-10-01

The crystal structures of the complexes of β-cyclodextrin with (+)- and (-)-camphors are presented. The comparison of the obtained crystal structures with available data for other complexes of β-cyclodextrin with chiral bicyclic monoterpenes (hydrocarbon (+)-fenchene and alcohols: (-)-isopinocampheol, and (+)-, and (-)-borneols) obtained from Cambridge Structural Database (CSD) shows the trend of alcohols to form dimeric complexes of 2:3 stoichiometry, while hydrocarbons and ketones prefer to form 2:2 host-guest inclusion complexes.

Modeling off-resonant nonlinear-optical cascading in mesoscopic thin films and guest-host molecular systems

NASA Astrophysics Data System (ADS)

Dawson, Nathan J.; Andrews, James H.; Crescimanno, Michael

2013-12-01

A model for off-resonant microscopic cascading of (hyper)polarizabilities is developed using a self-consistent field approach to study mesoscopic systems of nonlinear polarizable atoms and molecules. We find enhancements in the higher-order susceptibilities resulting from geometrical and boundary orientation effects. We include an example of the dependence on excitation beam cross sectional structure and a simplified derivation of the microscopic cascading of the nonlinear-optical response in guest-host systems.

X-Ray diffraction, spectroscopy and thermochemical characterization of the pharmaceutical paroxetine nitrate salt

NASA Astrophysics Data System (ADS)

Carvalho, Paulo S.; de Melo, Cristiane C.; Ayala, Alejandro P.; Ellena, Javier

2016-08-01

A comprehensive solid state study of Paroxetine nitrate hydrate, (PRX+·NO3-)H2O, is reported. This salt was characterized by a combination of methods, including Single crystal X-ray diffraction, Thermal analysis, Fourier transform infrared spectroscopy (FTIR) and Solubility measurements. (PRX+·NO3-)H2O crystallizes in the monoclinic C2 space group (Z‧ = 1) and its packing was analyzed in details, showing that the main supramolecular motif consists in a C22(4) chain formed by charge-assisted N+-H⋯O- hydrogen bonds. The salt formation and conformation features were also accuracy established via FTIR spectra. In comparison with the pharmaceutical approved (PRX+ṡCl-)ṡ0.5H2O, (PRX+ṡNO3-)ṡH2O showed a decrease of 24 °C in the drug melting peak and a slight reduction in its water solubility value.

Polarization response of clathrate hydrates capsulated with guest molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeng, Qun; Li, Jinshan, E-mail: ljs915@263.net, E-mail: myang@scu.edu.cn; Huang, Hui

2016-05-28

Clathrate hydrates are characterized by their water cages encapsulating various guest atoms or molecules. The polarization effect of these guest-cage complexes was studied with combined density functional theory and finite-field calculations. An addition rule was noted for these systems whose total polarizability is approximately equal to the polarizability sum of the guest and the cage. However, their distributional polarizability computed with Hirshfeld partitioning scheme indicates that the guest–cage interaction has considerable influence on their polarization response. The polarization of encapsulated guest is reduced while the polarization of water cage is enhanced. The counteraction of these two opposite effects leads tomore » the almost unchanged total polarizability. Further analysis reveals that the reduced polarizability of encapsulated guest results from the shielding effect of water cage against the external field and the enhanced polarizability of water cage from the enhanced bonding of hydrogen bonds among water molecules. Although the charge transfer through the hydrogen bonds is rather small in the water cage, the polarization response of clathrate hydrates is sensitive to the changes of hydrogen bonding strength. The guest encapsulation strengthens the hydrogen bonding network and leads to enhanced polarizability.« less

Supramolecular nanoreactors for intracellular singlet-oxygen sensitization

NASA Astrophysics Data System (ADS)

Swaminathan, Subramani; Fowley, Colin; Thapaliya, Ek Raj; McCaughan, Bridgeen; Tang, Sicheng; Fraix, Aurore; Burjor, Captain; Sortino, Salvatore; Callan, John F.; Raymo, Françisco M.

2015-08-01

An amphiphilic polymer with multiple decyl and oligo(ethylene glycol) chains attached to a common poly(methacrylate) backbone assembles into nanoscaled particles in aqueous environments. Hydrophobic anthracene and borondipyrromethene (BODIPY) chromophores can be co-encapsulated within the self-assembling nanoparticles and transported across hydrophilic media. The reversible character of the noncovalent bonds, holding the supramolecular containers together, permits the exchange of their components with fast kinetics in aqueous solution. Incubation of cervical cancer (HeLA) cells with a mixture of two sets of nanoparticles, pre-loaded independently with anthracene or BODIPY chromophores, results in guest scrambling first and then transport of co-entrapped species to the intracellular space. Alternatively, incubation of cells with the two sets of nanocarriers in consecutive steps permits the sequential transport of the anthracene and BODIPY chromophores across the plasma membrane and only then allows their co-encapsulation within the same supramolecular containers. Both mechanisms position the two sets of chromophores with complementary spectral overlap in close proximity to enable the efficient transfer of energy intracellularly from the anthracene donors to the BODIPY acceptors. In the presence of iodine substituents on the BODIPY platform, intersystem crossing follows energy transfer. The resulting triplet state can transfer energy further to molecular oxygen with the concomitant production of singlet oxygen to induce cell mortality. Furthermore, the donor can be excited with two near-infrared photons simultaneously to permit the photoinduced generation of singlet oxygen intracellularly under illumination conditions compatible with applications in vivo. Thus, these supramolecular strategies to control the excitation dynamics of multichromophoric assemblies in the intracellular environment can evolve into valuable protocols for photodynamic therapy.An amphiphilic polymer with multiple decyl and oligo(ethylene glycol) chains attached to a common poly(methacrylate) backbone assembles into nanoscaled particles in aqueous environments. Hydrophobic anthracene and borondipyrromethene (BODIPY) chromophores can be co-encapsulated within the self-assembling nanoparticles and transported across hydrophilic media. The reversible character of the noncovalent bonds, holding the supramolecular containers together, permits the exchange of their components with fast kinetics in aqueous solution. Incubation of cervical cancer (HeLA) cells with a mixture of two sets of nanoparticles, pre-loaded independently with anthracene or BODIPY chromophores, results in guest scrambling first and then transport of co-entrapped species to the intracellular space. Alternatively, incubation of cells with the two sets of nanocarriers in consecutive steps permits the sequential transport of the anthracene and BODIPY chromophores across the plasma membrane and only then allows their co-encapsulation within the same supramolecular containers. Both mechanisms position the two sets of chromophores with complementary spectral overlap in close proximity to enable the efficient transfer of energy intracellularly from the anthracene donors to the BODIPY acceptors. In the presence of iodine substituents on the BODIPY platform, intersystem crossing follows energy transfer. The resulting triplet state can transfer energy further to molecular oxygen with the concomitant production of singlet oxygen to induce cell mortality. Furthermore, the donor can be excited with two near-infrared photons simultaneously to permit the photoinduced generation of singlet oxygen intracellularly under illumination conditions compatible with applications in vivo. Thus, these supramolecular strategies to control the excitation dynamics of multichromophoric assemblies in the intracellular environment can evolve into valuable protocols for photodynamic therapy. Electronic supplementary information (ESI) available: Experimental procedures; crystallographic data; absorption and emission spectra; temporal absorbance profiles; singlet-oxygen measurements; intracellular fluorescence measurements; viability assays. See DOI: 10.1039/c5nr02672e

Supramolecular delivery of photoactivatable fluorophores in developing embryos

NASA Astrophysics Data System (ADS)

Zhang, Yang; Tang, Sicheng; Sansalone, Lorenzo; Thapaliya, Ek Raj; Baker, James D.; Raymo, Françisco M.

2017-02-01

The identification of noninvasive strategies to monitor dynamics within living organisms in real time is essential to elucidate the fundamental factors governing a diversity of biological processes. This study demonstrates that the supramolecular delivery of photoactivatable fluorophores in Drosophila melanogaster embryos allows the real-time tracking of translocating molecules. The designed photoactivatable fluorophores switch from an emissive reactant to an emissive product with spectrally-resolved fluorescence, under moderate blue-light irradiation conditions. These hydrophobic fluorescent probes can be encapsulated within supramolecular hosts and delivered to the cellular blastoderm of the embryos. Thus, the combination of supramolecular delivery and fluorescence photoactivation translates into a noninvasive method to monitor dynamics in vivo and can evolve into a general chemical tool to track motion in biological specimens.

Soluble Flavanthrone Derivatives: Synthesis, Characterization, and Application to Organic Light-Emitting Diodes.

PubMed

Kotwica, Kamil; Bujak, Piotr; Data, Przemyslaw; Krzywiec, Wojciech; Wamil, Damian; Gunka, Piotr A; Skorka, Lukasz; Jaroch, Tomasz; Nowakowski, Robert; Pron, Adam; Monkman, Andrew

2016-06-01

Simple modification of benzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine-8,16-dione, an old and almost-forgotten vat dye, by reduction of its carbonyl groups and subsequent O-alkylation, yields solution-processable, electroactive, conjugated compounds of the periazaacene type, suitable for the use in organic electronics. Their electrochemically determined ionization potential and electron affinity of about 5.2 and -3.2 eV, respectively, are essentially independent of the length of the alkoxyl substituent and in good agreement with DFT calculations. The crystal structure of 8,16-dioctyloxybenzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine (FC-8), the most promising compound, was solved. It crystallizes in space group P1‾ and forms π-stacked columns held together in the 3D structure by dispersion forces, mainly between interdigitated alkyl chains. Molecules of FC-8 have a strong tendency to self-organize in monolayers deposited on a highly oriented pyrolytic graphite surface, as observed by STM. 8,16-Dialkoxybenzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridines are highly luminescent, and all have photoluminescence quantum yields of about 80 %. They show efficient electroluminescence, and can be used as guest molecules with a 4,4'-bis(N-carbazolyl)-1,1'-biphenyl host in guest/host-type organic light-emitting diodes. The best fabricated diodes showed a luminance of about 1900 cd m(-12) , a luminance efficiency of about 3 cd A(-1) , and external quantum efficiencies exceeding 0.9 %. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The influence of self-assembling supramolecular structures on the passive membrane transport of ion-paired molecules.

PubMed

Benaouda, F; Brown, M B; Shah, B; Martin, G P; Jones, S A

2012-12-15

Weak ion-ion interactions, such as those associated with ion-pair formation, are difficult to isolate and characterise in the liquid state, but they have the potential to alter significantly the physicochemical behaviour of molecules in solution. The aim of this work was to gain a better understanding of how ion-ion interactions influenced passive membrane transport. The test system was composed of propylene (PG) glycol, water and diclofenac diethylamine (DDEA). Infrared spectroscopy was employed to determine the nature of the DDEA ion-pair interactions and the drug-vehicle association. Passive transport was assessed using homogeneous synthetic membranes. Solution-state analysis demonstrated that the ion-pair was unperturbed by vehicle composition changes, but the solvent-DDEA interactions were modified. DDEA-PG/water hydrogen bonding influenced the ion-pair solubility (X(dev)) and the solvent interactions slowed transport rate in PG-rich vehicles (0.84±0.05 μg cm(-2) h(-1), at ln(X(dev))=0.57). In water-rich co-solvents, the presence of strong water structuring facilitated a significant increase (p<0.05) in transmembrane penetration rate (e.g. 4.33±0.92 μg cm(-2) h(-1), at ln(X(dev))=-0.13). The data demonstrates that weak ion-ion interactions can result in the embedding of polar entities within a stable solvent complex and spontaneous supramolecular assembly should be considered when interpreting transmembrane transport processes of ionic molecules. Copyright © 2012 Elsevier B.V. All rights reserved.

