Experimental and theoretical studies on a novel helical architecture ...

Indian Academy of Sciences (India)

A novel two-dimensional (2D), layered, helical supramolecular architecture constructed via cooperative hydrogen bond and halogen bonds was synthesized and characterized: [(BMBA)₂(TPB)]n (1) [BMBA= 3-bromo-2-methylbenzoic acid, TPB = 1,2,3,4-tetra-(4-pyridyl)-butane]. Density functional theory (DFT) calculations ...

Constructional Efficiency in Al_Ahwaar Traditional Architecture

Directory of Open Access Journals (Sweden)

Usama Abdul-Mun'em Khuraibet

2016-03-01

Full Text Available Constructional Efficiency in architecture in general is one of the most important standard success for any structure and a measure of its continuity and relevance across time and space. Given the importance of Al-Ahwaar environment that owned the spatial, environmental, economic and social elements had a prominent impact in creation of architecture patterns form to create special architectural and structural environment, which had many qualities and ingredients that contributed to its continuity and existence over the years. From the premise that man and his environment is the main goal to any architectural style, Thus the research problem focusing on the lack of clarity of the previous literatures in its studies for the role of architectural styles in Al-Ahwaar in achieving constructional efficiency, despite the large number of studies on Al-Ahwaar architecture but it is mostly marked by non-clarity and lack in the constructional and technical aspects, Therefore, the research goal focusing on clarification of the impact of the techniques that used in formations Al_Ahwaar traditional architecture in order to reach to the constructional efficiency in various aspects such as technical, material, economical, and expressional. Assuming that achieving to the constructional efficiency at Al-Ahwaar traditional architecture depends on its characteristics and elements that contributed to the continuity of their patterns across time. The research depended on analytical method of a model of traditional architecture in Al-Ahwaar to reach those goals, as the study of these items aims to deepen the understanding of the designer to the requirements of each component in order to achieve integration together. These components must not conflict with each other, but it must be integrated during and after the design process until it comes out as a creative of architectural destination. al-ahwaar architecture, constructional efficiency, technical and material

Building constructions: architecture and nature

Directory of Open Access Journals (Sweden)

Mayatskaya Irina

2017-01-01

Full Text Available The problem of optimization of building structures is considered in architectural bionic modeling on the bionic principle basis. It is possible to get a reliable and durable constructions by studying the structure and the laws of organization of natural objects. Modern architects have created unique buildings using the bionic approach. There are such properties as symmetry, asymmetry, self-similarity and fractality used in the modern architecture. Using the methods of fractal geometry in the design of architectural forms allows finding a variety of constructive solutions.

Supramolecular architectures in layer-by-layer films of single-walled carbon nanotubes, chitosan and cobalt (II) phthalocyanine

Energy Technology Data Exchange (ETDEWEB)

Sousa Luz, Roberto A. de; Martins, Marccus Victor A.; Magalhaes, Janildo L. [Departamento de Quimica, Centro de Ciencias da Natureza, Universidade Federal do Piaui, Teresina - PI, CEP 64049-550 (Brazil); Siqueira, Jose R. [Instituto de Ciencias Exatas, Naturais e Educacao, Universidade Federal do Triangulo Mineiro, Uberaba - MG, CEP 38025-180, Brazil (Brazil); Zucolotto, Valtencir; Oliveira, Osvaldo N. [Instituto de Fisica de Sao Carlos, Universidade de Sao Paulo, Sao Carlos - SP, CEP 13560-970 (Brazil); Crespilho, Frank N. [Centro de Ciencias Naturais e Humanas, Universidade Federal do ABC, Santo Andre - SP, CEP 09210-170 (Brazil); Cantanhede da Silva, Welter, E-mail: welter@ufpi.edu.br [Departamento de Quimica, Centro de Ciencias da Natureza, Universidade Federal do Piaui, Teresina - PI, CEP 64049-550 (Brazil)

2011-11-01

Highlights: {yields} Platforms were assembled from cobalt phthalocyanine, chitosan and carbon nanotubes. {yields} Supramolecular organization of multilayer films was investigated. {yields} Increase of the supramolecular charge transfer after carbon nanotube incorporation. {yields} Functional modulation based on constitutional dynamic chemistry was achieved. - Abstract: The building of supramolecular structures in nanostructured films has been exploited for a number of applications, with the film properties being controlled at the molecular level. In this study, we report on the layer-by-layer (LbL) films combining cobalt (II) tetrasulfonated phthalocyanine (CoTsPc), chitosan (Chit) and single-walled carbon nanotubes (SWCNTs) in two architectures, {l_brace}Chit/CoTsPc{r_brace}{sub n} and {l_brace}Chit-SWCNTs/CoTsPc{r_brace}{sub n} (n = 1-10). The physicochemical properties of the films were evaluated and the multilayer formation was monitored with microgravimetry measurements using a quartz microbalance crystal and an electrochemical technique. According to atomic force microscopy (AFM) results, the incorporation of SWCNTs caused the films to be thicker, with a thickness ca. 3 fold that of a 2-bilayer LbL film with no SWCNTs. Cyclic voltammetry revealed a quasi-reversible, one electron process with E{sub 1/2} at -0.65 V (vs SCE) and an irreversible oxidation process at 0.80 V in a physiological medium for both systems, which can be attributed to [CoTsPc(I)]{sup 5-}/[CoTsPc(II)]{sup 4-} and CoTsPc(II) to CoTsPc(III), respectively. The {l_brace}Chit-SWCNTs/CoTsPc{r_brace}{sub 5} multilayer film exhibited an increased faradaic current, probably associated with the supramolecular charge transfer interaction between cobalt phthalocyanine and SWCNTs. The results demonstrate that an intimate contact at the supramolecular level between functional SWCNTs immobilized into biocompatible chitosan polymer and CoTsPc improves the electron flow from CoTsPc redox sites to the

From supramolecular polymers to multi-component biomaterials.

Science.gov (United States)

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

2017-10-30

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

Advanced customization in architectural design and construction

CERN Document Server

Naboni, Roberto

2015-01-01

This book presents the state of the art in advanced customization within the sector of architectural design and construction, explaining important new technologies that are boosting design, product and process innovation and identifying the challenges to be confronted as we move toward a mass customization construction industry. Advanced machinery and software integration are discussed, as well as an overview of the manufacturing techniques offered through digital methods that are acquiring particular significance within the field of digital architecture. CNC machining, Robotic Fabrication, and Additive Manufacturing processes are all clearly explained, highlighting their ability to produce personalized architectural forms and unique construction components. Cutting-edge case studies in digitally fabricated architectural realizations are described and, looking towards the future, a new model of 100% customized architecture for design and construction is presented. The book is an excellent guide to the profoun...

Supramolecular Architectures and Mimics of Complex Natural Folds Derived from Rationally Designed alpha-Helical Protein Structures

Science.gov (United States)

Tavenor, Nathan Albert

Protein-based supramolecular polymers (SMPs) are a class of biomaterials which draw inspiration from and expand upon the many examples of complex protein quaternary structures observed in nature: collagen, microtubules, viral capsids, etc. Designing synthetic supramolecular protein scaffolds both increases our understanding of natural superstructures and allows for the creation of novel materials. Similar to small-molecule SMPs, protein-based SMPs form due to self-assembly driven by intermolecular interactions between monomers, and monomer structure determines the properties of the overall material. Using protein-based monomers takes advantage of the self-assembly and highly specific molecular recognition properties encodable in polypeptide sequences to rationally design SMP architectures. The central hypothesis underlying our work is that alpha-helical coiled coils, a well-studied protein quaternary folding motif, are well-suited to SMP design through the addition of synthetic linkers at solvent-exposed sites. Through small changes in the structures of the cross-links and/or peptide sequence, we have been able to control both the nanoscale organization and the macroscopic properties of the SMPs. Changes to the linker and hydrophobic core of the peptide can be used to control polymer rigidity, stability, and dimensionality. The gaps in knowledge that this thesis sought to fill on this project were 1) the relationship between the molecular structure of the cross-linked polypeptides and the macroscopic properties of the SMPs and 2) a means of creating materials exhibiting multi-dimensional net or framework topologies. Separate from the above efforts on supramolecular architectures was work on improving backbone modification strategies for an alpha-helix in the context of a complex protein tertiary fold. Earlier work in our lab had successfully incorporated unnatural building blocks into every major secondary structure (beta-sheet, alpha-helix, loops and beta

Supramolecular chemistry and crystal engineering

Indian Academy of Sciences (India)

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

Thermolysis synthesis of pure phase NiO from novel sonochemical synthesized Ni(II) nano metal-organic supramolecular architecture.

Science.gov (United States)

Hanifehpour, Younes; Morsali, Ali; Mirtamizdoust, Babak; Joo, Sang Woo; Soltani, Behzad

2017-07-01

Nano-structures of a new supramolecular coordination compound of divalent nickel with the pyrazol (pzH) containing the terminal azide anions, [Ni(pzH) 2 (N 3 ) 2 ] (1), with discrete molecular architecture (DMA) in solid state was synthesized via sonochemical method. The new nanostructure was characterized by scanning electron microscopy, X-ray powder diffraction, IR, and elemental analysis. Compound 1 was structurally characterized by single crystal X-ray diffraction and the single-crystal X-ray data shows that the coordination number of Ni (II) ions is six, (NiN 6 ), with four N-donor atoms from neutral "pzH" ligands and two N-donors from two terminal azide anions. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The structure of the title complex was optimized by density functional theory calculations. Calculated structural parameters and IR spectra for the title complex are consistent with the crystal structure. The NiO nanoparticles were obtained by thermolysis of 1 at 180°C with oleic acid as a surfactant. Copyright © 2017 Elsevier B.V. All rights reserved.