Probing structural transition and guest dynamics of hydroquinone clathrates by temperature-dependent terahertz time-domain spectroscopy.

PubMed

Lee, Eui Su; Han, Kyu Won; Yoon, Ji-Ho; Jeon, Tae-In

2011-01-13

The structural transition from hydroquinone clathrates to crystalline α-form hydroquinone was observed up to the range of 3 THz frequency as a function of temperatures. We found that all three hydroquinone clathrates, CO(2)-, CH(4)-, and CO(2)/CH(4)-loaded hydroquinone clathrates, transform into the α-form hydroquinone at around 102 ± 7 °C. The resonance peak of the CO(2)-loaded hydroquinone clathrate at 2.15 THz decreases with increasing temperature, indicating that CO(2) guest molecules are readily released from the host framework prior to the structural transformation. This reveals that the hydroquinone clathrates may transform into the stable α-form hydroquinone via the metastable form of guest-free clathrate, which depends on guest molecules enclathrated in the cages of the host frameworks. A strong resonance of the α-form hydroquinone at 1.18 THz gradually shifts to the low frequency with increasing temperature and shifts back to the high frequency with decreasing temperature.

Polysaccharide Nanoparticles for Efficient siRNA Targeting in Cancer Cells by Supramolecular pKa Shift

NASA Astrophysics Data System (ADS)

Zhang, Ying-Ming; Yang, Yang; Zhang, Yu-Hui; Liu, Yu

2016-07-01

Biomacromolecular pKa shifting is considered as one of the most ubiquitous processes in biochemical events, e.g., the enzyme-catalyzed reaction and protein conformational stabilization. In this paper, we report on the construction of biocompatible polysaccharide nanoparticle with targeting ability and lower toxicity by supramolecular pKa shift strategy. This was realized through a ternary assembly constructed by the dual host‒guest interactions of an adamantane-bis(diamine) conjugate (ADA) with cucurbit[6]uril (CB[6]) and a polysaccharide. The potential application of such biocompatible nanostructure was further implemented by the selective transportation of small interfering RNA (siRNA) in a controlled manner. It is demonstrated that the strong encapsulation of the ADA’s diammonium tail by CB[6] not only reduced the cytotoxicity of the nano-scaled vehicle but also dramatically enhanced cation density through an obvious positive macrocycle-induced pKa shift, which eventually facilitated the subsequent siRNA binding. With a targeted polysaccharide shell containing a cyclodextrin‒hyaluronic acid conjugate, macrocycle-incorporated siRNA polyplexes were specifically delivered into malignant human prostate PC-3 cells. The supramolecular polysaccharide nanoparticles, the formation of which was enabled and promoted by the complexation-assisted pKa shift, may be used as a versatile tool for controlled capture and release of biofunctional substrates.

Supramolecular control of the spin-dependent dynamics of long-lived charge-separated states at the micellar interface as studied by magnetic field effect.

PubMed

Miura, Tomoaki

2013-05-30

Spin selectivity in long-lived charge separation at the micellar interface is studied using the magnetic field effect (MFE). An amphiphilic viologen is complexed with a nonionic surfactant to form a supramolecular acceptor cage, of which the size is controlled by the acceptor concentration, as confirmed by dynamic light scattering measurement. Photoinduced electron transfer (ET) from a guest polyaromatic molecule to the viologen moiety is observed spin-dependently with time-resolved fluorescence (trFL) and transient absorption (TA). A negative MFE on the radical yield is successfully observed, which indicates generation of singlet-born long-lived radical pair that is realized by supramolecular control of the donor-acceptor (D-A) distances. The dominance of the singlet-precursor MFE is sensitive to the acceptor concentration, which presumably affects the D-A distance as well as the cage size. However, theoretical analysis of the MFE gives large recombination rates of ca. 10(8) s(-1), which indicate the contribution of spin-allowed recombination of the pseudocontact radical pair generated by still active in-cage diffusion. Dependence of the viologen concentration and alkyl chain length on the recombination and escape dynamics is discussed in terms of precursor spin states and the microenvironments in the cage.

Analysis of the phase solubility diagram of a phenacetin/competitor/beta-cyclodextrin ternary system, involving competitive inclusion complexation.

PubMed

Ono, N; Hirayama, F; Arima, H; Uekama, K

2001-01-01

The competitive inclusion complexations in the ternary phenacetin/competitors/beta-cyclodextrin (beta-CyD) systems were investigated by the solubility method, where m-bromobenzoic acid (m-BBA) and o-toluic acid (o-TA) were used as competitors. The solubility changes of the drug and competitors as a function of beta-CyD concentration in the ternary systems were formulated using their stability constants and intrinsic solubilities. The decrease in solubility of phenacetin by the addition of competitors could be quantitatively simulated by the formulation, when both drug and competitor give A(L) type solubility diagrams. On the other hand, when one of the guests gives a B(S) type solubility diagram, its solubility change was clearly reflected in that of the another guest, i.e., phenacetin gave an A(L) type solubility diagram in the binary phenacetin/beta-CyD system and o-TA gave a B(S) type diagram in the binary o-TA/beta-CyD system, but in the ternary phenacetin/o-TA/beta-CyD system, a new plateau region appeared in the original A(L) type diagram of phenacetin. This was explained by the solubilization theory of Higuchi and Connors. The solubility analysis of the ternary drug/competitor/CyD systems may be particularly useful for determination of the stability constant of a drug whose physicochemical and spectroscopic analyses are difficult, because they can be calculated by monitoring the solubility change of a competitor, without monitoring that of a drug. Furthermore, the present results suggest that attention should be paid to the type of the phase solubility diagram, as well as the magnitude of the stability constant and the solubility of the complex, for a rational formulation design of CyD complexes.

Functional Nanofibers via Electospinning: New Materials and Processes

NASA Astrophysics Data System (ADS)

Manasco, Joshua Lee

Cyclodextrins are fascinating, amphiphilic molecules that are of considerable interest due to their ability to be used in a variety of applications ranging from pharmaceuticals and cosmetics to foods and agriculture. These are ring-shaped sugar molecules possess a hydrophobic cavity and a hydrophilic exterior which imparts them water solubility. There are three main types of naturally occurring cyclodextrins namely alpha-, beta- and gamma- CD which have 6, 7 and 8 member rings, respectively. Owing to their hydrophobic interior, cyclodextrin molecules encapsulate hydrophobic guest molecules (from small to macromolecules) to form host-guest supermolecular structures. Chemically modified CDs are often preferred to the natural forms, particularly methylated (MbetaCD) and hydroxypropylated (HPbetaCD) cyclodextrins, for their enhanced solubility and chemical stability. Electrostatic spinning (electrospinning) of nanofibers has drawn significant research attention in recent decades. This technique involves the stretching of a polymer solution or melt in a high electric field to produce fibers on the nanoscale. These 1-Dimensional nanostructures possess extraordinary surface-to-weight ratio and find applications that vary from filtration membranes and tissue scaffolding materials to drug delivery and many others. The scope of this research attempts to leverage the unique features of CDs with the high aspect ratio of nanofibers to create functional nanomaterials. The present study can be divided into three sections. In the first part, we establish that CDs can be electrospun without the need for a "carrier" polymer. This discovery may serve to extend the horizon of what is currently considered "electrospinnable" from macromolecules now to small molecules. The ability to electrospin CDs led to their incorporation of other polymers to create bicomponent fibers with poly (vinyl alcohol) (PVA) and polyacrylonitrile (PAN). In the case of PVA we demonstrate the ability to not only to control the fiber properties based on PVA/CD ratio, but also crosslink these fibers to create water resistant fiber mats. Furthermore, the use of these fibers as rapid dissolving membranes for drug delivery is explored. Additionally, CDs are investigated for use as a porogen for PAN and carbon fibers. We find that CDs are particularly good candidates for us as porogens due to their amorphous nature and versatility to be dissolved in various solvent system. By nature, solution electrospinning is a low-throughput, solvent intensive process. In the last part we attempt to alleviate this issue by designing an extrusion based melt electrospinning device. We show that submicron fibers of polycaprolactone are possible through this technique without the use of organic solvents.

Preparation and Physicochemical Characterization of an Inclusion Complex Between Dimethylated β-Cyclodextrin and a Drug Lead From a New Class of Orally Active Antimalarial 3,5-Diaryl-2-Aminopyridines.

PubMed

Joseph, Laurelle M; Chibale, Kelly; Caira, Mino R

2016-11-01

Cyclodextrins (CDs) were used to increase the aqueous solubility of a recently discovered orally active 3,5-diaryl-2-aminopyridine antimalarial drug lead (MMP). Phase-solubility studies using β-CD, hydroxypropyl-β-CD, and heptakis(2,6-di-O-methyl)-β-CD (DIMEB) as potential solubilizers for MMP yielded solubility enhancement factors of 17, 49, and 65, respectively, at 25°C with CD concentrations ∼20 mM. A crystalline complex, DIMEB⋅MMP⋅2H 2 O, was prepared and characterized by thermal and single-crystal X-ray analyses. The latter technique revealed preferential encapsulation of the hydrophobic methylsulfonylphenyl moiety of MMP within the CD cavity and protrusion of the more polar methoxypyridinyl and aminopyridine residues from the cavity. This inclusion mode results in a DIMEB complex with a new packing arrangement and an intricate network of intermolecular hydrogen bonds linking guest residues that protrude from 2 1 -related host cavities. A summary of the results of the performance of the inclusion complex in preliminary pharmacokinetic and efficacy tests in mouse models is provided. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

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

PubMed

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.

Resolving the Magnetic Asymmetry of the Inner Space in Self-assembled Dimeric Capsules Based on Tetraurea-calix[4]pyrrole Components.

PubMed

Espelt, Mónica; Aragay, Gemma; Ballester, Pablo

2015-01-01

The encapsulation of N,N, N',N'-tetramethyl-1,5-pentanediamine-N,N'-dioxide 2 in a non-chiral capsular assembly formed by dimerization of tetraurea-calix[4]pyrrole 1a produced the observation of the N-methyl groups of the encapsulated guest as two separated singlets resonating highly upfield in the (1)H NMR spectrum. In order to clarify the origin of the observed signal splitting we assembled and studied a series of structurally related dimeric capsules. We used the tetraurea-calix[4]pyrrole 1a , the enantiomerically pure tetraurea-calix[4] pyrrole R-1b and the tetraurea-bisloop calix[4]pyrrole 1c as components of the produced assemblies. The (1)H NMR spectra of the assembled encapsulation complexes with bis-N-oxide 2 evidenced diverse splitting patterns of the N-methyl groups. In addition, 2D EXSY/ROESY NMR experiments revealed the existence of chemical exchange processes involving the separated methyl signals of the encapsulated guest. The capsular assemblies were mainly stabilized by a belt of eight head-to-tail hydrogen-bonded urea groups. The interconversion between the two senses of rotation of the unidirectionally oriented urea groups was slow on the (1)H NMR timescale. These characteristics determined the appearance of a new asymmetry element (supramolecular conformational chirality) in the assemblies that accounted for some of the magnetic asymmetries featured by the capsule's inner space. The racemization of the supramolecular chirality element was fast on the EXSY timescale and produced the chemical exchange processes detected for the encapsulation complexes.