Supramolecular nano-architectures and two-dimensional/three-dimensional aggregation of a bolaamphiphilic diacid at the air/water interface

International Nuclear Information System (INIS)

Jiao Tifeng; Liu Minghua

2005-01-01

The spreading behavior and nano-architectures of a bolaamphiphilic diacid, 1, 13-tridecandicarboxylic acid (TDA) on water surface and the subphase containing Eu(III) ion were investigated. It was found that although TDA itself could not spread on water surface, it could form an ultrathin film on the aqueous subphase containing Eu(III) ion. In addition, interesting nano-architectures were observed for the transferred film on mica surface. It was found that the formation and change of the nano-architectures were depended on the surface pressure and concentration of Eu(III) ion in the subphase. A rectangular slide morphology was observed for the film spread on an aqueous subphase containing lower concentration of Eu(III), while a walnut-like nano-architectures were observed for the film spread on a higher concentration of Eu(III) ion. Flower structure was observed at a higher surface pressure. The nano-architecture can be further regulated through mixing TDA with octadecylamine (OA) in which linear fiber nanostructure was obtained. It was revealed that while the nano-architectures were formed mainly through a three dimensional aggregation in the case of TDA/Eu(III) films, a two-dimensional aggregation occurred when TDA was mixed with OA. A series of methods such as atomic force microscope, field emission scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction were used to characterize the supramolecular structures. A possible mechanism for the formation of these nano-architectures was discussed

Building inorganic supramolecular architectures using principles adopted from the organic solid state

Directory of Open Access Journals (Sweden)

Marijana Đaković

2018-01-01

Full Text Available In order to develop transferable and practical avenues for the assembly of coordination complexes into architectures with specific dimensionality, a strategy utilizing ligands capable of simultaneous metal coordination and self-complementary hydrogen bonding is presented. The three ligands used, 2(1H-pyrazinone, 4(3H-pyrimidinone and 4(3H-quinazolinone, consistently deliver the required synthetic vectors in a series of CdII coordination polymers, allowing for reproducible supramolecular synthesis that is insensitive to the different steric and geometric demands from potentially disruptive counterions. In all nine crystallographically characterized compounds presented here, directional intermolecular N—H...O hydrogen bonds between ligands on adjacent complex building blocks drive the assembly and orientation of discrete building blocks into largely predictable topologies. Furthermore, whether the solids are prepared from solution or through liquid-assisted grinding, the structural outcome is the same, thus emphasizing the robustness of the synthetic protocol. The details of the molecular recognition events that take place in this series of compounds have been clearly delineated and rationalized in the context of calculated molecular electrostatic potential surfaces.

Architecture between construction and expression

Directory of Open Access Journals (Sweden)

Luca Lanini

2015-11-01

Full Text Available I think that the problem is basically the same as always: to redefine the relationship between Construction and Expression. On one hand, construction is considered an endeavor, on the other hand, a tendency to contest architecture only with expression. The relationship between architecture and control of urban phenomena is a relationship that has been gradually lost in the past three decades and has been replaced by the relationship between finance and planning. A useful object is very different from a building: for its time and costs of construction. Buildings are expected to last many years and are paid with everybody’s taxes, a design object’s lifespan is perhaps fifty years, then it’s ready to be modernized or for the landfill ... I believe that the main tool that a designer must have, beyond necessary technical skills, is the capacity of his/her own critical thought.

Supramolecular luminescence from oligofluorenol-based supramolecular polymer semiconductors.

Science.gov (United States)

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

2013-11-13

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

Supramolecular Luminescence from Oligofluorenol-Based Supramolecular Polymer Semiconductors

Directory of Open Access Journals (Sweden)

Guang-Wei Zhang

2013-11-01

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

Surface-Assisted Self-Assembly Strategies Leading to Supramolecular Hydrogels.

Science.gov (United States)

Vigier-Carrière, Cécile; Boulmedais, Fouzia; Schaaf, Pierre; Jierry, Loïc

2018-02-05

Localized molecular self-assembly processes leading to the growth of nanostructures exclusively from the surface of a material is one of the great challenges in surface chemistry. In the last decade, several works have been reported on the ability of modified or unmodified surfaces to manage the self-assembly of low-molecular-weight hydrogelators (LMWH) resulting in localized supramolecular hydrogel coatings mainly based on nanofiber architectures. This Minireview highlights all strategies that have emerged recently to initiate and localize LMWH supramolecular hydrogel formation, their related fundamental issues and applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Host-guest supramolecular nanosystems for cancer diagnostics and therapeutics.

Science.gov (United States)

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.

Insight into the Supramolecular Architecture of Intact Diatom Biosilica from DNP-Supported Solid-State NMR Spectroscopy.

Science.gov (United States)

Jantschke, Anne; Koers, Eline; Mance, Deni; Weingarth, Markus; Brunner, Eike; Baldus, Marc

2015-12-07

Diatom biosilica is an inorganic/organic hybrid with interesting properties. The molecular architecture of the organic material at the atomic and nanometer scale has so far remained unknown, in particular for intact biosilica. A DNP-supported ssNMR approach assisted by microscopy, MS, and MD simulations was applied to study the structural organization of intact biosilica. For the first time, the secondary structure elements of tightly biosilica-associated native proteins in diatom biosilica were characterized in situ. Our data suggest that these proteins are rich in a limited set of amino acids and adopt a mixture of random-coil and β-strand conformations. Furthermore, biosilica-associated long-chain polyamines and carbohydrates were characterized, thereby leading to a model for the supramolecular organization of intact biosilica. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Topological dynamics in supramolecular rotors.

Science.gov (United States)

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

2014-08-13

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

Digital fabrication in architecture, engineering and construction

CERN Document Server

Caneparo, Luca

2014-01-01

Digital technologies are changing the relationship between design and construction: with computer models, CAD/CAM, and prototyping, designers can gain direct control of building and construction processes. The ability to digitally model designs, and thus to use those models directly in the context of production, creates a synthesis between design and construction in keeping with the tradition of the close relationship between design and craftsmanship, between the quality of the design and the rules of the craft. The evolution of the culture of design and construction is the underlying theme of this book. The aim is to discuss the direction that innovation is now taking, with a particular focus on today’s cutting-edge architectures. The method addresses the ways in which different societies have dealt with the issues of their age regarding design and construction, the different contributions provided by various techniques, and with them the meanings expressed by the architecture. As building design using dig...

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

Science.gov (United States)

Lehn, Jean-Marie

2012-01-01

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

PRINCIPLES OF ECOLOGICAL CONSTRUCTION IN FACHWERK ARCHITECTURE

Directory of Open Access Journals (Sweden)

Shubina Elena Vasil'evna

2013-04-01

Full Text Available The authors consider the ecological aspects of application of Fachwerk, a traditional structural system, in the present-day construction. The authors have identified the potential and defined the principal development and modernization trends of the Fachwerk architecture. The author provides arguments of outstanding contemporary architects in support of the statement that the Fachwerk architecture is friendly to humans and it does not deliver any damage to the environment. Fachwerk complies with the criteria of sustainable development; therefore, it may be retained in the future architecture.

Stability of Hydrogen-Bonded Supramolecular Architecture under High Pressure Conditions: Pressure-Induced Amorphization in Melamine-Boric Acid Adduct

International Nuclear Information System (INIS)

Wang, K.; Duan, D.; Wang, R.; Lin, A.; Cui, Q.; Liu, B.; Cui, T.; Zou, B.; Zhang, X.

2009-01-01

The effects of high pressure on the structural stability of the melamine-boric acid adduct (C3N6H6 2H3BO3, M 2B), a three-dimensional hydrogen-bonded supramolecular architecture, were studied by in situ synchrotron X-ray diffraction (XRD) and Raman spectroscopy. M 2B exhibited a high compressibility and a strong anisotropic compression, which can be explained by the layerlike crystal packing. Furthermore, evolution of XRD patterns and Raman spectra indicated that the M 2B crystal undergoes a reversible pressure-induced amorphization (PIA) at 18 GPa. The mechanism for the PIA was attributed to the competition between close packing and long-range order. Ab initio calculations were also performed to account for the behavior of hydrogen bonding under high pressure.

Painting Supramolecular Polymers in Organic Solvents by Super-resolution Microscopy

Science.gov (United States)

2018-01-01

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

Facile preparation of luminescent and intelligent gold nanodots based on supramolecular self-assembly

International Nuclear Information System (INIS)

Shi Yunfeng; Li Sujuan; Zhou Yahui; Zhai Qingpan; Hu Mengyue; Cai Fensha; Du Jimin; Liang Jiamiao; Zhu Xinyuan

2012-01-01

A new strategy for preparing luminescent and intelligent gold nanodots based on supramolecular self-assembly is described in this paper. The supramolecular self-assembly was initiated through electrostatic interactions and ion pairing between palmitic acid and hyperbranched poly(ethylenimine). The resulting structures not only have the dynamic reversible properties of supramolecules but also possess torispherical and highly branched architectures. Thus they can be regarded as a new kind of ideal nanoreactor for preparing intelligent Au nanodots. By preparing Au nanodots within this kind of supramolecular self-assembly, the environmental sensitivity of intelligent polymers and the optical, electrical properties of Au nanodots can be combined, endowing the Au nanodots with intelligence. In this paper, a supramolecular self-assembly process based on dendritic poly(ethylenimine) and palmitic acid was designed and then applied to prepare fluorescent and size-controlled Au nanodots. The pH response of Au nanodots embodied by phase transfer from oil phase to water phase was also investigated. (paper)

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

Science.gov (United States)

Ciesielski, Artur; Samorì, Paolo

2011-04-01

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

Revealing the Supramolecular Nature of Side-Chain Terpyridine-Functionalized Polymer Networks

Directory of Open Access Journals (Sweden)

Jérémy Brassinne

2015-01-01

Full Text Available Nowadays, finely controlling the mechanical properties of polymeric materials is possible by incorporating supramolecular motifs into their architecture. In this context, the synthesis of a side-chain terpyridine-functionalized poly(2-(dimethylaminoethyl methacrylate is reported via reversible addition-fragmentation chain transfer polymerization. By addition of transition metal ions, concentrated aqueous solutions of this polymer turn into metallo-supramolecular hydrogels whose dynamic mechanical properties are investigated by rotational rheometry. Hence, the possibility for the material to relax mechanical constrains via dissociation of transient cross-links is brought into light. In addition, the complex phenomena occurring under large oscillatory shear are interpreted in the context of transient networks.

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

Directory of Open Access Journals (Sweden)

Dirk G Kurth

2008-01-01

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

Bio-inspired supramolecular materials by orthogonal self-assembly of hydrogelators and phospholipids

NARCIS (Netherlands)

Boekhoven, J.; Brizard, AMA; Stuart, M. C A; Florusse, L.J.; Raffy, G.; Del Guerzo, A.; van Esch, J.H.

2016-01-01

The orthogonal self-assembly of multiple components is a powerful strategy towards the formation of complex biomimetic architectures, but so far the rules for designing such systems are unclear. Here we show how to identify orthogonal self-assembly at the supramolecular level and describe

Architectonics: Design of Molecular Architecture for Functional Applications.