A fluorometric assay for alkaline phosphatase activity based on β-cyclodextrin-modified carbon quantum dots through host-guest recognition.

PubMed

Tang, Cong; Qian, Zhaosheng; Huang, Yuanyuan; Xu, Jiamin; Ao, Hang; Zhao, Meizhi; Zhou, Jin; Chen, Jianrong; Feng, Hui

2016-09-15

A convenient, reliable and highly sensitive assay for alkaline phosphatase (ALP) activity in the real-time manner is developed based on β-cyclodextrin-modified carbon quantum dots (β-CD-CQDs) nanoprobe through specific host-guest recognition. Carbon quantum dots were first functionalized with 3-aminophenyl boronic acid to produce boronic acid-functionalized CQDs, and then further modified with hydropropyl β-cyclodextrins (β-CD) through B-O bonds to form β-CD-CQDs nanoprobe. p-Nitrophenol phosphate disodium salt is used as the substrate of ALP, and can hydrolyze to p-nitrophenol under the catalysis of ALP. The resulting p-nitrophenol can enter the cavity of β-CD moiety in the nanoprobe due to their specific host-guest recognition, where photoinduced electron transfer process between p-nitrophenol and CQDs takes place to efficiently quench the fluorescence of the probe. The correlation between quenched fluorescence and ALP level can be used to establish quantitative evaluation of ALP activity in a broad range from 3.4 to 100.0U/L with the detection limit of 0.9U/L. This assay shows a high sensitivity to ALP even in the presence of a very high concentration of glucose. This study demonstrates a good electron donor/acceptor pair, which can be used to design general detection strategy through PET process, and also broadens the application of host-guest recognition for enzymes detection in clinical practice. Copyright © 2016 Elsevier B.V. All rights reserved.

Polyoxometalates paneling through {Mo2O2S2} coordination: cation-directed conformations and chemistry of a supramolecular hexameric scaffold.

PubMed

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 as "glue" to maintain the POM units connected through the conformationally inward-directed {Mo(2)O(2)S(2)} linkers. © 2011 American Chemical Society

Configurational Isomerism in Polyoxovanadates.

PubMed

Mahnke, Lisa K; Kondinski, Aleksandar; Warzok, Ulrike; Näther, Christian; van Leusen, Jan; Schalley, Christoph A; Monakhov, Kirill Yu; Kögerler, Paul; Bensch, Wolfgang

2018-03-05

A water-soluble derivative of the polyoxovanadate {V 15 E 6 O 42 } (E=semimetal) archetype enables the study of cluster shell rearrangements driven by supramolecular interactions. A reaction unique to E=Sb, induced exclusively by ligand metathesis in peripheral [Ni(ethylenediamine) 3 ] 2+ counterions, results in the formation of the metastable α 1 * configurational isomer of the {V 14 Sb 8 O 42 } cluster type. Contrary to all other polyoxovanadate shell architectures, this isomer comprises an inward-oriented vanadyl group and is ca. 50 and 12 kJ mol -1 higher in energy than the previously isolated α and β isomers, respectively. We discuss this unexpected reaction in light of supramolecular Sb-O⋅⋅⋅V and Sb-O⋅⋅⋅Sb contacts manifested in {V 14 Sb 8 O 42 } 2 dimers detected in the solid state. ESI MS experiments confirm the stability of these dimers also in solution and in the gas phase. DFT calculations indicate that other, as of yet elusive isomers of {V 14 Sb 8 }, might be accessible as well. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Considerable fluorescence enhancement upon supramolecular complex formation between berberine and p-sulfonated calixarenes

NASA Astrophysics Data System (ADS)

Megyesi, Mónika; Biczók, László

2006-06-01

Remarkably strong binding of berberine to 4-sulfonatocalix[8]arene was found in aqueous solution, which led to fluorescence quantum yield increase of a factor about 40 at pH 2. The hypsochromic shift of the fluorescence maximum implied that berberine sensed less polar microenvironment when confined to SCX8. The stability of the supramolecular complex significantly diminished when sulfocalixarenes of smaller ring size served as host compounds but the pH affected the association strength to a much lesser extent. All berberine complexes proved to be barely fluorescent at pH 12.2 because of excited state quenching by the hosts via electron transfer.

Curcumin complexation with cyclodextrins by the autoclave process: Method development and characterization of complex formation.

PubMed

Hagbani, Turki Al; Nazzal, Sami

2017-03-30

One approach to enhance curcumin (CUR) aqueous solubility is to use cyclodextrins (CDs) to form inclusion complexes where CUR is encapsulated as a guest molecule within the internal cavity of the water-soluble CD. Several methods have been reported for the complexation of CUR with CDs. Limited information, however, is available on the use of the autoclave process (AU) in complex formation. The aims of this work were therefore to (1) investigate and evaluate the AU cycle as a complex formation method to enhance CUR solubility; (2) compare the efficacy of the AU process with the freeze-drying (FD) and evaporation (EV) processes in complex formation; and (3) confirm CUR stability by characterizing CUR:CD complexes by NMR, Raman spectroscopy, DSC, and XRD. Significant differences were found in the saturation solubility of CUR from its complexes with CD when prepared by the three complexation methods. The AU yielded a complex with expected chemical and physical fingerprints for a CUR:CD inclusion complex that maintained the chemical integrity and stability of CUR and provided the highest solubility of CUR in water. Physical and chemical characterizations of the AU complexes confirmed the encapsulated of CUR inside the CD cavity and the transformation of the crystalline CUR:CD inclusion complex to an amorphous form. It was concluded that the autoclave process with its short processing time could be used as an alternate and efficient methods for drug:CD complexation. Copyright © 2017 Elsevier B.V. All rights reserved.

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry.

PubMed

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

NASA Astrophysics Data System (ADS)

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.

Recent development and biomedical applications of self-healing hydrogels.

PubMed

Wang, Yinan; Adokoh, Christian K; Narain, Ravin

2018-01-01

Hydrogels are of special importance, owing to their high-water content and various applications in biomedical and bio-engineering research. Self-healing properties is a common phenomenon in living organisms. Their endowed property of being able to self-repair after physical/chemical/mechanical damage to fully or partially its original properties demonstrates their prospective therapeutic applications. Due to complicated preparation and selection of suitable materials, the application of many host-guest supramolecular polymeric hydrogels are so limited. Thus, the design and construction of self-repairing material are highly desirable for effectively increase in the lifetime of a functional material. However, recent advances in the field of materials science and bioengineering and nanotechnology have led to the design of biologically relevant self-healing hydrogels for therapeutic applications. This review focuses on the recent development of self-healing hydrogels for biomedical application. Areas covered: The strategies of making self-healing hydrogels and their healing mechanisms are discussed. The significance of self-healing hydrogel for biomedical application is also highlighted in areas such as 3D/4D printing, cell/drug delivery, as well as soft actuators. Expert opinion: Materials that have the ability to self-repair damage and regain the desired mechanical properties, have been found to be excellent candidate materials for a range of biomedical uses especially if their unique characteristics are similar to that of soft-tissues. Self-healing hydrogels have been synthesized and shown to exhibit similar characteristics as human tissues, however, significant improvement is required in the fabrication process from inexpensive and nontoxic/non-hazardous materials and techniques, and, in addition, further fine-tuning of the self-healing properties are needed for specific biomedical uses.

Cyclodextrins as versatile building blocks for regenerative medicine.

PubMed

Alvarez-Lorenzo, Carmen; García-González, Carlos A; Concheiro, Angel

2017-12-28

Cyclodextrins (CDs) are one of the most versatile substances produced by nature, and it is in the aqueous biological environment where the multifaceted potential of CDs can be completely unveiled. CDs form inclusion complexes with a variety of guest molecules, including polymers, producing very diverse biocompatible supramolecular structures. Additionally, CDs themselves can trigger cell differentiation to distinct lineages depending on the substituent groups and also promote salt nucleation. These features together with the affinity-driven regulated release of therapeutic molecules, growth factors and gene vectors explain the rising interest for CDs as building blocks in regenerative medicine. Supramolecular poly(pseudo)rotaxane structures and zipper-like assemblies exhibit outstanding viscoelastic properties, performing as syringeable implants. The sharp shear-responsiveness of the supramolecular assemblies is opening new avenues for the design of bioinks for 3D printing and also of electrospun fibers. CDs can also be transformed into polymerizable monomers to prepare alternative nanostructured materials. The aim of this review is to analyze the role that CDs may play in regenerative medicine through the analysis of the last decade research. Most applications of CD-based scaffolds are focussed on non-healing bone fractures, cartilage reparation and skin recovery, but also on even more challenging demands such as neural grafts. For the sake of clarity, main sections of this review are organized according to the architecture of the CD-based scaffolds, mainly syringeable supramolecular hydrogels, 3D printed scaffolds, electrospun fibers, and composites, since the same scaffold type may find application in different tissues. Copyright © 2017 Elsevier B.V. All rights reserved.

Electroluminescence from completely horizontally oriented dye molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Komino, Takeshi; Center for Organic Photonics and Electronics Research, Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395; Japan Science and Technology Agency, ERATO, Adachi Molecular Exciton Engineering Project, 744 Motooka, Nishi, Fukuoka 819-0395

2016-06-13

A complete horizontal molecular orientation of a linear-shaped thermally activated delayed fluorescent guest emitter 2,6-bis(4-(10Hphenoxazin-10-yl)phenyl)benzo[1,2-d:5,4-d′] bis(oxazole) (cis-BOX2) was obtained in a glassy host matrix by vapor deposition. The orientational order of cis-BOX2 depended on the combination of deposition temperature and the type of host matrix. Complete horizontal orientation was obtained when a thin film with cis-BOX2 doped in a 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP) host matrix was fabricated at 200 K. The ultimate orientation of guest molecules originates from not only the kinetic relaxation but also the kinetic stability of the deposited guest molecules on the film surface during film growth. Utilizing the ultimatemore » orientation, a highly efficient organic light-emitting diode with the external quantum efficiency of 33.4 ± 2.0% was realized. The thermal stability of the horizontal orientation of cis-BOX2 was governed by the glass transition temperature (T{sub g}) of the CBP host matrix; the horizontal orientation was stable unless the film was annealed above T{sub g}.« less

Dual emissions from MnS clusters confined in the sodalite nanocage of a chalcogenide-based semiconductor zeolite.