Science.gov (United States)

Avinash, M B; Govindaraju, Thimmaiah

2018-02-20

biomolecules like amino acids and nucleobases as auxiliaries. Naphthalenediimide (NDI), perylenediimide (PDI), and few other molecular systems serve as functional modules. The effects of stereochemistry and minute structural modifications in the molecular designs on the supramolecular interactions, and construction of self-assembled zero-dimensional (OD), one-dimensional (1D), and two-dimensional (2D) nano- and microarchitectures like particles, spheres, cups, bowls, fibers, belts, helical belts, supercoiled helices, sheets, fractals, and honeycomb-like arrays are discussed in extensive detail. Additionally, we present molecular systems that showcase the elegant designs of coassembly, templated assembly, hierarchical assembly, transient self-assembly, chiral denaturation, retentive helical memory, self-replication, supramolecular regulation, supramolecular speciation, supernon linearity, dynamic pathway complexity, supramolecular heterojunction, living supramolecular polymerization, and molecular machines. Finally, we describe the molecular engineering principles learnt over the years that have led to several applications, namely, organic electronics, self-cleaning, high-mechanical strength, and tissue engineering.

3D Printing Polymers with Supramolecular Functionality for Biological Applications.

Science.gov (United States)

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

2017-09-11

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

Synergy in supramolecular chemistry

CERN Document Server

Nabeshima, Tatsuya

2014-01-01

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

Integral Facade Construction. Towards a new product architecture for curtain walls

Directory of Open Access Journals (Sweden)

Tillmann Klein

2013-06-01

Full Text Available Curtain wall constructions are one of the most applied facade constructions today. Independently attached to the primary load bearing structure of the building they protect the building’s interior from external climate conditions and allow great design freedom. With continuously rising requirements in terms of energy savings the constructional principle has reached its limits and strategies for improvement are needed. Incrementally evolved over time it is closely related to the architectural design and building processes. Based on literature research and stakeholder interviews the dissertation maps out the traditional and craftsmanship related facade design and construction process currently employed. In a next step, future challenges for facade constructions to cope with a changing market environment are identified. A facade function tree is developed and the theory of product architecture is applied to create a comparative basis for analysing different historical and contemporary facade products and systems. The function tree as well as the analysis clearly show how the fragmented market structures has influenced contemporary facade construction and leads to extremely modular product architectures. Numerous case studies for a new approach are conducted and summarised in several matrices. The case studies show how different modular and integral constructional strategies can respond to the future challenges. The pros and cons of different facade solutions, their potential for innovation and robustness in terms of market conditions are investigated. The dissertation concludes that a greater diversity of fa.ade types with a more integral construction is needed to meet the sometimes conflicting future challenges. If this can be realised, a greater diversity of more integral design and construction processes will evolve simultaneously. The role of the different stakeholders will change and a new way of educating architects or facade specialists

THE MATRILINEAL ARCHITECTURAL VALUES ON THE CONSTRUCTION OF THE MINANGKABAU HOUSE

Directory of Open Access Journals (Sweden)

HARDONO Setiawan

2014-07-01

Full Text Available This article studies the relationship between the custom of inheritance system based on the mother’s side bloodline or better known as the matrilineal system and the construction of the Western Sumatera Minangkabau house. The architectural components and the construction of the house is often related to the matrilineal custom concept which lies n the philosophy of beliefs, perspective and strong ritual. The objectives of this research are to identify and analyze matrilineal values and its relationships with the process of the construction and architectural features of the Minangkabau house. The process of the constructing the Minangkabau house involves completing, gathering building materials to the part of building the house. This research used repeated research methodology, past researches analysis and ethnographic methods. Data collection is done through observational processes, interviews and photo taking at various research locations. These research methodologies had verify the compatibility of matrilineal elements to the architectural features of the construction of the Minangkabau house.

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

Directory of Open Access Journals (Sweden)

Yue Zheng

2016-05-01

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

A two-dimensional layered Cd(II) coordination polymer with a three-dimensional supramolecular architecture incorporating mixed multidentate N- and O-donor ligands.

Science.gov (United States)

Huang, Qiu-Ying; Su, Ming-Yang; Meng, Xiang-Ru

2015-06-01

The combination of N-heterocyclic and multicarboxylate ligands is a good choice for the construction of metal-organic frameworks. In the title coordination polymer, poly[bis{μ2-1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole-κ(2)N(3):N(4)}(μ4-butanedioato-κ(4)O(1):O(1'):O(4):O(4'))(μ2-butanedioato-κ(2)O(1):O(4))dicadmium], [Cd(C4H4O4)(C9H8N6)]n, each Cd(II) ion exhibits an irregular octahedral CdO4N2 coordination geometry and is coordinated by four O atoms from three carboxylate groups of three succinate (butanedioate) ligands and two N atoms from two 1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole (bimt) ligands. Cd(II) ions are connected by two kinds of crystallographically independent succinate ligands to generate a two-dimensional layered structure with bimt ligands located on each side of the layer. Adjacent layers are further connected by hydrogen bonding, leading to a three-dimensional supramolecular architecture in the solid state. Thermogravimetric analysis of the title polymer shows that it is stable up to 529 K and then loses weight from 529 to 918 K, corresponding to the decomposition of the bimt ligands and succinate groups. The polymer exhibits a strong fluorescence emission in the solid state at room temperature.

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

Science.gov (United States)

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

2016-06-01

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

From supramolecular electrochemistry to molecular-level devices

Energy Technology Data Exchange (ETDEWEB)

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

2004-09-15

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

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

NARCIS (Netherlands)

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

2011-01-01

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

Progress in the Supramolecular Architecture-directed Synthesis of Perfect Ladder Polysiloxanes

Institute of Scientific and Technical Information of China (English)

C; C; Han

2007-01-01

1 Introduction Ladder polysiloxanes (LPSs) including organo-bridged ladder polyorganosiloxanes (R-OLPSs, R is side group) and ladder polyorganosilsesquioxanes (R-LPSQs) have intrigued polymer chemists for about 50 years due to their excellent resistance to all kinds of degradations. However, their synthesis has been a great challenge to polymer chemists. Here, we describe a new approach based on supramolecular concerted interactions as follows.2 Results2.1 Synthesis of Perfect R-OLPSsA series of real ...

Diverse Supramolecular Nanofiber Networks Assembled by Functional Low-Complexity Domains.

Science.gov (United States)

An, Bolin; Wang, Xinyu; Cui, Mengkui; Gui, Xinrui; Mao, Xiuhai; Liu, Yan; Li, Ke; Chu, Cenfeng; Pu, Jiahua; Ren, Susu; Wang, Yanyi; Zhong, Guisheng; Lu, Timothy K; Liu, Cong; Zhong, Chao

2017-07-25

Self-assembling supramolecular nanofibers, common in the natural world, are of fundamental interest and technical importance to both nanotechnology and materials science. Despite important advances, synthetic nanofibers still lack the structural and functional diversity of biological molecules, and the controlled assembly of one type of molecule into a variety of fibrous structures with wide-ranging functional attributes remains challenging. Here, we harness the low-complexity (LC) sequence domain of fused in sarcoma (FUS) protein, an essential cellular nuclear protein with slow kinetics of amyloid fiber assembly, to construct random copolymer-like, multiblock, and self-sorted supramolecular fibrous networks with distinct structural features and fluorescent functionalities. We demonstrate the utilities of these networks in the templated, spatially controlled assembly of ligand-decorated gold nanoparticles, quantum dots, nanorods, DNA origami, and hybrid structures. Owing to the distinguishable nanoarchitectures of these nanofibers, this assembly is structure-dependent. By coupling a modular genetic strategy with kinetically controlled complex supramolecular self-assembly, we demonstrate that a single type of protein molecule can be used to engineer diverse one-dimensional supramolecular nanostructures with distinct functionalities.

Construction Morphology and the Parallel Architecture of Grammar

Science.gov (United States)

Booij, Geert; Audring, Jenny

2017-01-01

This article presents a systematic exposition of how the basic ideas of Construction Grammar (CxG) (Goldberg, 2006) and the Parallel Architecture (PA) of grammar (Jackendoff, 2002]) provide the framework for a proper account of morphological phenomena, in particular word formation. This framework is referred to as Construction Morphology (CxM). As…

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

Science.gov (United States)

Cho, Eunae; Jung, Seunho

2015-10-27

In this review, a comprehensive overview of advances in the supramolecular complexes of carbohydrates and poorly soluble drugs is presented. Through the complexation process, poorly soluble drugs could be efficiently delivered to their desired destinations. Carbohydrates, the most abundant biomolecules, have diverse physicochemical properties owing to their inherent three-dimensional structures, hydrogen bonding, and molecular recognition abilities. In this regard, oligosaccharides and their derivatives have been utilized for the bioavailability enhancement of hydrophobic drugs via increasing the solubility or stability. By extension, polysaccharides and their derivatives can form self-assembled architectures with poorly soluble drugs and have shown increased bioavailability in terms of the sustained or controlled drug release. These supramolecular systems using carbohydrate will be developed consistently in the field of pharmaceutical and medical application.

Synthesis, Crystal Structures, and Photoluminescent Properties of Two Supramolecular Architectures Based on Difunctional Ligands Containing Imidazolyl and Carboxyl Groups

Directory of Open Access Journals (Sweden)

Mei-An Zhu

2017-07-01

Full Text Available Two new supramolecular architectures, namely, [Cd(L12(H2O]n (1 and [Ni(L22(H2O]n (2, were synthesized by the reaction of corresponding metal salts of CdCl2·2.5H2O and NiCl2·6H2O with 2-(1H-imidazol-4-ylbenzoic acid (HL1 and 3-(1H-imidazol-4-ylbenzoic acid (HL2 respectively, and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and powder X-ray diffraction (PXRD. Both HL1 and HL2 ligands are deprotonated to be L1- and L2- anions that coordinate with Cd(II and Ni(II atoms to form two-dimensional (2D layer structure. Topologically, complex 1 is a 2D network with (4, 4 sql topology, while 2 is a typical 63-hcb topology net. Complex 1 exhibits intense light blue emission in the solid state at room temperature.

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

Science.gov (United States)

Anslyn, Eric V

2016-01-01

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

Effect of H-bonding on order amplification in the growth of a supramolecular polymer in water

NARCIS (Netherlands)

Garzoni, M.; Baker, M.B.; Leenders, C.M.A.; Voets, I.K.; Albertazzi, Lorenzo; Palmans, A.R.A.; Meijer, E.W.; Pavan, G.M.

2016-01-01

While a great deal of knowledge on the roles of hydrogen bonding and hydrophobicity in proteins has resulted in the creation of rationally designed and functional peptidic structures, the roles of these forces on purely synthetic supramolecular architectures in water have proven difficult to

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-02-28

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

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

International Nuclear Information System (INIS)

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

2017-01-01

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

Computation-Guided Design of a Stimulus-Responsive Multienzyme Supramolecular Assembly.