PubMed

Hu, Dandan; Zhang, Yingying; Lin, Jian; Hou, Yike; Li, Dongsheng; Wu, Tao

2017-03-21

A new host-guest hybrid system with MnS clusters confined in a chalcogenide-based semiconductor zeolite was for the first time constructed and its photoluminescence (PL) properties were also investigated. The existence of MnS clusters in the nanopores of the semiconductor zeolite was revealed by UV-Vis absorption spectroscopy, steady-state fluorescence analysis, Raman as well as Fourier transform infrared (FTIR) spectroscopy. The aggregation state of the entrapped MnS clusters at different measurement temperatures was probed by electron paramagnetic resonance (EPR) spectroscopy. Of significant importance is the fact that the entrapped MnS clusters displayed dual emissions at 518 nm (2.39 eV) and 746 nm (1.66 eV), respectively, and the long-wavelength emission has never been observed in other MnS-confined host-guest systems. These two emission peaks displayed tunable PL intensity affected by the loading level and measurement temperature. This can be explained by the different morphologies of MnS clusters with different aggregation states at the corresponding loading level or measurement temperature. The current study opens a new avenue to construct inorganic chalcogenide cluster involved host-guest systems with a semiconductor zeolite as the host matrix.

A Highly Selective and Strong Anti-Interference Host-Guest Complex as Fluorescent Probe for Detection of Amantadine by Indicator Displacement Assay.

PubMed

Zhu, Linzhao; Zhao, Zhiyong; Zhang, Xiongzhi; Zhang, Haijun; Liang, Feng; Liu, Simin

2018-04-18

Amantadine (AMA) and its derivatives are illicit veterinary drugs that are hard to detect at very low concentrations. Developing a fast, simple and highly sensitive method for the detection of AMA is highly in demand. Here, we designed an anthracyclic compound (ABAM) that binds to a cucurbit[7]uril (CB[7]) host with a high association constant of up to 8.7 × 10⁸ M −1 . The host-guest complex was then used as a fluorescent probe for the detection of AMA. Competition by AMA for occupying the cavity of CB[7] allows ABAM to release from the CB[7]-ABAM complex, causing significant fluorescence quenching of ABAM (indicator displacement assay, IDA). The linear range of the method is from 0.000188 to 0.375 μg/mL, and the detection limit can be as low as 6.5 × 10 −5 μg/mL (0.35 nM). Most importantly, due to the high binding affinity between CB[7] and ABAM, this fluorescence host-guest system shows great anti-interference capacity. Thus, we are able to accurately determine the concentration of AMA in various samples, including pharmaceutical formulations.

Bioorganometallic chemistry. 5. Molecular recognition of aromatic amino acid guests by Cp{sup *} Rh-nucleobase/nucleoside/nucleotide cyclic trimer hosts in aqueous solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, H.; Maestre, M.F.; Fish, R.H.

We report what we believe is the first example of bioorganometallic hosts, 1-4, [Cp{sup *}Rh(9-methyladenine)]{sub 3}(OTf){sub 3} (1), [Cp{sup *}Rh(Me-5`-AMP)]{sub 3} (4), being able to recognize aromatic amino acid guests L-tryptophan (L-Trp) and L-phenylalanine (L-Phe) in aqueous media at pH 7. Results show that the molecular recognition of aromatic amino acids with bioorganometallic hosts 1-4 in aqueous solution, as studied by {sup 1}H NMR and NOE techniques, occurs predominately via a {pi}-{pi} interaction, and, in the case of L-Trp, additional electronic/hydrophobic interactions with hosts are possible. 7 refs., 1 fig., 1 tab.

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

PubMed Central

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

Molecular printboards: monolayers of beta-cyclodextrins on silicon oxide surfaces.

PubMed

Onclin, Steffen; Mulder, Alart; Huskens, Jurriaan; Ravoo, Bart Jan; Reinhoudt, David N

2004-06-22

Monolayers of beta-cyclodextrin host molecules have been prepared on SiO2 surfaces. An ordered and stable cyano-terminated monolayer was modified in three consecutive surface reactions. First, the cyanide groups were reduced to their corresponding free amines using Red Al as a reducing agent. Second, 1,4-phenylene diisothiocyanate was used to react with the amine monolayer where it acts as a linking molecule, exposing isothiocyanates that can be derivatized further. Finally, per-6-amino beta-cyclodextrin was reacted with these isothiocyanate functions to yield a monolayer exposing beta-cyclodextrin. All monolayers were characterized by contact angle measurements, ellipsometric thickness measurements, Brewster angle Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry, which indicate the formation of a densely packed cyclodextrin surface. It was demonstrated that the beta-cyclodextrin monolayer could bind suitable guest molecules in a reversible manner. A fluorescent molecule (1), equipped with two adamantyl groups for complexation, was adsorbed onto the host monolayer from solution to form a monolayer of guest molecules. Subsequently, the guest molecules were desorbed from the surface by competition with increasing beta-cyclodextrin concentration in solution. The data were fitted using a model. An intrinsic binding constant of 3.3 +/- 1 x 10(5) M(-1) was obtained, which corresponds well to previously obtained results with a divalent guest molecule on beta-cyclodextrin monolayers on gold. In addition, the number of guest molecules bound to the host surface was determined, and a surface coverage of ca. 30% was found.

Vesicular gold assemblies based on host-guest inclusion and its controllable release of doxorubicin

NASA Astrophysics Data System (ADS)

Ha, Wei; Kang, Yang; Peng, Shu-Lin; Ding, Li-Sheng; Zhang, Sheng; Li, Bang-Jing

2013-12-01

We have developed a kind of gold nanoparticle (AuNP) in which polyethylene glycol (PEG) and poly(N-isopropylacrylamide) (PNIPAM) are attached on the surface of a gold nanocrystal through the host-guest inclusion between adamantane groups (ADA) and β-cyclodextrin (β-CD). The resulting AuNPs become amphiphilic in water above body temperature and self-assemble into vesicles. It is found that these vesicles can load doxorubicin (Dox) effectively. With a decrease in temperature, the PNIPAM shifted from hydrophobic to hydrophilic, causing Au vesicles to disassemble into stable small AuNPs, triggering the release of Dox. These hybrid vesicles, combining polymer functionality with the intriguing properties of AuNPs, can first release free Dox and AuNP/Dox at a site of a tumor through the application of either simple ice packs or deeply penetrating cryoprobes, then the AuNP/Dox can be taken in by tumor cells and destroy them like miniature munitions. Furthermore, these vesicles showed other therapeutic possibilities due to the presence of gold. We believe that the development of such multi-functional vesicles will provide new and therapeutically useful means for medical applications.

Manganese(III) Formate: A Three-Dimensional Framework That Traps Carbon Dioxide Molecules.

PubMed

Cornia, Andrea; Caneschi, Andrea; Dapporto, Paolo; Fabretti, Antonio C; Gatteschi, Dante; Malavasi, Wanda; Sangregorio, Claudio; Sessoli, Roberta

1999-06-14

Carbon dioxide, formic acid, and water molecules are trapped in the crystal lattice of manganese(III) formate (see 1), which was obtained by reducing permanganate with formic acid. Each CO 2 guest molecule exhibits four C-H⋅⋅⋅O-C-O interactions with the three-dimensional host framework of Mn(HCOO) 3 units. Compound 1 undergoes an antiferromagnetic phase transition at 27 K. © 1999 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Self-assembly of cationic multidomain peptide hydrogels: supramolecular nanostructure and rheological properties dictate antimicrobial activity

NASA Astrophysics Data System (ADS)

Jiang, Linhai; Xu, Dawei; Sellati, Timothy J.; Dong, He

2015-11-01

Hydrogels are an important class of biomaterials that have been widely utilized for a variety of biomedical/medical applications. The biological performance of hydrogels, particularly those used as wound dressing could be greatly advanced if imbued with inherent antimicrobial activity capable of staving off colonization of the wound site by opportunistic bacterial pathogens. Possessing such antimicrobial properties would also protect the hydrogel itself from being adversely affected by microbial attachment to its surface. We have previously demonstrated the broad-spectrum antimicrobial activity of supramolecular assemblies of cationic multi-domain peptides (MDPs) in solution. Here, we extend the 1-D soluble supramolecular assembly to 3-D hydrogels to investigate the effect of the supramolecular nanostructure and its rheological properties on the antimicrobial activity of self-assembled hydrogels. Among designed MDPs, the bactericidal activity of peptide hydrogels was found to follow an opposite trend to that in solution. Improved antimicrobial activity of self-assembled peptide hydrogels is dictated by the combined effect of supramolecular surface chemistry and storage modulus of the bulk materials, rather than the ability of individual peptides/peptide assemblies to penetrate bacterial cell membrane as observed in solution. The structure-property-activity relationship developed through this study will provide important guidelines for designing biocompatible peptide hydrogels with built-in antimicrobial activity for various biomedical applications.Hydrogels are an important class of biomaterials that have been widely utilized for a variety of biomedical/medical applications. The biological performance of hydrogels, particularly those used as wound dressing could be greatly advanced if imbued with inherent antimicrobial activity capable of staving off colonization of the wound site by opportunistic bacterial pathogens. Possessing such antimicrobial properties would also protect the hydrogel itself from being adversely affected by microbial attachment to its surface. We have previously demonstrated the broad-spectrum antimicrobial activity of supramolecular assemblies of cationic multi-domain peptides (MDPs) in solution. Here, we extend the 1-D soluble supramolecular assembly to 3-D hydrogels to investigate the effect of the supramolecular nanostructure and its rheological properties on the antimicrobial activity of self-assembled hydrogels. Among designed MDPs, the bactericidal activity of peptide hydrogels was found to follow an opposite trend to that in solution. Improved antimicrobial activity of self-assembled peptide hydrogels is dictated by the combined effect of supramolecular surface chemistry and storage modulus of the bulk materials, rather than the ability of individual peptides/peptide assemblies to penetrate bacterial cell membrane as observed in solution. The structure-property-activity relationship developed through this study will provide important guidelines for designing biocompatible peptide hydrogels with built-in antimicrobial activity for various biomedical applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05233e

Improved Optical and Morphological Properties of Vinyl-Substituted Hybrid Silica Materials Incorporating a Zn-Metalloporphyrin.