Science.gov (United States)

Yang, Lu; Dolan, Elliott M; Tan, Sophia K; Lin, Tianyun; Sontag, Eduardo D; Khare, Sagar D

2017-10-18

The construction of stimulus-responsive supramolecular complexes of metabolic pathway enzymes, inspired by natural multienzyme assemblies (metabolons), provides an attractive avenue for efficient and spatiotemporally controllable one-pot biotransformations. We have constructed a phosphorylation- and optically responsive metabolon for the biodegradation of the environmental pollutant 1,2,3-trichloropropane. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Towards supramolecular engineering of functional nanomaterials: pre-programming multi-component 2D self-assembly at solid-liquid interfaces.

Science.gov (United States)

Ciesielski, Artur; Palma, Carlos-Andres; Bonini, Massimo; Samorì, Paolo

2010-08-24

Materials with a pre-programmed order at the supramolecular level can be engineered with a sub-nanometer precision making use of reversible non- covalent interactions. The intrinsic ability of supramolecular materials to recognize and exchange their constituents makes them constitutionally dynamic materials. The tailoring of the materials properties relies on the full control over the self-assembly behavior of molecular modules exposing recognition sites and incorporating functional units. In this review we focus on three classes of weak-interactions to form complex 2D architectures starting from properly designed molecular modules: van der Waals, metallo-ligand and hydrogen bonding. Scanning tunneling microscopy studies will provide evidence with a sub-nanometer resolution, on the formation of responsive multicomponent architectures with controlled geometries and properties. Such endeavor enriches the scientist capability of generating more and more complex smart materials featuring controlled functions and unprecedented properties.

Chiral supramolecular organization from a sheet-like achiral gel: a study of chiral photoinduction.

Science.gov (United States)

Royes, Jorge; Polo, Víctor; Uriel, Santiago; Oriol, Luis; Piñol, Milagros; Tejedor, Rosa M

2017-05-31

Chiral photoinduction in a photoresponsive gel based on an achiral 2D architecture with high geometric anisotropy and low roughness has been investigated. Circularly polarized light (CPL) was used as a chiral source and an azobenzene chromophore was employed as a chiral trigger. The chiral photoinduction was studied by evaluating the preferential excitation of enantiomeric conformers of the azobenzene units. Crystallographic data and density functional theory (DFT) calculations show how chirality is transferred to the achiral azomaterials as a result of the combination of chiral photochemistry and supramolecular interactions. This procedure could be applied to predict and estimate chirality transfer from a chiral physical source to a supramolecular organization using different light-responsive units.

Constructing an I and C Upgrade Architecture for Korea Standard Nuclear Power Plants

International Nuclear Information System (INIS)

Suh, Yong Suk; Hur, Seop; Kim, Dong Hoon; Sung, Chan Ho; Kang, Hyun Tai; Lee, Jae Ki; Cho, Chang Hwan

2008-01-01

This paper presents three architectures of the KSNP I and C upgrade. The architectures are constructed with an adoption of PLCs and DCS technology and 3-phase upgrade strategy. The 3-phase upgrade strategy is established to ensure the safety of the upgrade. Based on the architecture, the cabinet configuration is being constructed. From the configuration, it is expected to figure out how to optimize the layout of the cabinets. It is required to study the performance and safety design requirements of the upgrade further

Supramolecular core-shell nanoparticles for photoconductive device applications

Science.gov (United States)

Cheng, Chih-Chia; Chen, Jem-Kun; Shieh, Yeong-Tarng; Lee, Duu-Jong

2016-08-01

We report a breakthrough discovery involving supramolecular-based strategies to construct novel core-shell heterojunction nanoparticles with hydrophilic adenine-functionalized polythiophene (PAT) as the core and hydrophobic phenyl-C61-butyric acid methyl ester (PCBM) as the shell, which enables the conception of new functional supramolecular assemblies for constructing functional nanomaterials for applications in optoelectronic devices. The generated nanoparticles exhibit uniform spherical shape, well-controlled tuning of particle size with narrow size distributions, and excellent electrochemical stability in solution and the solid state owing to highly efficient energy transfer from PAT to PCBM. When the PAT/PCBM nanoparticles were fabricated into a photoconducting layer in an electronic device, the resulting device showed excellent electric conduction characteristics, including an electrically-tunable voltage-controlled switch, and high short-circuit current and open-circuit voltage. These observations demonstrate how the self-assembly of PAT/PCBM into specific nanostructures may help to promote efficient charge generation and transport processes, suggesting potential for a wide variety of applications as a promising candidate material for bulk heterojunction polymer devices.

Identification of a Supramolecular Functional Architecture of Streptococcus mutans Adhesin P1 on the Bacterial Cell Surface*

Science.gov (United States)

Heim, Kyle P.; Sullan, Ruby May A.; Crowley, Paula J.; El-Kirat-Chatel, Sofiane; Beaussart, Audrey; Tang, Wenxing; Besingi, Richard; Dufrene, Yves F.; Brady, L. Jeannine

2015-01-01

P1 (antigen I/II) is a sucrose-independent adhesin of Streptococcus mutans whose functional architecture on the cell surface is not fully understood. S. mutans cells subjected to mechanical extraction were significantly diminished in adherence to immobilized salivary agglutinin but remained immunoreactive and were readily aggregated by fluid-phase salivary agglutinin. Bacterial adherence was restored by incubation of postextracted cells with P1 fragments that contain each of the two known adhesive domains. In contrast to untreated cells, glutaraldehyde-treated bacteria gained reactivity with anti-C-terminal monoclonal antibodies (mAbs), whereas epitopes recognized by mAbs against other portions of the molecule were masked. Surface plasmon resonance experiments demonstrated the ability of apical and C-terminal fragments of P1 to interact. Binding of several different anti-P1 mAbs to unfixed cells triggered release of a C-terminal fragment from the bacterial surface, suggesting a novel mechanism of action of certain adherence-inhibiting antibodies. We also used atomic force microscopy-based single molecule force spectroscopy with tips bearing various mAbs to elucidate the spatial organization and orientation of P1 on living bacteria. The similar rupture lengths detected using mAbs against the head and C-terminal regions, which are widely separated in the tertiary structure, suggest a higher order architecture in which these domains are in close proximity on the cell surface. Taken together, our results suggest a supramolecular organization in which additional P1 polypeptides, including the C-terminal segment originally identified as antigen II, associate with covalently attached P1 to form the functional adhesive layer. PMID:25666624

Identification of a supramolecular functional architecture of Streptococcus mutans adhesin P1 on the bacterial cell surface.

Science.gov (United States)

Heim, Kyle P; Sullan, Ruby May A; Crowley, Paula J; El-Kirat-Chatel, Sofiane; Beaussart, Audrey; Tang, Wenxing; Besingi, Richard; Dufrene, Yves F; Brady, L Jeannine

2015-04-03

P1 (antigen I/II) is a sucrose-independent adhesin of Streptococcus mutans whose functional architecture on the cell surface is not fully understood. S. mutans cells subjected to mechanical extraction were significantly diminished in adherence to immobilized salivary agglutinin but remained immunoreactive and were readily aggregated by fluid-phase salivary agglutinin. Bacterial adherence was restored by incubation of postextracted cells with P1 fragments that contain each of the two known adhesive domains. In contrast to untreated cells, glutaraldehyde-treated bacteria gained reactivity with anti-C-terminal monoclonal antibodies (mAbs), whereas epitopes recognized by mAbs against other portions of the molecule were masked. Surface plasmon resonance experiments demonstrated the ability of apical and C-terminal fragments of P1 to interact. Binding of several different anti-P1 mAbs to unfixed cells triggered release of a C-terminal fragment from the bacterial surface, suggesting a novel mechanism of action of certain adherence-inhibiting antibodies. We also used atomic force microscopy-based single molecule force spectroscopy with tips bearing various mAbs to elucidate the spatial organization and orientation of P1 on living bacteria. The similar rupture lengths detected using mAbs against the head and C-terminal regions, which are widely separated in the tertiary structure, suggest a higher order architecture in which these domains are in close proximity on the cell surface. Taken together, our results suggest a supramolecular organization in which additional P1 polypeptides, including the C-terminal segment originally identified as antigen II, associate with covalently attached P1 to form the functional adhesive layer. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

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

Directory of Open Access Journals (Sweden)

Eric V. Anslyn

2016-02-01

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

Logic of historical development of the formation process of architectural and construction solutions

Directory of Open Access Journals (Sweden)

Baranov Valeriy Aleksandrovich

2014-05-01

Full Text Available In research field of development processes of architectural and construction decisions (ACD there is already very considerable scientific, normative and technical material. And still in the end of the research boom in this area (the 90th many authors stated their weak return in practical design. High methodological potential gives understanding of the act of ACD formation as a special kind of activity, and its structure - as historical phenomenon that allows to put two main methodological principles in the basis of the research: the principle of activity and the principle of level organization of historically formed objects. As a result it was succeeded to reveal 6 main stages of historical development of ACD formation process and 6 levels of its modern organization. Origin stage - is the transition from animal to human construction and emergence of the first stage of ACD formation - a measurement. The reproductive stage is characterized by centuries-old reproduction of steady volume forms of constructions. At a composite stage professional presentation detaches external form of a construction from architectural and construction actions and techniques. There occurs transformation into a subject of architectural and construction activity and creation of a method of composition on this basis. At a constructive stage engineers are involved in construction process, there is a change of style of thinking, emergence of construction designs and emergence of a new function of ACD means of configuration, and, at last, final allocation and separation of architectural and construction design from construction. Technological stage is a product of industrialization of construction on which systematization is carried out not only on the level of subject, but also in respect to the operational contents that leads to emergence of ACD program formation. At the sixth, methodological stage of development of ASP, a leading way change of the ACD formation becomes a

The dominant role of side chains in supramolecular double helical organisation in synthetic tripeptides

Science.gov (United States)

Sharma, Ankita; Tiwari, Priyanka; Dutt Konar, Anita

2018-06-01

Peptide self-assembled nanostructures have attracted attention recently owing to their promising applications in diversified avenues. To validate the importance of sidechains in supramolecular architectural stabilization, herein this report describes the self-assembly propensities involving weak interactions in a series of model tripeptides Boc-Xaa-Aib-Yaa-OMe I-IV, (where Xaa = 4-F-Phe/NMeSer/Ile & Yaa = Tyr in peptide I-III respectively and Xaa = 4-F-Phe & Yaa = Ile in peptide IV) differing in terminal side chains. The solid state structural analysis reveals that tripeptide (I) displays supramolecular preference for double helical architecture. However, when slight modification has been introduced in the N-terminal side chains disfavour the double helical organisation (Peptide II and III). Indeed the peptides display sheet like ensemble within the framework. Besides replacement of C-terminal Tyr by Ile in peptide I even do not promote the architecture, emphasizing the dominant role of balance of side chains in stabilizing double helical organisation. The CD measurements, concentration dependant studies, NMR titrations and ROESY spectra are well in agreement with the solid state conformational investigation. Moreover the morphological experiments utilizing FE-SEM, support the heterogeneity present in the peptides. Thus this work may not only hold future promise in understanding the structure and function of neurodegenerative diseases but also assist in rational design of protein modification in biologically active peptides.

The supramolecular architecture of tris(naphthalene-1,5-diaminium) bis(5-aminonaphthalen-1-aminium) octakis[hydrogen (5-carboxypyridin-3-yl)phosphonate].

Science.gov (United States)

Wilk, Magdalena; Janczak, Jan; Videnova-Adrabinska, Veneta

2012-09-01

The asymmetric unit of the title compound, 3C(10)H(12)N(2)(2+)·2C(10)H(11)N(2)(+)·8C(6)H(5)NO(5)P(-), contains one and a half naphthalene-1,5-diaminium cations, in which the half-molecule has inversion symmetry, one 5-aminonaphthalen-1-aminium cation and four hydrogen (5-carboxypyridin-3-yl)phosphonate anions. The crystal structure is layered and consists of hydrogen-bonded anionic monolayers between which the cations are arranged. The acid monoanions are organized into one-dimensional chains along the [101] direction via hydrogen bonds established between the phosphonate sites. (C)O-H···N(py) hydrogen bonds (py is pyridine) crosslink the chains to form an undulating (010) monolayer. The cations serve both to balance the charge of the anionic network and to connect neighbouring layers via multiple hydrogen bonds to form a three-dimensional supramolecular architecture.

Architectural Intention as the Mediator of Lean Housing Construction

DEFF Research Database (Denmark)

Frier, Marie; Kirkegaard, Poul Henning; Fisker, Anna Marie

2008-01-01

In recent years a number of companies have taken up the challenge of producing prefab houses using lean principles, hereby incorporating value driven production theory as the means to optimize construction processes. However, the value of home is dependent on architectural qualities and interior ...

Organic semi-conducting architectures for supramolecular electronics

NARCIS (Netherlands)

Leclère, P.E.L.G.; Surin, M.; Jonkheijm, P.; Henze, O.; Schenning, A.P.H.J.; Biscarini, F.; Grimsdale, A.C.; Feast, W.J.; Meijer, E.W.; Müllen, K.; Brédas, J.L.; Lazzaroni, R.

2004-01-01

The properties of organic electronic materials in the solid-state are determined not only by those of individual molecules but also by those of ensembles of molecules. The ability to control the architectures of these ensembles is thus essential for optimizing the properties of conjugated materials

Self-assembling multivalency : supramolecular polymers assembled from monovalent mannose-labelled discotic molecules

NARCIS (Netherlands)

Petkau - Milroy, K.; Brunsveld, L.

2013-01-01

Supramolecular synthesis, the "bottom-up" construction of higher-order structures from monomeric building blocks, represents a flexible approach for the generation of multivalent materials. Here, monovalent building blocks decorated with a single bioactive ligand were synthesized. In water, these

Rheology of Supramolecular Polymers

DEFF Research Database (Denmark)

Shabbir, Aamir

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

Preparation of supramolecular hydrogel-enzyme hybrids exhibiting biomolecule-responsive gel degradation.

Science.gov (United States)

Shigemitsu, Hajime; Fujisaku, Takahiro; Onogi, Shoji; Yoshii, Tatsuyuki; Ikeda, Masato; Hamachi, Itaru

2016-09-01

Hydrogelators are small, self-assembling molecules that form supramolecular nanofiber networks that exhibit unique dynamic properties. Development of supramolecular hydrogels that degrade in response to various biomolecules could potentially be used for applications in areas such as drug delivery and diagnostics. Here we provide a synthetic procedure for preparing redox-responsive supramolecular hydrogelators that are used to create hydrogels that degrade in response to oxidizing or reducing conditions. The synthesis takes ∼2-4 d, and it can potentially be carried out in parallel to prepare multiple hydrogelator candidates. This described solid-phase peptide synthesis protocol can be used to produce previously described hydrogelators or to construct a focused molecular library to efficiently discover and optimize new hydrogelators. In addition, we describe the preparation of redox-responsive supramolecular hydrogel-enzyme hybrids that are created by mixing aqueous solutions of hydrogelators and enzymes, which requires 2 h for completion. The resultant supramolecular hydrogel-enzyme hybrids exhibit gel degradation in response to various biomolecules, and can be rationally designed by connecting the chemical reactions of the hydrogelators with enzymatic reactions. Gel degradation in response to biomolecules as triggers occurs within a few hours. We also describe the preparation of hydrogel-enzyme hybrids arrayed on flat glass slides, enabling high-throughput analysis of biomolecules such as glucose, uric acid, lactate and so on by gel degradation, which is detectable by the naked eye. The protocol requires ∼6 h to prepare the hydrogel-enzyme hybrid array and to complete the biomolecule assay.

Combining supramolecular chemistry with biology

NARCIS (Netherlands)

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

2010-01-01

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

[Supramolecular Agents for Theranostics].

Science.gov (United States)

Deyev, S M; Lebedenko, E N

2015-01-01

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

Supramolecular Host-Guest System as Ratiometric Fe3+ Ion Sensor Based on Water-Soluble Pillar[5]arene.

Science.gov (United States)

Yao, Qianfang; Lü, Baozhong; Ji, Chendong; Cai, Yang; Yin, Meizhen

2017-10-18

Developing a specific, ratiometric, and reversible detection method for metal ions is significant to guard against the threat of metal-caused environmental pollution and organisms poisoning. Here a supramolecular host-guest system (WP5⊃G) based on water-soluble pillar[5]arene (WP5) and water-soluble quaternized perylene diimide derivative (G) was constructed. Morphological transformation was achieved during the process of adding WP5 into G aqueous solution, and a fluorescence "turn-off" phenomenon was observed which was caused by supramolecular photoinduced electron transfer (PET). Meanwhile, hydrophobic effect and electrostatic interaction played important roles in this supramolecular process, which was confirmed by isothermal titration calorimeter (ITC) and ζ potential experiments. Furthermore, the supramolecular host-guest system could be a "turn-on" fluorescent probe for Fe 3+ ion detection through the process of interdicting supramolecular PET. Moreover, the Fe 3+ ion detection showed specific, ratiometric, and reversible performances with a detection limit of 2.13 × 10 -7 M, which might have great potentials in biological and environmental monitoring.

Main-chain supramolecular block copolymers.

Science.gov (United States)

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

2011-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-02-10

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

Chiroptical studies on supramolecular chirality of molecular aggregates.

Science.gov (United States)

Sato, Hisako; Yajima, Tomoko; Yamagishi, Akihiko

2015-10-01

The attempts of applying chiroptical spectroscopy to supramolecular chirality are reviewed with a focus on vibrational circular dichroism (VCD). Examples were taken from gels, solids, and monolayers formed by low-molecular mass weight chiral gelators. Particular attention was paid to a group of gelators with perfluoroalkyl chains. The effects of the helical conformation of the perfluoroalkyl chains on the formation of chiral architectures are reported. It is described how the conformation of a chiral gelator was determined by comparing the experimental and theoretical VCD spectra together with a model proposed for the molecular aggregation in fibrils. The results demonstrate the potential utility of the chiroptical method in analyzing organized chiral aggregates. © 2015 Wiley Periodicals, Inc.

Architectural switches in plant thylakoid membranes.

Science.gov (United States)

Kirchhoff, Helmut

2013-10-01

Recent progress in elucidating the structure of higher plants photosynthetic membranes provides a wealth of information. It allows generation of architectural models that reveal well-organized and complex arrangements not only on whole membrane level, but also on the supramolecular level. These arrangements are not static but highly responsive to the environment. Knowledge about the interdependency between dynamic structural features of the photosynthetic machinery and the functionality of energy conversion is central to understanding the plasticity of photosynthesis in an ever-changing environment. This review summarizes the architectural switches that are realized in thylakoid membranes of green plants.

Supramolecularly assembled water layers stabilized by sebacic anions in complexes of Zn(II) and Co(II)

Institute of Scientific and Technical Information of China (English)

无

2010-01-01

Two three-dimensional supramolecular water architectures,[Zn(phen)3]2 ·[Zn(C10H16O4)·(H2O)3]·(C10H16O4)2·20H2O(1) and [Co(phen)3]2 ·[Co(H2O)6]·(C10H16O4)3·30H2O(2)[phen=1,10-Phenanthroline,C10H16O4=sebacic dianion],have been synthesized and characterized by IR,elemental analysis,thermogravimetric analysis,and single-crystal X-ray diffractions.The two structures both contain extensive hydrogen bonding between water molecules as well as between water molecules and sebacic anions.The water molecules and sebacic acid O atoms assembled 2D supramolecular corrugated sheets with different morphology in the two complexes.

Construction of Architectural Structures in Cultural Heritage Protection Zones

Science.gov (United States)

Zagroba, Marek; Gawryluk, Dorota

2017-10-01

The article raises issues of constructing contemporary architectural structures in cultural heritage protection zones, using the case study of a building located within the campus of the University of Warmia and Mazury in Olsztyn, Poland. Questions revolving around the construction of this building arise from the need to preserve the surrounding historic heritage, and deal with landscaping, architectural and construction solutions as well as interior design. All these problems grow in importance when dealing with such unique buildings like the discussed example of a laboratory building for the Civil Engineering Department, built on a site within a conservation zone of the university campus. The specific character of the building and the specialist equipment with which it was to be furnished (a resistance testing machine, a 17-meter-long wave flume) necessitated a series of analyses. In turn, the fact that the new building was to be erected in the conservation zone meant that collaboration with the Heritage Conservation Office had to be undertaken at the stage of making the plan and continued during the construction works. The Heritage Officer’s recommendations concerning the building’s shape, divisions, dimensions, materials used, etc., created a situation where the team of designers and architects had to become engaged in the process of landscape and spatial management. The above requirements concerned the functions of the building and its siting on a land parcel that was difficult to handle, also because of the protected trees growing there. Other constraints included the small size of this site, the developed surroundings, and the pre-defined programme of functions and use of the new building. All the above circumstances made the task difficult and demanded good coordination between individual teams of engineers and architects, both at the stage of making the plan and during the construction works. Many of the heritage protection zones are spoilt with

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

Science.gov (United States)

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

2018-01-01

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

A Supramolecular Approach toward Bioinspired PAMAM-Dendronized Fusion Toxins.