PubMed

Dudás, Zoltán; Fagadar-Cosma, Eugenia; Len, Adél; Románszki, Loránd; Almásy, László; Vlad-Oros, Beatrice; Dascălu, Daniela; Krajnc, Andraž; Kriechbaum, Manfred; Kuncser, Andrei

2018-04-06

This work is focused on a novel class of hybrid materials exhibiting enhanced optical properties and high surface areas that combine the morphology offered by the vinyl substituted silica host, and the excellent absorption and emission properties of 5,10,15,20-tetrakis( N -methyl-4-pyridyl)porphyrin-Zn(II) tetrachloride as a water soluble guest molecule. In order to optimize the synthesis procedure and the performance of the immobilized porphyrin, silica precursor mixtures of different compositions were used. To achieve the requirements regarding the hydrophobicity and the porous structure of the gels for the successful incorporation of porphyrin, the content of vinyltriacetoxysilane was systematically changed and thoroughly investigated. Substitution of the silica gels with organic groups is a viable way to provide new properties to the support. An exhaustive characterization of the synthesized silica samples was realised by complementary physicochemical methods, such as infrared spectroscopy (FT-IR), absorption spectroscopy (UV-Vis) and photoluminescence, nuclear magnetic resonance spectroscopy ( 29 Si-MAS-NMR) transmission and scanning electron microscopy (TEM and SEM), nitrogen absorption (BET), contact angle (CA), small angle X ray and neutron scattering (SAXS and SANS). All hybrids showed an increase in emission intensity in the wide region from 575 to 725 nm (Q bands) in comparison with bare porphyrin. By simply tuning the vinyltriacetoxysilane content, the hydrophilic/hydrophobic profile of the hybrid materials was changed, while maintaining a high surface area. Good control of hydrophobicity is important to enhance properties such as dispersion, stability behaviour, and resistance to water, in order to achieve highly dispersible systems in water for biomedical applications.

A bambusuril macrocycle that binds anions in water with high affinity and selectivity.

PubMed

Yawer, Mirza Arfan; Havel, Vaclav; Sindelar, Vladimir

2015-01-02

Synthetic receptors that function in water are important for the qualitative and quantitative detection of anions, which may act as pollutants in the environment or play important roles in biological processes. Neutral receptors are particularly appealing because they are often more selective than positively charged receptors; however, their affinity towards anions in pure water is only in range of 1-10(3)  L mol(-1) . The anion-templated synthesis of a water-soluble bambusuril derivative is shown to be an outstanding receptor for various inorganic anions in pure water, with association constants of up to 10(7)  L mol(-1) . Furthermore, the macrocycle discriminates between anions with unprecedented selectivity (up to 500 000-fold). We anticipate that the combination of remarkable affinity and selectivity of this macrocycle will enable the efficient detection and isolation of diverse anions in aqueous solutions, which is not possible with current supramolecular systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schibilla, Frauke; Voskuhl, Jens; Fokina, Natalie A.

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. Here, 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 triamantanemore » 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.« less

Diffusion-Limited Cargo Loading of an Engineered Protein Container.

PubMed

Zschoche, Reinhard; Hilvert, Donald

2015-12-30

The engineered bacterial nanocompartment AaLS-13 is a promising artificial encapsulation system that exploits electrostatic interactions for cargo loading. In order to study its ability to take up and retain guests, a pair of fluorescent proteins was developed which allows spectroscopic determination of the extent of encapsulation by Förster resonance energy transfer (FRET). The encapsulation process is generally complete within a second, suggesting low energetic barriers for proteins to cross the capsid shell. Formation of intermediate aggregates upon mixing host and guest in vitro complicates capsid loading at low ionic strength, but can be sidestepped by increasing salt concentrations or diluting the components. Encapsulation of guests is completely reversible, and the position of the equilibrium is easily tuned by varying the ionic strength. These results, which challenge the notion that AaLS-13 is a continuous rigid shell, provide valuable information about cargo loading that will guide ongoing efforts to engineer functional host-guest complexes. Moreover, it should be possible to adapt the protein FRET pair described in this report to characterize functional capsid-cargo complexes generated by other encapsulation systems.

The creation of modulated monoclinic aperiodic composites in n-alkane/urea compounds

DOE PAGES

Mariette, Céline; Guérin, Laurent; Rabiller, Philippe; ...

2014-09-12

n-Dodecane/urea is a member of the prototype series of n-alkane/urea inclusion compounds. At room temperature, it presents a quasi-one dimensional liquid-like state for the confined guest molecules within the rigid, hexagonal framework of the urea host. At lower temperatures, we report the existence of two other phases. Below T c=248 K there appears a phase with rank four superspace group P6 122(00γ), the one typically observed at room temperature in n-alkane/urea compounds with longer guest molecules. A misfit parameter, defined by the ratio γ=c h/c g (c host/c guest), is found to be 0.632±0.005. Below T c1=123 K, a monoclinicmore » modulated phase is created with a constant shift along c of the guest molecules in adjacent channels. The maximal monoclinic space group for this structure is P12 11(α0γ). We discuss analogies and differences with n-heptane/urea, which also presents a monoclinic, modulated low-temperature phase.« less

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

DOE PAGES

Schibilla, Frauke; Voskuhl, Jens; Fokina, Natalie A.; ...

2017-11-06

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. Here, 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 triamantanemore » 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.« less

Investigation of the effect of cucurbit[7]uril complexation on the photophysical and acid-base properties of the antimalarial drug quinine.

PubMed

Mallick, Suman; Pal, Kaushik; Chandra, Falguni; Koner, Apurba L

2016-11-09

Host-guest complexation of mono and dicationic quinine with cucurbit[7]uril (CB7), a water-soluble macrocyclic host molecule, has been investigated. Job's plot, time-resolved anisotropy as well as concentration dependent NMR titration confirm the binding of two CB7 macrocycles with one quinine molecule. The binding affinity of dicationic quinine with CB7 is one order of magnitude higher than the binding constant of mono-cationic quinine. Such preferential binding results in one unit pK a shift in the ground-state of the quinoline ring. However, using fluorescence spectroscopy we have obtained two acid-dissociation constants, one for quinoline ring nitrogen and the other for the nitrogen of the quinuclidine moiety. In the excited state, CB7 complexation causes one unit pK a shift for the quinoline ring and 1.9 unit shift for the quinuclidine moiety. Interestingly, a large enhancement of fluorescence lifetime and anisotropy of quinine at pH 2.7 and pH 9.0 upon CB7 complexation was observed due to the restriction of conformational flexibility. Moreover, at pH 3.0, a large fluorescence enhancement of quinine due to CB7 complexation was observed and it was quite significant as compared to that of quinine in 0.1 (M) HCl without CB7. We believe that this study of quinine complexation with CB7 will reduce phototoxicity, increase bioavailability and offer an alternative standard for quantum yield measurements in an amiable condition.

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

PubMed

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.

Imparting biomolecules to a metal-organic framework material by controlled DNA tetrahedron encapsulation

PubMed Central

Jia, Yongmei; Wei, Benmei; Duan, Ruixue; Zhang, Ying; Wang, Boya; Hakeem, Abdul; Liu, Nannan; Ou, Xiaowen; Xu, Shaofang; Chen, Zhifei; Lou, Xiaoding; Xia, Fan

2014-01-01

Recently, the incorporation of biomolecules in Metal-organic frameworks (MOFs) attracts many attentions because of controlling the functions, properties and stability of trapped molecules. Although there are few reports on protein/MOFs composites and their applications, none of DNA/MOFs composite is reported, as far as we know. Here, we report a new composite material which is self-assembled from 3D DNA (guest) and pre-synthesized MOFs (host) by electrostatic interactions and hydrophilic interactions in a well-dispersed fashion. Its biophysical characterization is well analyzed by fluorescence spectroscopy, quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). This new composite material keeps 3D DNA nanostructure more stable than only 3D DNA nanostructure in DI water at room temperature, and stores amounts of genetic information. It will make DNA as a guest for MOFs and MOFs become a new platform for the development of DNA nanotechnology. PMID:25090047

Theoretical insights into aggregation-induced helicity modulation of a perylene bisimide derivative.

PubMed

Liang, Lijun; Li, Xin

2018-02-12

Formation of helical chiroptical self-assemblies via noncovalent interaction is a widely observed phenomenon in nature, the mechanism of which remains insufficiently understood. Employing an amphiphilic perylene-sugar dyad molecule (PBI-HAG) as an example, we report that the modulatable supramolecular helicity may emerge from an aggregating process that is dominated by competition between two types of noncovalent interaction: hydrogen bonding and π-π stacking. The interplay between these two driving forces, which is greatly affected by the solvent environment, determines the morphology the supramolecular assembly of PBI-HAGs. In particular, a non-layered supramolecular structure was formed in octane owing to stabilization effects of intermolecular hydrogen bonds, whereas a layered supramolecular structure was formed in water because of energetically favorable π-π stacking of aromatic rings. The formation of distinct supramolecular architectures in different solvents was reinforced by simulated circular dichroism spectra, which show opposite signals consistent with experimental observations. The results of this study could help us understand aggregation-induced supramolecular chirality of noncovalent self-assemblies. Graphical abstract Left Typical structures of amphiphilic perylene-sugar dyad (PBI-HAG) aggregates in different octane and water. Right Simulated CD and UV-Vis spectra of core PBIs aggregates in octane and water.

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

NASA Astrophysics Data System (ADS)

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.

Preparation, characterization, and luminescence of (SBA-15) immobilized pepsin

NASA Astrophysics Data System (ADS)

Zhai, Qing-Zhou; Sun, Si-Jia

2014-12-01

SBA-15 mesoporous silica was synthesized by hydrothermal method and its surface was methylated by treatment with methyltrimethoxysilane. Pepsin was immobilized on the obtained materials giving host-guest composite materials (SBA-15)-pepsin and (methylated SBA-15)-pepsin. The optimum conditions for preparation of these materials were established. Methylated SBA-15 (M-SBA-15) has improved immobilization efficiency of enzyme compared to initial SBA-15 silica. It was shown that with the gradual increase of NaCl solution ionic strength the immobilized amount of enzyme was reduced. Powder X-ray diffraction and Fourier transform infrared spectroscopy showed that the host frameworks in the prepared host-guest composite materials are intact and the ordered structure was retained. Scanning electron microscopic studies revealed fibrous morphologic characteristics of the SBA-15 and the immobilized pepsin composite materials. The average particle diameter of (SBA-15)-pepsin composite was 338 ± 10 and 343 ± 10 nm for (M-SBA-15)-pepsin. The low temperature N2 adsorption-desorption study at 77 K showed that the pore sizes and specific surface areas of the host-guest composite materials were smaller than those before the introduction of the enzyme, suggesting that the immobilized enzyme occupied a definite position in the host material pore channels. The UV-vis solid diffuse reflectance and luminescence studies showed that the enzyme was successfully immobilized on to the host material and that after the immobilization of enzyme on SBA-15 the conformation of pepsin macromolecule has not been changed.

Complexation and Structure Elucidation of the Axial Conformers of Mono- and (±)-trans-1,2-Disubstituted Cyclohexanes by Enantiopure Alleno-Acetylenic Cage Receptors.

PubMed

Gropp, Cornelius; Trapp, Nils

2018-04-25

Single crystal X-ray diffraction is a powerful method to unambiguously characterize the structure of molecules with atomic resolution. Herein, we review the molecular recognition of the (di)axial conformers of Mono- and (±)-trans-1,2-disubstituted cyclohexanes by enantiopure alleno-acetylenic cage receptors in solution and in the solid state. Single crystals of the host-guest complexes suitable for X-ray diffraction allow for the first time to study the dihedral angles of a series of Mono- and (±)-trans-1,2-disubstituted cyclohexanes in their (di)axial chair conformation. Theoretical studies indicate negligible influence of the host structure on the guest conformation, suggesting that the structural information obtained from the host-guest complexes give insight into the innate structures of Mono- and (±)-trans-1,2-disubstituted cyclohexanes. Strong deviation of the dihedral angles a,a(X-C(1)-C(2)-X) from the idealized 180° are observed, accompanied by substantial flattening of the ring dihedral angles ρ(X-C(1)-C(2)-C(3)).