Science.gov (United States)

Kuan, Seah Ling; Förtsch, Christina; Ng, David Yuen Wah; Fischer, Stephan; Tokura, Yu; Liu, Weina; Wu, Yuzhou; Koynov, Kaloian; Barth, Holger; Weil, Tanja

2016-06-01

Nature has provided a highly optimized toolbox in bacterial endotoxins with precise functions dictated by their clear structural division. Inspired by this streamlined design, a supramolecular approach capitalizing on the strong biomolecular (streptavidin (SA))-biotin interactions is reported herein to prepare two multipartite fusion constructs, which involves the generation 2.0 (D2) or generation 3.0 (D3) polyamidoamine-dendronized transporter proteins (dendronized streptavidin (D3SA) and dendronized human serum albumin (D2HSA)) non-covalently fused to the C3bot1 enzyme from Clostridium botulinum, a potent and specific Rho-inhibitor. The fusion constructs, D3SA-C3 and D2HSA-C3, represent the first examples of dendronized protein transporters that are fused to the C3 enzyme, and it is successfully demonstrated that the C3 Rho-inhibitor is delivered into the cytosol of mammalian cells as determined from the characteristic C3-mediated changes in cell morphology and confocal microscopy. The design circumvents the low uptake of the C3 enzyme by eukaryotic cells and holds great promise for reprogramming the properties of toxin enzymes using a supramolecular approach to broaden their therapeutic applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

48 CFR 227.7107-1 - Architectural designs and data clauses for architect-engineer or construction contracts.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 3 2010-10-01 2010-10-01 false Architectural designs and... construction involving architect-engineer services, is to obtain a unique architectural design of a building, a... CONTRACTING REQUIREMENTS PATENTS, DATA, AND COPYRIGHTS Rights in Technical Data 227.7107-1 Architectural...

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

Science.gov (United States)

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

2016-05-01

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

Multivalency in supramolecular chemistry and nanofabrication

NARCIS (Netherlands)

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

2004-01-01

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

Evolutionary, Unconscious Design Support for the Architectural, Engineering and Construction Industry

NARCIS (Netherlands)

Van de Ruitenbeek, H.K.M.

2012-01-01

The Architecture, Engineering and Construction (AEC) industry is a complex system in which carpenters, structural designers, architects, modellers, cost estimators, planners, politicians and many others act apart together in project-specific virtual enterprises. There is a large amount of actors, an

Two 8-Hydroxyquinolinate Based Supramolecular Coordination Compounds: Synthesis, Structures and Spectral Properties

Directory of Open Access Journals (Sweden)

Chengfeng Zhu

2017-03-01

Full Text Available Two new Cr(III complexes based on 2-substituted 8-hydroxyquinoline ligands, namely [Cr(L13] (1, (HL1=(E-2-[2-(4-nitro-phenyl-vinyl]-8-hydroxy-quinoline and [Cr(L23] (2, (HL2=(E-2-[2-(4-chloro-phenylvinyl]-8-hydroxy-quinoline, were prepared by a facile hydrothermal method and characterized thoroughly by single crystal X-ray diffraction, powder X-ray diffraction, FTIR, TGA, ESI-MS, UV-Visible absorption spectra and fluorescence emission spectra. Single crystal X-ray diffraction analyses showed that the two compounds featured 3D supramolecular architectures constructed from noncovalent interactions, such as π···π stacking, C-H···π, C-H···O, C-Cl···π, C-H···Cl interactions. The thermogravimetric analysis and ESI-MS study of compounds 1 and 2 suggested that the Cr(III complexes possessed good stability both in solid and solution. In addition, the ultraviolet and fluorescence response of the HL1 and HL2 shown marked changes upon their complexation with Cr(III ion, which indicated that the two 8-hydroxyquinolinate based ligand are promising heavy metal chelating agent for Cr3+.

A supramolecular miktoarm star polymer based on porphyrin metal complexation in water.

Science.gov (United States)

Hou, Zhanyao; Dehaen, Wim; Lyskawa, Joël; Woisel, Patrice; Hoogenboom, Richard

2017-07-25

A novel supramolecular miktoarm star polymer was successfully constructed in water from a pyridine end-decorated polymer (Py-PmDEGA) and a metalloporphyrin based star polymer (ZnTPP-(PEG) 4 ) via metal-ligand coordination. The Py-PmDEGA moiety was prepared via a combination of reversible addition-fragmentation chain transfer polymerization (RAFT) and subsequent aminolysis and Michael addition reactions to introduce the pyridine end-group. The ZnTPP(PEG) 4 star-polymer was synthesized by the reaction between tetrakis(p-hydroxyphenyl)porphyrin and toluenesulfonyl-PEG, followed by insertion of a zinc ion into the porphyrin core. The formation of a well-defined supramolecular AB 4 -type miktoarm star polymer was unambiguously demonstrated via UV-Vis spectroscopic titration, isothermal titration calorimetry (ITC) and diffusion ordered NMR spectroscopy (DOSY).

Functional supramolecular polymers for biomedical applications.

Science.gov (United States)

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

2015-01-21

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

Research in the Laboratory of Supramolecular Chemistry: functional nanostructures, sensors, and catalysts.

Science.gov (United States)

Severin, Kay

2011-01-01

This article summarizes research activities in the Laboratory of Supramolecular Chemistry (LCS) at the EPFL. Three topics will be discussed: a) the construction of functional nanostructures by multicomponent self-assembly processes, b) the development of chemosensors using specific receptors or ensembles of crossreactive sensors, and c) the investigation of novel synthetic procedures with organometallic catalysts.

Constructing service-oriented architecture adoption maturity matrix using Kano model

Science.gov (United States)

Hamzah, Mohd Hamdi Irwan; Baharom, Fauziah; Mohd, Haslina

2017-10-01

Commonly, organizations adopted Service-Oriented Architecture (SOA) because it can provide a flexible reconfiguration and can reduce the development time and cost. In order to guide the SOA adoption, previous industry and academia have constructed SOA maturity model. However, there is a limited number of works on how to construct the matrix in the previous SOA maturity model. Therefore, this study is going to provide a method that can be used in order to construct the matrix in the SOA maturity model. This study adapts Kano Model to construct the cross evaluation matrix focused on SOA adoption IT and business benefits. This study found that Kano Model can provide a suitable and appropriate method for constructing the cross evaluation matrix in SOA maturity model. Kano model also can be used to plot, organize and better represent the evaluation dimension for evaluating the SOA adoption.

Magnetism: a supramolecular function

International Nuclear Information System (INIS)

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

1996-01-01

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

Magnetism: a supramolecular function

Energy Technology Data Exchange (ETDEWEB)

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

1996-11-01

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

Graphene controlled H- and J-stacking of perylene dyes into highly stable supramolecular nanostructures for enhanced photocurrent generation

DEFF Research Database (Denmark)

Gan, Shiyu; Zhong, Lijie; Engelbrekt, Christian

2014-01-01

We report a new method for controlling H- and J-stacking in supramolecular self-assembly. Graphene nanosheets act as structure inducers to direct the self-assembly of a versatile organic dye, perylene into two distinct types of functional nanostructures, i.e. one-dimensional nanotubes via J......-stacking and two-dimensional branched nanobuds through H-stacking. Graphene integrated supramolecular nanocomposites are highly stable and show significant enhancement of photocurrent generation in these two configurations of photosensing devices, i.e. solid-state optoelectronic constructs and liquid...

A new configurational bias scheme for sampling supramolecular structures

Energy Technology Data Exchange (ETDEWEB)

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

2014-12-28

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

Multicomponent hydrogen-bonding organic solids constructed from 6-hydroxy-2-naphthoic acid and N-heterocycles: Synthesis, structural characterization and synthon discussion

Science.gov (United States)

Zong, Yingxia; Shao, Hui; Pang, Yanyan; Wang, Debao; Liu, Kang; Wang, Lei

2016-07-01

Seven novel multicomponent crystals involving various substituted organic amine molecules and 6-hydroxy-2-naphthoic acid were prepared and characterized by using single crystal X-ray diffraction, infrared and thermogravimetric analyses (TGA). Crystal structures with 1,4-bis(imidazol) butane (L1) 1, 1,4-bis(imidazol-1-ylmethyl)benzene (L2) 2, 1-phenyl piperazine 3, 2-amino-4-hydroxy-6-methyl pyrimidine 4, 4,4'-bipyridine 5, 5,5'-dimethyl-2,2'-dipyridine 6, 2-amino-4,6-dimethyl pyrimidine 7 were determined. Among the seven molecular complexes, total proton transfer from 6-hydroxy-2-naphthoic acid to coformer has occurred in crystals 1-4, while the remaining were cocrystals. X-ray single-crystal structures of these complexes reveal that strong hydrogen bonding O-H···O/N-H···O/O-H···N and weak C-H···O/C-H···π/π···π intermolecular interactions direct the packing modes of molecular crystals together. The analysis of supramolecular synthons in the present structures shows that some classical supramolecular synthons like pyridine-carboxylic acid heterosynthon R22 (7) and aminopyridine-carboxylic acid heterosynthon R22 (8), are again observed in constructing the hydrogen-bonding networks in this paper. Besides, we noticed that water molecules act as a significant hydrogen-bonding connector in constructing supramolecular architectures of 3, 4, 6, and 7.

Supramolecular materials based on hydrogen-bonded polymers

NARCIS (Netherlands)

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

2007-01-01

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

Design of Molecular Materials: Supramolecular Engineering

Science.gov (United States)

Simon, Jacques; Bassoul, Pierre

2001-02-01

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

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

Science.gov (United States)

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

2017-04-01

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

Selective hydrolysis of phosphate monoester by a supramolecular phosphatase formed by the self-assembly of a bis(Zn(2+)-cyclen) complex, cyanuric acid, and copper in an aqueous solution (cyclen = 1,4,7,10-tetraazacyclododecane).

Science.gov (United States)

Zulkefeli, Mohd; Suzuki, Asami; Shiro, Motoo; Hisamatsu, Yosuke; Kimura, Eiichi; Aoki, Shin

2011-10-17

In Nature, organized nanoscale structures such as proteins and enzymes are formed in aqueous media via intermolecular interactions between multicomponents. Supramolecular and self-assembling strategies provide versatile methods for the construction of artificial chemical architectures for controlling reaction rates and the specificities of chemical reactions, but most are designed in hydrophobic environments. The preparation of artificial catalysts that have potential in aqueous media mimicking natural enzymes such as hydrolases remains a great challenge in the fields of supramolecular chemistry. Herein, we describe that a dimeric Zn(2+) complex having a 2,2'-bipyridyl linker, cyanuric acid, and a Cu(2+) ion automatically assembles in an aqueous solution to form a 4:4:4 complex, which is stabilized by metal-ligand coordination bonds, π-π-stacking interactions, and hydrogen bonding and contains μ-Cu(2)(OH)(2) cores analogous to the catalytic centers of phosphatase, a dinuclear metalloenzyme. The 4:4:4 complex selectively accelerates the hydrolysis of a phosphate monoester, mono(4-nitrophenyl)phosphate, at neutral pH.

Enhanced intermolecular forces in supramolecular polymer nanocomposites

Directory of Open Access Journals (Sweden)

F. Lin

2017-09-01

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

Expanding Application of Perforated Metal Materials in Construction and Architecture

Science.gov (United States)

Mironovs, V.; Tatarinov, A.; Gorbacova, S.

2017-10-01

Perforated metal materials (PMM) combine a range of properties, including rigidity, strength, lightweight, small thickness, a dosed transparency and decorative attractiveness. All these bring new application effects in construction industry and architecture. Nowadays, PMM are widely used in design of facades and interiors all over the world, becoming more popular in Latvia as well. The paper touches several aspects of PMM applications, including its decoration function, shadowing of sunlight, sound and noise barrier function and the problem of corrosion when exploited outdoors. Possible perfection may include using different coatings, multi-layer design variants and integration with other constructional materials in order to provide better sound absorption, corrosion resistance and functionality.

Programming supramolecular biohybrids as precision therapeutics.

Science.gov (United States)

Ng, David Yuen Wah; Wu, Yuzhou; Kuan, Seah Ling; Weil, Tanja

2014-12-16

chains available for grafting with molecules of interest. Additionally, we are equipped with analytical tools to map the fingerprint of the protein chain, directly elucidating the structure at the molecular level. Contrary to conventional polymers, these biopolymers facilitate a more systematic avenue to investigate engineered macromolecules, with greater detail and accuracy. In this regard, we focus on denaturing serum albumin, an abundant blood protein, and exploit its peptidic array of functionalities to program supramolecular architectures for bioimaging, drug and gene delivery. Ultimately, we seek to assimilate the evolutionary advantage of these protein based biopolymers with the limitless versatility of synthetic chemistry to merge the best of both worlds.

The Situation with Use of Wood Constructions in Contemporary Latvian Architecture

Directory of Open Access Journals (Sweden)

Antra Viluma

2017-05-01

Full Text Available Wood is a historic building material used throughout the Baltic States. Latvia’s forests cover 52% of the country and there are more than 30 producers of timber constructions materials, but during the last two decades the use wood in Latvian architecture has declined when compared to other countries in Europe. In particular – Latvian architects avoid the use of timber in public and multi-unit apartment buildings. Wood is a sustainable and technically appropriate building material for many types of buildings including complex construction, but in Latvian architecture it is used more in facades as a finishing material. This study analyses buildings built during the last few decades, conducted a number of interviews and found that the percentage of wooden buildings in the total building volume in Latvia is less than 5% in both apartment buildings and public sector buildings. Restrictive legislation and negative stereotypes were mentioned as reasons as to why architects avoid the use of wood. For the survey results seven Latvian Museum of Contemporary Art competition projects were analysed as well.

Synthesis, Crystal Structure and Water Vapor Adsorption Properties of a Porous Supramolecular Architecture

Directory of Open Access Journals (Sweden)

Rui Qiao

2017-10-01

Full Text Available A new complex, [Cu4(HL4(H2O14] (1, H3L·HCl = 5-((4-carboxypiperidin-1-ylmethylisophthalic acid hydrochloride, has been prepared and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and powder X-ray diffraction (PXRD. The result of the X-ray diffraction analysis reveals that the complex crystallizes in monoclinic, space group C2/c and three unique Cu(II atoms that are connected by partially deprotonated HL2− anion to form a cyclic structure. The rich hydrogen bonding and π-π non-covalent packing interactions extend cyclic units into a three-dimensional (3D supramolecular polymer. Moreover, the thermogravimetric (TG analysis and water vapor adsorption property of 1 were also discussed.

Solvent induced supramolecular anisotropy in molecular gels

Energy Technology Data Exchange (ETDEWEB)

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

2017-06-15

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

Solvent induced supramolecular anisotropy in molecular gels

International Nuclear Information System (INIS)

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

2017-01-01

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

Synthesis and Characterization of thermo/pH-responsive Supramolecular G-Quadruplexes for the Construction of Supramolecular Hacky Sacks for Biorelevant Applications

Science.gov (United States)

Negron Rios, Luis M.

The impact of size, shape, and distribution of lipophilic regions on the surfaces of nanoscopic objects that are amphiphilic or patchy (such as proteins) are yet to be fully understood. One of the reasons for this is the lack of an appropriate model systems in which to probe this question. Our group has previously reported 2'-deoxyguanosine (8ArG) derivatives that self-assemble in aqueous media into discrete supramolecular hexadecamers that show the lower critical solution temperature (LCST) phenomenon. The LCST phenomenon is a convenient and rigorous strategy to measure the hydrophobicity of a system. Although these SGQs are potentially attractive for biomedical applications like drug-delivery, the narrow window of physiological temperatures complicates their implementation. This moved us to redesign the constituent 8ArG subunits to incorporate imidazole moieties that would lead to pH-responsive SGQs, working isothermally. Upon reaching a threshold temperature (Lower Critical Solution Temperature, LCST) at pH 7, these dual-responsive SGQs further self-assemble to form nano/micro hydrogel globules that we called them supramolecular hacky sacks (SHS). However, we can isolate kinetically stable versions of these SHS by lowering the ionic strength of the medium (i.e., from the molar to the millimolar range) in a process that we term "fixing the SHS", in which these SHS maintain their integrity (size and shape) and stability without the requirement of crosslinking agents. After structural characterization and in vitro studies of SHS, we performed encapsulation studies of DOX, rhodamine, dsDNA (F26T), thrombin binding aptamer (TBA) and dextran (3 kDa) Texas Red conjugate. Then we performed in vivo studies of cell internalization and drug delivery with neuroblastoma SY-SH5Y. The performed studies will bring new approaches for the development of new biotechnology for fundamental applications and the emerging of novel therapeutic agents for biomedical applications.

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

Science.gov (United States)

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

2014-08-14

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

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.

Science.gov (United States)

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.

Incorporation and Effects of Nanoparticles in a Supramolecular Polymer

Science.gov (United States)

2016-05-01

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

A polythreaded Ag(I) coordination polymer: A rare three-dimensional Pseudo-polyrotaxana constructed from the same components

Energy Technology Data Exchange (ETDEWEB)

Im, Han Su; Lee, Eunji; Lee, Shim Sung; Kim, Tae Ho; Park, Ki Min [Research Institute of Natural Science and Dept. of Chemistry, Gyeongsang National University, Jinju (Korea, Republic of); Moon, Suk Hee [Dept. of Food and Nutrition, Kyungnam College of Information and Technology, Busan (Korea, Republic of)

2017-01-15

In supramolecular chemistry, a lot of mechanically poly-threaded coordination polymers, such as polyrotaxanes, based on self-assembly of organic ligands and transition metal ions have attracted great attention over the past two decades because of their fascinating architectures as well as their potential application in material science. Among them, 1D + 2D → 3D pseudo-polyrotaxane constructed by the penetration of 1D coordination polymer chains into 1D channels formed by parallel stacking of 2D porous coordination layers is a quite rare topology. Until now, only a few examples of 1D + 2D → 3D pseudo-polyrotaxanes have been reported.

A polythreaded Ag(I) coordination polymer: A rare three-dimensional Pseudo-polyrotaxana constructed from the same components

International Nuclear Information System (INIS)

Im, Han Su; Lee, Eunji; Lee, Shim Sung; Kim, Tae Ho; Park, Ki Min; Moon, Suk Hee

2017-01-01

In supramolecular chemistry, a lot of mechanically poly-threaded coordination polymers, such as polyrotaxanes, based on self-assembly of organic ligands and transition metal ions have attracted great attention over the past two decades because of their fascinating architectures as well as their potential application in material science. Among them, 1D + 2D → 3D pseudo-polyrotaxane constructed by the penetration of 1D coordination polymer chains into 1D channels formed by parallel stacking of 2D porous coordination layers is a quite rare topology. Until now, only a few examples of 1D + 2D → 3D pseudo-polyrotaxanes have been reported

Exploring the Applications of Bio-Eco Architecture for Sustainable Design and Construction process

OpenAIRE

M. M. Naguib; M. A. M. Hanafi

2013-01-01

It has been commonly noted that the main perception of nature influenced forms isbasically aesthetic while little concern is given to the importance of inspiring from naturein the construction and structural performance of buildings as well as in the naturalecological architectural solutions, thus, this paper will focus on bio-inspired architectureapproach which embraces the eco-friendly practices of sustainable construction, the useof natural materials and the energy conservation by mimickin...

Tetrathiafulvalene- (TTF-) Derived Oligopyrrolic Macrocycles

DEFF Research Database (Denmark)

Jana, Atanu; Ishida, Masatoshi; Park, Jung Su

2017-01-01

After the epochal discovery of the “organic metal”, namely, tetrathiafulvalene (TTF)–7,7,8,8-tetracyano-p-quinodimethane (TCNQ) dyad in 1973, scientists have made efforts to derivatize TTF for constructing various supramolecular architectures to control the charge-transfer processes by adjusting...... the donor–acceptor strength of the dyads for numerous applications. The interesting inherent electronic donor properties of TTFs control the overall electrochemical properties of the supramolecular structures, leading to the construction of highly efficient optoelectronic materials, photovoltaic solar cells...

CITY ARCHITECTURE AS WAY OF CONSTRUCTION AND DECONSTRUCTION OF SOCIAL PRACTICES IN THE CITY

Directory of Open Access Journals (Sweden)

Ivanova V. V.

2017-06-01

Full Text Available In this article urban architecture, acting as a «natural physical borders of mankind», creates a certain discourse of social practices that construct and define reality, forming views and values. Moreover, that discourse can be deconstructed and problematized through representation of the urban architecture, which provides an opportunity to explore different ways of forming those social practices among citizens. Thus, the main idea of this study is to examine the way in which social practices could be seen as a reflection of citizen’s actions, which, on the one hand, are set up by the urban construction as an objective structure and, on the other hand, modal behavior which are formed by the influence of a certain structure of thought and ideas. To implement the objectives of the study, we use the discourse analysis as a method of analyzing the meanings through which an attempt of deconstruction of practices of urban life is made, the analysis of themes which are brought up to reveal the featured characteristics and values of urban architecture and ways of its coding.