Star-Shaped Conjugated Molecules with Oxa- or Thiadiazole Bithiophene Side Arms.

PubMed

Kotwica, Kamil; Kostyuchenko, Anastasia S; Data, Przemyslaw; Marszalek, Tomasz; Skorka, Lukasz; Jaroch, Tomasz; Kacka, Sylwia; Zagorska, Malgorzata; Nowakowski, Robert; Monkman, Andrew P; Fisyuk, Alexander S; Pisula, Wojciech; Pron, Adam

2016-08-08

Star-shaped conjugated molecules, consisting of a benzene central unit symmetrically trisubstituted with either oxa- or thiadiazole bithiophene groups, were synthesized as promising molecules and building blocks for application in (opto)electronics and electrochromic devices. Their optical (Eg (opt)) as well as electrochemical (Eg (electro)) band gaps depended on the type of the side arm and the number of solubilizing alkyl substituents. Oxadiazole derivatives showed Eg (opt) slightly below 3 eV and by 0.2 eV larger than those determined for thiadiazole-based compounds. The presence of alkyl substituents in the arms additionally lowered the band gap. The obtained compounds were efficient electroluminophores in guest/host-type light-emitting diodes. They also showed a strong tendency to self-organize in monolayers deposited on graphite, as evidenced by scanning tunneling microscopy. The structural studies by X-ray scattering revealed the formation of supramolecular columnar stacks in which the molecules were organized. Differences in macroscopic alignment in the specimen indicated variations in the self-assembly mechanism between the molecules. The compounds as trifunctional monomers were electrochemically polymerized to yield the corresponding polymer network. As shown by UV/Vis-NIR spectroelectrochemical studies, these networks exhibited reversible electrochromic behavior both in the oxidation and in the reduction modes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A facile strategy to design zeolite L crystals with tunable morphology and surface architecture.

PubMed

Lupulescu, Alexandra I; Kumar, Manjesh; Rimer, Jeffrey D

2013-05-01

Tailoring the anisotropic growth rates of materials to achieve desired structural outcomes is a pervasive challenge in synthetic crystallization. Here we discuss a method to selectively control the growth of zeolite crystals, which are used extensively in a wide range of industrial applications. This facile method cooperatively tunes crystal properties, such as morphology and surface architecture, through the use of inexpensive, commercially available chemicals with specificity for binding to crystallographic surfaces and mediating anisotropic growth. We examined over 30 molecules as potential zeolite growth modifiers (ZGMs) of zeolite L (LTL type) crystallization. ZGM efficacy was quantified through a combination of macroscopic (bulk) and microscopic (surface) investigations that identified modifiers capable of dramatically altering the cylindrical morphology of LTL crystals. We demonstrate an ability to tailor properties critical to zeolite performance, such as external porous surface area, crystal shape, and pore length, which can enhance sorbate accessibility to LTL pores, tune the supramolecular organization of guest-host composites, and minimize the diffusion path length, respectively. We report that a synergistic combination of ZGMs and the judicious adjustment of synthesis parameters produce LTL crystals with unique surface features, and a range of length-to-diameter aspect ratios spanning 3 orders of magnitude. A systematic examination of different ZGM structures and molecular compositions (i.e., hydrophobicity and binding moieties) reveal interesting physicochemical properties governing their efficacy and specificity. Results of this study suggest this versatile strategy may prove applicable for a host of framework types to produce unrivaled materials that have eluded more conventional techniques.

Water-Soluble Nanoparticle Receptors Supramolecularly Coded for Acidic Peptides.

PubMed

Fa, Shixin; Zhao, Yan

2018-01-02

Sequence-specific recognition of peptides is of enormous importance to many chemical and biological applications, but has been difficult to achieve due to the minute differences in the side chains of amino acids. Acidic peptides are known to play important roles in cell growth and gene expression. In this work, we report molecularly imprinted micelles coded with molecular recognition information for the acidic and hydrophobic side chains of acidic peptides. The imprinted receptors could distinguish acidic amino acids from other polar and nonpolar amino acids, with dissociation constants of tens of nanomolar for biologically active peptides containing up to 18 amino acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dielectric anomaly and relaxation natures in a Zn-Cr pillar-layered metal-organic framework with cages and channels

NASA Astrophysics Data System (ADS)

Xue, Chen; Yao, Zhi-Yuan; Liu, Shao-Xian; Luo, Hong-Bin; Zou, Yang; Li, Li; Ren, Xiao-Ming

2017-06-01

A bimetallic metal-organic framework (MOF) with the formula [Zn3btc2{Cr3O(isonic)6(H2O)2(OH)}]·(DMF)15.5(H2O)8 (H3btc=1,3,5-benzenetricarboxylic acid; isonic=isonicotinicate) shows a pillar-layered structure. The monolayer consists of hexagon-like rings formed by the [Zn(isonic)2(btc)2] tetrahedral and the consecutive monolayers are pillared by trigonal-prismatic clusters of [Cr3O(isonic)6(H2O)2(OH)]through the remaining binding sites of the Zn2+ ions. DMF and water molecules are confined in the cages and channels. TGA indicates that the lattice DMF and water molecules begin to be released at temperatures above 363 K. Dielectric measurements were carried out in the range of 173-363 K and 1-107 Hz for three successive thermal cycles. The dielectric spectroscopy obtained in the first thermal cycle was different from that observed in the next two thermal cycles, while the dielectric spectra in the last two thermal cycles were almost identical. The dielectric nature of this MOF is discussed in detail for each thermal cycle. Since MOFs are unique host-guest systems in which the structure of the host framework is designable and the guests are exchangeable, it is no doubt those MOFs are materials with a variety of dielectric natures. This study gives a fresh impetus to achieve MOFs-based dielectric materials.

Supramolecular complexation for environmental control.

PubMed

Albelda, M Teresa; Frías, Juan C; García-España, Enrique; Schneider, Hans-Jörg

2012-05-21

Supramolecular complexes offer a new and efficient way for the monitoring and removal of many substances emanating from technical processes, fertilization, plant and animal protection, or e.g. chemotherapy. Such pollutants range from toxic or radioactive metal ions and anions to chemical side products, herbicides, pesticides to drugs including steroids, and include degradation products from natural sources. The applications involve usually fast and reversible complex formation, due to prevailing non-covalent interactions. This is of importance for sensing as well as for separation techniques, where the often expensive host compounds can then be reused almost indefinitely. Immobilization of host compounds, e.g. on exchange resins or on membranes, and their implementation in smart new materials hold particular promise. The review illustrates how the design of suitable host compounds in combination with modern sensing and separation methods can contribute to solve some of the biggest problems facing chemistry, which arise from the everyday increasing pollution of the environment.

Impact of helical organization on the photovoltaic properties of oligothiophene supramolecular polymers† †Electronic supplementary information (ESI) available: Synthesis and characterization of 3 and 4, UV-vis spectra, solar cell device properties and AFM images. See DOI: 10.1039/c7sc05093c

PubMed Central

Ouchi, Hayato; Kizaki, Takahiro; Yamato, Masaki; Lin, Xu; Hoshi, Nagahiro; Silly, Fabien; Kajitani, Takashi; Fukushima, Takanori

2018-01-01

Helical self-assembly of functional π-conjugated molecules offers unique photochemical and electronic properties in the spectroscopic level, but there are only a few examples that demonstrate their positive impact on the optoelectronic device level. Here, we demonstrate that hydrogen-bonded tapelike supramolecular polymers of a barbiturated oligo(alkylthiophene) show notable improvement in their photovoltaic properties upon organizing into helical nanofibers. A tapelike hydrogen-bonded supramolecular array of barbiturated oligo(butylthiophene) molecules was directly visualized by STM at a liquid–solid interface. TEM, AFM and XRD revealed that the tapelike supramolecular polymers further organize into helical nanofibers in solution and bulk states. Bulk heterojunction solar cells of the helical nanofibers and soluble fullerene showed a power conversion efficiency of 4.5%, which is markedly high compared to that of the regioisomer of butyl chains organizing into 3D lamellar agglomerates. PMID:29780493

Modified β-Cyclodextrin Inclusion Complex to Improve the Physicochemical Properties of Albendazole. Complete In Vitro Evaluation and Characterization

PubMed Central

García, Agustina; Leonardi, Darío; Salazar, Mario Oscar; Lamas, María Celina

2014-01-01

The potential use of natural cyclodextrins and their synthetic derivatives have been studied extensively in pharmaceutical research and development to modify certain properties of hydrophobic drugs. The ability of these host molecules of including guest molecules within their cavities improves notably the physicochemical properties of poorly soluble drugs, such as albendazole, the first chosen drug to treat gastrointestinal helminthic infections. Thus, the aim of this work was to synthesize a beta cyclodextrin citrate derivative, to analyze its ability to form complexes with albendazole and to evaluate its solubility and dissolution rate. The synthesis progress of the cyclodextrin derivative was followed by electrospray mass spectrometry and the acid-base titration of the product. The derivative exhibited an important drug affinity. Nuclear magnetic resonance experiments demonstrated that the tail and the aromatic ring of the drug were inside the cavity of the cyclodextrin derivative. The inclusion complex was prepared by spray drying and full characterized. The drug dissolution rate displayed exceptional results, achieving 100% drug release after 20 minutes. The studies indicated that the inclusion complex with the cyclodextrin derivative improved remarkably the physicochemical properties of albendazole, being a suitable excipient to design oral dosage forms. PMID:24551084

The effect of mechanical grinding on the formation, crystalline changes and dissolution behaviour of the inclusion complex of telmisartan and β-cyclodextrins.

PubMed

Borba, Paola Aline Amarante; Pinotti, Marihá; Andrade, George Ricardo Santana; da Costa, Nivan Bezerra; Olchanheski Junior, Luiz Renato; Fernandes, Daniel; de Campos, Carlos Eduardo Maduro; Stulzer, Hellen Karine

2015-11-20

Telmisartan (TEL) was entrapped into β-cyclodextrin aiming the improvement of its biopharmaceutical properties of low solubility. A solid state grinding process was used to prepare the molecular inclusion complex (MIC) for up to 30min. The inclusion ratio of drug and β-cyclodextrin was established as 1:2 and 1:3 (mol/mol) by phase solubility study and Job Plot. DSC, XRPD and FTIR confirmed the molecular interactions between TEL and β-cyclodextrin. Computer molecular modeling supports the presence of hydrogen bonds between guest and host and demonstrated the most probable complexes configuration. MIC_1:2_30 and MIC_1:3_30 enhanced the dissolution rate of the drug achieving a delivery rate comparable with the reference medicine available in the market (81% and 87% in 5min, for MIC_1:3_30 and Micardis(®), respectively). These formulations showed rapid and effective antihypertensive effect against angiotensin II in rats up to 180min, with statistically significant results against placebo and control in the first 30min after administration. Copyright © 2015 Elsevier Ltd. All rights reserved.

Molecular structures of the inclusion complexes beta-cyclodextrin-1,2-bis(4-aminophenyl)ethane and beta-cyclodextrin-4,4'-diaminobiphenyl; packing of dimeric beta-cyclodextrin inclusion complexes.

PubMed

Giastas, Petros; Yannakopoulou, Konstantina; Mavridis, Irene M

2003-04-01

The present investigation is part of an ongoing study on the influence of the long end-functonalized guest molecules DBA and BNZ in the crystal packing of beta-cyclodextrin (betaCD) dimeric complexes. The title compounds are 2:2 host:guest complexes showing limited host-guest hydrogen bonding at the primary faces of the betaCD dimers. Within the betaCD cavity the guests exhibit mutual pi...pi interactions and between betaCD dimers perpendicular NH...pi interactions. The DBA guest molecule exhibits one extended and two bent conformations in the complex. The BNZ guest molecule is not planar inside betaCD, in contrast to the structure of BNZ itself, which indicates that the cavity isolates the molecules and forbids the pi...pi stacking of the aromatic rings. NMR spectroscopy studies show that in aqueous solution both DBA and BNZ form strong complexes that have 1:1 stoichiometry and structures similar to the solid state ones. The relative packing of the dimers is the same in both complexes. The axes of two adjacent dimers form an angle close to 20 degrees and have a lateral displacement approximately 2.45 A, both of which characterize the screw-channel mode of packing. Although the betaCD/BNZ complex indeed crystallizes in a space group characterizing the latter mode, the betaCD/DBA complex crystallizes in a space group with novel dimensions not resembling any of the packing modes reported so far. The new lattice is attributed to the three conformations exhibited by the guest in the crystals. However, this lattice can be transformed into another, which is isostructural to that of the betaCD/BNZ inclusion complex, if the conformation of the guest is not taken into account.

Synthesis and crystal structures of inclusion compounds of 2,2'-dithiosalicylic acid and triethylamine/tripropylamine

NASA Astrophysics Data System (ADS)

Yang, Y. X.; Li, H. Y.; Wu, J. F.

2015-12-01

Herein we reported two new inclusion compounds of 2,2'-dithiosalicylic acid (C14H10O4S2, DTSA) and triethylamine and tripropylamine, [C14H8O4S 2 2- · [N+(C2H5)3]2 · H2O] (1) and [C14H10O4S2 · C14H8O4S 2 2- · [N+(C3H7)3]2] (2). Compound 1: triclinic P overline 1, a = 8.2159(2), b = 12.5724(3), c = 14.9203(3) Å, α = 97.0390(10), β = 101.4310(10)°, γ = 101.3370(10)°, V = 1460.06(6) Å3, Z = 2, R 1 = 0.0526, wR 2 = 0.1495; Compound 2: monoclinic P21/ c, a = 20.5178(13), b = 15.3623(8), c = 15.5529(9) Å, β = 102.036(3)°, V = 4794.5(5) Å3, Z = 4, R 1 = 0.0533, wR 2 = 0.1252. In these two crystal structures, DTSA utilizes conventional O-H···O hydrogen bonds to link to generate varied host lattices, in which the central N atoms of the guest amine molecules accept the protons of DTSA to form the corresponding cations to act as the couterions to develop the stable crystal structures. Noticeably, except Van der Waals forces usually existing between the host and guest molecules, the central N atoms of the guests of the two compounds can construct strong N-H…O hydrogen bonds with the related host molecules, which further enforce the host-guest interactions to help form the final inclusion compounds.

Adsorption and separation of reactive aromatic isomers and generation and stabilization of their radicals within cadmium(II)-triazole metal-organic confined space in a single-crystal-to-single-crystal fashion.

PubMed

Liu, Qi-Kui; Ma, Jian-Ping; Dong, Yu-Bin

2010-05-26

A series of reactive group functionalized aromatics, namely 2-furaldehyde, 3-furaldehyde, 2-thenaldehyde, 3-thenaldehyde, o-toluidine, m-toluidine, p-toluidine, and aniline, can be absorbed by a CdL(2) (1; L = 4-amino-3,5-bis(4-pyridyl-3-phenyl)-1,2,4-triazole) porous framework in both vapor and liquid phases to generate new G(n) [symbol: see text] CdL(2) (n = 1, 2) host-guest complexes. In addition, the CdL(2) framework can be a shield to protect the active functional group (-CHO and -NH(2)) substituted guests from reaction with the outside medium containing their reaction partners. That is, aldehyde-substituted guests within the CdL(2) host become "stable" in the aniline phase and vice versa. Moreover, 1 displays a very strict selectivity for these reactive group substituted aromatic isomers and can completely separate these guest isomers under mild conditions (i.e., 2-furaldehyde vs 3-furaldehyde, 2-thenaldehyde vs 3-thenaldehyde, and o-toluidine vs m-toluidine vs p-toluidine). All adsorptions and separations are directly performed on the single crystals of 1. More interestingly, these reactive group substituted aromatics readily transform to the corresponding radicals within the CdL(2) host upon ambient light or UV light (355 nm) irradiation. Furthermore, the generated organic radicals are alive for 1 month within the interior cavity in air under ambient conditions. Simple organic radicals are highly reactive short-lived species, and they cannot be generally isolated and conserved under ambient conditions. Thus, the CdL(2) host herein could be considered as a radical generator and storage vessel.

How the guest molecules in nanoporous Zn(II) metal-organic framework can prevent agglomeration of ZnO nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moeinian, Maryam; Akhbari, Kamran, E-mail: akhbari.k@khayam.ut.ac.ir

The host and the apohost framework of [Zn{sub 2}(BDC){sub 2}(H{sub 2}O){sub 2}·(DMF){sub 2}]{sub n} (1·2H{sub 2}O·2DMF), (BDC{sup 2−}=benzene-1,4-dicarboxylate and DMF=N,N-Dimethylformamide), were synthesized and subsequently used for preparation of ZnO nanomaterials. With calcination of the host framework of 1·2H{sub 2}O·2DMF, ZnO nanoparticles were obtained. By the same process on the apohost framework of 1, agglomerated nanoparticles of ZnO were formed. These nano-structures were characterized by X-ray powder diffraction (XRD) and Scanning electron microscopy (SEM). These results indicate that with removal of the guest DMF and coordinated H{sub 2}O molecules from the one-dimensional channels of 1·2H{sub 2}O·2DMF, the tendency of nanoparticles tomore » agglomerate increases and the role of this MOF in preparation of ZnO nanoparticles from this precursor was reduced. - Graphical abstract: Nano-porous zinc(II) MOF with guest DMF and coordinated H{sub 2}O molecules has been synthesized and characterized. The host and the apohost framework of it were used for preparation of ZnO nanomaterials. The role of these species in preparation of ZnO nanoparticles from the host framework is probably similar to the role of polymeric stabilizers in formation of nanoparticles. - Highlights: • Nanoparticles of ZnO were fabricated from nanoporous metal-organic framework. • The effect of guest DMF and coordinated H{sub 2}O molecules on this process was studied. • The effect of them in formation nanoparticle is similar to polymeric stabilizers.« less

Preparation of graphite intercalation compounds containing oligo and polyethers

NASA Astrophysics Data System (ADS)

Zhang, Hanyang; Lerner, Michael M.

2016-02-01

Layered host-polymer nanocomposites comprising polymeric guests between inorganic sheets have been prepared with many inorganic hosts, but there is limited evidence for the incorporation of polymeric guests into graphite. Here we report for the first time the preparation, and structural and compositional characterization of graphite intercalation compounds (GICs) containing polyether bilayers. The new GICs are obtained by either (1) reductive intercalation of graphite with an alkali metal in the presence of an oligo or polyether and an electrocatalyst, or (2) co-intercalate exchange of an amine for an oligo or polyether in a donor-type GIC. Structural characterization of products using powder X-ray diffraction, Raman spectroscopy, and thermal analyses supports the formation of well-ordered, first-stage GICs containing alkali metal cations and oligo or polyether bilayers between reduced graphene sheets.Layered host-polymer nanocomposites comprising polymeric guests between inorganic sheets have been prepared with many inorganic hosts, but there is limited evidence for the incorporation of polymeric guests into graphite. Here we report for the first time the preparation, and structural and compositional characterization of graphite intercalation compounds (GICs) containing polyether bilayers. The new GICs are obtained by either (1) reductive intercalation of graphite with an alkali metal in the presence of an oligo or polyether and an electrocatalyst, or (2) co-intercalate exchange of an amine for an oligo or polyether in a donor-type GIC. Structural characterization of products using powder X-ray diffraction, Raman spectroscopy, and thermal analyses supports the formation of well-ordered, first-stage GICs containing alkali metal cations and oligo or polyether bilayers between reduced graphene sheets. Electronic supplementary information (ESI) available: Domain size, additional Raman spectra info, compositional calculation, and packing fractions. See DOI: 10.1039/c5nr08226a

Understanding decomposition and encapsulation energies of structure I and II clathrate hydrates

NASA Astrophysics Data System (ADS)

Alavi, Saman; Ohmura, Ryo

2016-10-01

When compressed with water or ice under high pressure and low temperature conditions, some gases form solid gas hydrate inclusion compounds which have higher melting points than ice under those pressures. In this work, we study the balance of the guest-water and water-water interaction energies that lead to the formation of the clathrate hydrate phases. In particular, molecular dynamics simulations with accurate water potentials are used to study the energetics of the formation of structure I (sI) and II (sII) clathrate hydrates of methane, ethane, and propane. The dissociation enthalpy of the clathrate hydrate phases, the encapsulation enthalpy of methane, ethane, and propane guests in the corresponding phases, and the average bonding enthalpy of water molecules are calculated and compared with accurate calorimetric measurements and previous classical and quantum mechanical calculations, when available. The encapsulation energies of methane, ethane, and propane guests stabilize the small and large sI and sII hydrate cages, with the larger molecules giving larger encapsulation energies. The average water-water interactions are weakened in the sI and sII phases compared to ice. The relative magnitudes of the van der Waals potential energy in ice and the hydrate phases are similar, but in the ice phase, the electrostatic interactions are stronger. The stabilizing guest-water "hydrophobic" interactions compensate for the weaker water-water interactions and stabilize the hydrate phases. A number of common assumptions regarding the guest-cage water interactions are used in the van der Waals-Platteeuw statistical mechanical theory to predict the clathrate hydrate phase stability under different pressure-temperature conditions. The present calculations show that some of these assumptions may not accurately reflect the physical nature of the interactions between guest molecules and the lattice waters.

Understanding decomposition and encapsulation energies of structure I and II clathrate hydrates.

PubMed

Alavi, Saman; Ohmura, Ryo

2016-10-21

When compressed with water or ice under high pressure and low temperature conditions, some gases form solid gas hydrate inclusion compounds which have higher melting points than ice under those pressures. In this work, we study the balance of the guest-water and water-water interaction energies that lead to the formation of the clathrate hydrate phases. In particular, molecular dynamics simulations with accurate water potentials are used to study the energetics of the formation of structure I (sI) and II (sII) clathrate hydrates of methane, ethane, and propane. The dissociation enthalpy of the clathrate hydrate phases, the encapsulation enthalpy of methane, ethane, and propane guests in the corresponding phases, and the average bonding enthalpy of water molecules are calculated and compared with accurate calorimetric measurements and previous classical and quantum mechanical calculations, when available. The encapsulation energies of methane, ethane, and propane guests stabilize the small and large sI and sII hydrate cages, with the larger molecules giving larger encapsulation energies. The average water-water interactions are weakened in the sI and sII phases compared to ice. The relative magnitudes of the van der Waals potential energy in ice and the hydrate phases are similar, but in the ice phase, the electrostatic interactions are stronger. The stabilizing guest-water "hydrophobic" interactions compensate for the weaker water-water interactions and stabilize the hydrate phases. A number of common assumptions regarding the guest-cage water interactions are used in the van der Waals-Platteeuw statistical mechanical theory to predict the clathrate hydrate phase stability under different pressure-temperature conditions. The present calculations show that some of these assumptions may not accurately reflect the physical nature of the interactions between guest molecules and the lattice waters.

Nano-Assemblies of Modified Cyclodextrins and Their Complexes with Guest Molecules: Incorporation in Nanostructured Membranes and Amphiphile Nanoarchitectonics Design

PubMed Central

Zerkoune, Leïla; Angelova, Angelina; Lesieur, Sylviane

2014-01-01

A variety of cyclodextrin-based molecular structures, with substitutions of either primary or secondary faces of the natural oligosaccharide macrocycles of α-, β-, or γ-cyclodextrins, have been designed towards innovative applications of self-assembled cyclodextrin nanomaterials. Amphiphilic cyclodextrins have been obtained by chemical or enzymatic modifications of their macrocycles using phospholipidyl, peptidolipidyl, cholesteryl, and oligo(ethylene oxide) anchors as well as variable numbers of grafted hydrophobic hydrocarbon or fluorinated chains. These novel compounds may self-assemble in an aqueous medium into different types of supramolecular nanoassemblies (vesicles, micelles, nanorods, nanospheres, and other kinds of nanoparticles and liquid crystalline structures). This review discusses the supramolecular nanoarchitectures, which can be formed by amphiphilic cyclodextrin derivatives in mixtures with other molecules (phospholipids, surfactants, and olygonucleotides). Biomedical applications are foreseen for nanoencapsulation of drug molecules in the hydrophobic interchain volumes and nanocavities of the amphiphilic cyclodextrins (serving as drug carriers or pharmaceutical excipients), anticancer phototherapy, gene delivery, as well as for protection of instable active ingredients through inclusion complexation in nanostructured media. PMID:28344245

Functionalization of Mechanochemically Passivated Germanium Nanoparticles via "Click" Chemistry

NASA Astrophysics Data System (ADS)

Purkait, Tapas Kumar

Germanium nanoparticles (Ge NPs) may be fascinating for their electronic and optoelectronic properties, as the band gap of Ge NPs can be tuned from the infrared into the visible range of solar spectru. Further functionalization of those nanoparticles may potentially lead to numerous applications ranging from surface attachment, bioimaging, drug delivery and nanoparticles based devices. Blue luminescent germanium nanoparticles were synthesized from a novel top-down mechanochemical process using high energy ball milling (HEBM) of bulk germanium. Various reactive organic molecules (such as, alkynes, nitriles, azides) were used in this process to react with fresh surface and passivate the surface through Ge-C or Ge-N bond. Various purification process, such as gel permeation chromatography (GPC), Soxhlet dailysis etc. were introduced to purify nanoparticles from molecular impurities. A size separation technique was developed using GPC. The size separated Ge NPs were characterize by TEM, small angle X-ray scattering (SAXS), UV-vis absorption and photoluminescence (PL) emission spectroscopy to investigate their size selective properties. Germanium nanoparticles with alkyne termini group were prepared by HEBM of germanium with a mixture of n-alkynes and alpha, o-diynes. Additional functionalization of those nanoparticles was achieved by copper(I) catalyzed azide-alkyne "click" reaction. A variety of organic and organometallic azides including biologically important glucals have been reacted in this manner resulting in nanopartilces adorned with ferrocenyl, trimethylsilyl, and glucal groups. Additional functionalization of those nanoparticles was achieved by reactions with various azides via a Cu(I) catalyzed azide-alkyne "click" reaction. Various azides, including PEG derivatives and cylcodextrin moiety, were grafted to the initially formed surface. Globular nanoparticle arrays were formed through interparticle linking via "click" chemistry or "host-guest" chemistry. Copper(I) catalyzed "click" chemistry also can be explored with azido-terminated Ge NPs which were synthesized by azidation of chloro-terminated Ge NPs. Water soluble PEGylated Ge NPs were synthesized by "click" reaction for biological application. PEGylated Ge NP clusters were prepared using alpha, o-bis alkyno or bis-azido polyethylene glycol (PEG) derivatives by copper catalyzed "click" reaction via inter-particle linking. These nanoparticles were further functionalized by azido beta-cyclodextrin (beta-CD) and azido adamantane via alkyne-azide "click" reactions. Nanoparticle clusters were made from the functionalized Ge NPs by "host-guest" chemistry of beta-CD functionalized Ge NPs either with adamantane functionalized Ge NPs or fullerene, C60.

A Statistical Analysis of the PPII Propensity of Amino Acid Guests in Proline-Rich Peptides

PubMed Central

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

2011-01-01

There has been considerable debate about the intrinsic PPII propensity of amino-acid residues in denatured polypeptides. Experimentally, the propensity scale is based on the behavior of guest amino-acid residues placed in the middle of polyproline hosts. We have used classical molecular dynamics simulations, with state-of-the-art force fields to carry out a comprehensive analysis of the conformational equilibria of the proline-based host oligopeptides with single guests. The tracked structural characteristics include the PPII content, the cis/trans isomerization of the prolyl bonds, the puckering of the pyrrolidine rings of the proline residues, and the secondary structural motifs. We find no evidence for an intrinsic PPII propensity in any of the guest amino acids other than proline. Instead, the PPII content as derived from experiments may be explained in terms of: 1), a local correlation between the dihedral angles of the guest amino acid and the proline residue immediately preceding it; and 2), a nonlocal correlation between the cis/trans states of the peptide bonds. In terms of the latter, we find that the presence of a guest (other than proline, tyrosine, or tryptophan) increases the trans content of most of the prolyl bonds, which results in an effective increase of the peptide PPII content. With respect to the local dihedral correlations, we find that these are well described in terms of the so-called odds-ratio statistic. Expressed in terms of free energy language, the PPII content based on the odds-ratio of the relevant residues correlate well with the experimentally measured PPII content. PMID:21320454

Cooperativity and complexity in the binding of anions and cations to a tetratopic ion-pair host.

PubMed

Howe, Ethan N W; Bhadbhade, Mohan; Thordarson, Pall

2014-05-21

Cooperative interactions play a very important role in both natural and synthetic supramolecular systems. We report here on the cooperative binding properties of a tetratopic ion-pair host 1. This host combines two isophthalamide anion recognition sites with two unusual "half-crown/two carbonyl" cation recognition sites as revealed by the combination of single-crystal X-ray analysis of the free host and the 1:2 host:calcium cation complex, together with two-dimensional NMR and computational studies. By systematically comparing all of the binding data to several possible binding models and focusing on four different variants of the 1:2 binding model, it was in most cases possible to quantify these complex cooperative interactions. The data showed strong negative cooperativity (α = 0.01-0.05) of 1 toward chloride and acetate anions, while for cations the results were more variable. Interestingly, in the competitive (CDCl3/CD3OD (9:1, v/v)) solvent, the addition of calcium cations to the tetratopic ion-pair host 1 allosterically switched "on" chloride binding that is otherwise not present in this solvent system. The insight into the complexity of cooperative interactions revealed in this study of the tetratopic ion-pair host 1 can be used to design better cooperative supramolecular systems for information transfer and catalysis.

Large scale affinity calculations of cyclodextrin host-guest complexes: Understanding the role of reorganization in the molecular recognition process

PubMed Central

Wickstrom, Lauren; He, Peng; Gallicchio, Emilio; Levy, Ronald M.

2013-01-01

Host-guest inclusion complexes are useful models for understanding the structural and energetic aspects of molecular recognition. Due to their small size relative to much larger protein-ligand complexes, converged results can be obtained rapidly for these systems thus offering the opportunity to more reliably study fundamental aspects of the thermodynamics of binding. In this work, we have performed a large scale binding affinity survey of 57 β-cyclodextrin (CD) host guest systems using the binding energy distribution analysis method (BEDAM) with implicit solvation (OPLS-AA/AGBNP2). Converged estimates of the standard binding free energies are obtained for these systems by employing techniques such as parallel Hamitionian replica exchange molecular dynamics, conformational reservoirs and multistate free energy estimators. Good agreement with experimental measurements is obtained in terms of both numerical accuracy and affinity rankings. Overall, average effective binding energies reproduce affinity rank ordering better than the calculated binding affinities, even though calculated binding free energies, which account for effects such as conformational strain and entropy loss upon binding, provide lower root mean square errors when compared to measurements. Interestingly, we find that binding free energies are superior rank order predictors for a large subset containing the most flexible guests. The results indicate that, while challenging, accurate modeling of reorganization effects can lead to ligand design models of superior predictive power for rank ordering relative to models based only on ligand-receptor interaction energies. PMID:25147485

Supramolecular Control over the Interparticle Distance in Gold Nanoparticle Arrays by Cyclodextrin Polyrotaxanes

PubMed Central

Paulo Coelho, Joao; Osío Barcina, José; Aicart, Emilio; Tardajos, Gloria; Cruz-Gil, Pablo; Salgado, Cástor; Díaz-Núñez, Pablo

2018-01-01

Amphiphilic nonionic ligands, synthesized with a fixed hydrophobic moiety formed by a thiolated alkyl chain and an aromatic ring, and with a hydrophilic tail composed of a variable number of oxyethylene units, were used to functionalize spherical gold nanoparticles (AuNPs) in water. Steady-state and time-resolved fluorescence measurements of the AuNPs in the presence of α-cyclodextrin (α-CD) revealed the formation of supramolecular complexes between the ligand and macrocycle at the surface of the nanocrystals. The addition of α-CD induced the formation of inclusion complexes with a high apparent binding constant that decreased with the increasing oxyethylene chain length. The formation of polyrotaxanes at the surface of AuNPs, in which many α-CDs are trapped as hosts on the long and linear ligands, was demonstrated by the formation of large and homogeneous arrays of self-assembled AuNPs with hexagonal close packing, where the interparticle distance increased with the length of the oxyethylene chain. The estimated number of α-CDs per polyrotaxane suggests a high rigidization of the ligand upon complexation, allowing for nearly perfect control of the interparticle distance in the arrays. This degree of supramolecular control was extended to arrays formed by AuNPs stabilized with polyethylene glycol and even to binary arrays. Electromagnetic simulations showed that the enhancement and distribution of the electric field can be finely controlled in these plasmonic arrays. PMID:29547539