Supramolecular architecture based on [Fe(CN)6]3- metallotectons and melaminium synthons

Science.gov (United States)

Krichen, Firas; Walha, Siwar; Lhoste, Jérôme; Bulou, Alain; Kabadou, Ahlem; Goutenoire, François

2017-10-01

Assembly involving [Fe(CN)6]3- metallotectons as building units and melaminium organic cation has been envisioned in order to elaborate a hybrid supramolecular based on ionic H-bonds with formula {(H-mel)4[Fe(CN)6]Cl} (H-mel+: melaminium cation). The compound has been prepared by diffusion method and characterized by single-crystal X-ray diffraction, EDX analysis, and Raman-IR spectroscopies with assignment from ab initio calculations. The melaminium exhibit self cationic coupling with cyclic hydrogen bonds to give a one dimensional {[H-mel]+}∝ synthon. Therefore, these cationic ribbons are inter-linked via hydrogen bonds by the anionic tectons [Fe(CN)6]3- and chlorine anion resulting on a 3D network. Molecular hirshfeld surfaces revealed that the crystal structure has been supported mainly by Nsbnd H⋯N and Nsbnd H⋯Cl intermolecular Hydrogen bonds and by favoured C⋯C and C⋯N weak interactions.

Supramolecular systems chemistry

NARCIS (Netherlands)

Mattia, Elio; Otto, Sijbren

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

Non-equilibrium supramolecular polymerization.

Science.gov (United States)

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

2017-09-18

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

Hydrogen bonded supra-molecular framework in inorganic-organic hybrid compounds: Syntheses, structures, and photoluminescent properties

Science.gov (United States)

Yan, Li; Liu, Wei; Li, Chuanbi; Wang, Yifei; Ma, Li; Dong, Qinqin

2013-03-01

Two novel compounds constructed from aromatic acid and N-Heterocyclic ligands have been synthesized by hydrothermal reaction: [Cd(mip)(1,8-NDC)(H2O)]2 (1) [mip = 2-(3-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, 1,8-NDC = naphthalene-1,8-dicarboxylic acid] and Cd(mip)2(NTC)2 (2) [NTC = nicotinic acid]. Compounds 1 and 2 are characterized by elemental analysis, IR, single crystal X-ray diffraction and thermogravimetric analysis (TGA). Single-crystal X-ray investigation reveals that compounds 1-2 are 0 dimensional (0D) structures, and the existence of hydrogen bonds and π-π interactions lead the 0D to 2D novel framework. Hydrogen bonds and π-π interactions are powerful non-covalent intermolecular interactions for directing supra-molecular architectures. TG analysis shows clear courses of weight loss, which corresponds to the decomposition of different ligands. At room temperature, compound 1 exhibits emission at 449 nm upon excitation at 325 nm, and compound 2 shows a strong emission at 656 nm upon excitation at 350 nm. Fluorescent spectrum displays that compounds 1 and 2 are potential luminescent materials.

Supramolecular biomaterials : a modular approach towards tissue engineering

NARCIS (Netherlands)

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

2007-01-01

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

Using Ecotech Architecture as an Effective Tool for Sustainability in Construction Industry

Directory of Open Access Journals (Sweden)

A. S. Mozhdegani

2017-10-01

Full Text Available Ecotech architecture can be used as an effective strategy to minimize energy consumption and enhance the satisfaction of construction industry beneficiaries in the Middle East. The use of ecotech principles has been employed in different parts of the world. However, following a universal approach is not possible as local conditions are always to be considered Applications and examples of ecotech architecture are investigated in this paper. A proposed building design for the Cheetgar region in Tehran is also briefly demonstrated. A further insight on Masdar city in Abhu Dabi is provided. An overall discussion is made and key conclusions are drawn.

Supramolecular effects in dendritic systems containing photoactive groups

Directory of Open Access Journals (Sweden)

GIANLUCA CAMILLO AZZELLINI

2000-03-01

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

Evolutionary, Unconscious Design Support for the Architectural, Engineering and Construction Industry

OpenAIRE

Van de Ruitenbeek, H.K.M.

2012-01-01

The Architecture, Engineering and Construction (AEC) industry is a complex system in which carpenters, structural designers, architects, modellers, cost estimators, planners, politicians and many others act apart together in project-specific virtual enterprises. There is a large amount of actors, an overwhelming number of ongoing processes, distributed, decentralised organisations and a variety of projects. This complicates efficient communication and supply chain integration which, according...

Tuning Gas Adsorption Properties of Zeolite-like Supramolecular Assemblies with gis Topology via Functionalization of Isoreticular Metal–Organic Squares

KAUST Repository

Wang, Shuang; Belmabkhout, Youssef; Cairns, Amy; Li, Guanghua; Huo, Qisheng; Liu, Yunling; Eddaoudi, Mohamed

2017-01-01

A strategy based on metal-ligand directed assembly of metal-organic squares (MOSs), built-up from four-membered ring (4MR) secondary building units (SBUs), has been employed for the design and construction of isoreticular zeolite-like supramolecular

Engineering responsive supramolecular biomaterials: Toward smart therapeutics.

Science.gov (United States)

Webber, Matthew J

2016-09-01

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

Synthesis and Crystal Structure of an Unprecedented Supramolecular Complex[Co(μ2-ClO4)2(H2O)2]·2MA

Institute of Scientific and Technical Information of China (English)

XU,Jing; BAI,Zhengshuai; SUN,Weiyin

2009-01-01

A new supramolecular framework[Co(μ2-C104)2(H2O)2]·2MA(1)[MA=melamine(C3H6N6)]has been syn-thesized by a hydrothermal method.Interestingly,there ale inorganic and organic building blocks with two different supramolecular synthons:(a)2D(4,4)network constructed by infinite inorganic 1D chains through interchain hy-drogen bonding interactions;(b)1D zigzag organic chains formed by hydrogen bonds, which further stack up through,ππ-interactions between the two adjacent MA molecules.The entire structure of 1 is a 3D supramolecular framework resulting from the presence of abundant hydrogen bonds between infinite[CO(μ2-C1O4)2(H2O)2]n chains and zigzag MA chains in different sheets.1 gives a nice example of supramolecular framework based on non-covalent interactions including hydrogen bonding and π-π interactions.

Construction of a Hierarchical Architecture of Covalent Organic Frameworks via a Postsynthetic Approach.

Science.gov (United States)

Zhang, Gen; Tsujimoto, Masahiko; Packwood, Daniel; Duong, Nghia Tuan; Nishiyama, Yusuke; Kadota, Kentaro; Kitagawa, Susumu; Horike, Satoshi

2018-02-21

Covalent organic frameworks (COFs) represent an emerging class of crystalline porous materials that are constructed by the assembly of organic building blocks linked via covalent bonds. Several strategies have been developed for the construction of new COF structures; however, a facile approach to fabricate hierarchical COF architectures with controlled domain structures remains a significant challenge, and has not yet been achieved. In this study, a dynamic covalent chemistry (DCC)-based postsynthetic approach was employed at the solid-liquid interface to construct such structures. Two-dimensional imine-bonded COFs having different aromatic groups were prepared, and a homogeneously mixed-linker structure and a heterogeneously core-shell hollow structure were fabricated by controlling the reactivity of the postsynthetic reactions. Solid-state nuclear magnetic resonance (NMR) spectroscopy and transmission electron microscopy (TEM) confirmed the structures. COFs prepared by a postsynthetic approach exhibit several functional advantages compared with their parent phases. Their Brunauer-Emmett-Teller (BET) surface areas are 2-fold greater than those of their parent phases because of the higher crystallinity. In addition, the hydrophilicity of the material and the stepwise adsorption isotherms of H 2 O vapor in the hierarchical frameworks were precisely controlled, which was feasible because of the distribution of various domains of the two COFs by controlling the postsynthetic reaction. The approach opens new routes for constructing COF architectures with functionalities that are not possible in a single phase.

Supramolecular tunneling junctions

NARCIS (Netherlands)

Wimbush, K.S.

2012-01-01

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

Reversible Self-Assembly of Supramolecular Vesicles and Nanofibers Driven by Chalcogen-Bonding Interactions.

Science.gov (United States)

Chen, Liang; Xiang, Jun; Zhao, Yue; Yan, Qiang

2018-05-29

Chalcogen-bonding interactions have been viewed as new noncovalent forces in supramolecular chemistry. However, harnessing chalcogen bonds to drive molecular self-assembly processes is still unexplored. Here we report for the first time a novel class of supra-amphiphiles formed by Te···O or Se···O chalcogen-bonding interactions, and their self-assembly into supramolecular vesicles and nanofibers. A quasi-calix[4]chalcogenadiazole (C4Ch) as macrocyclic donor and a tailed pyridine N-oxide surfactant as molecular acceptor are designed to construct the donor-acceptor complex via chalcogen-chalcogen connection between the chalcogenadiazole moieties and oxide anion. The affinity of such chalcogen-bonding can dictate the geometry of supra-amphiphiles, driving diverse self-assembled morphologies. Furthermore, the reversible disassembly of these nanostructures can be promoted by introducing competing anions, such as halide ions, or by decreasing the systemic pH value.

Supramolecular Photodimerization of Coumarins

Directory of Open Access Journals (Sweden)

Koichi Tanaka

2012-02-01

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

Directed supramolecular surface assembly of SNAP-tag fusion proteins

NARCIS (Netherlands)

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

2012-01-01

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

Directed Supramolecular Surface Assembly of SNAP-tag Fusion Proteins

NARCIS (Netherlands)

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

2012-01-01

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

Temperature-Induced, Selective Assembly of Supramolecular Colloids in Water

NARCIS (Netherlands)

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

2017-01-01

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

Supramolecular fluorene based materials

NARCIS (Netherlands)

Abbel, R.J.

2008-01-01

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

Influence of the supramolecular architecture on the magnetic properties of a DyIII single-molecule magnet: an ab initio investigation

Directory of Open Access Journals (Sweden)

Julie Jung

2014-11-01

Full Text Available Single-crystal angular-resolved magnetometry and wavefunction-based calculations have been used to reconsider the magnetic properties of a recently reported DyIII-based single-molecule magnet, namely [Dy(hfac3(L1] with hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonate and L1 = 2-(4,5-bis(propylthio-1,3-dithiol-2-ylidene-6-(pyridin-2-yl-5H-[1,3]dithiolo[4',5':4,5]benzo[1,2-d]imidazole. The magnetic susceptibility and magnetization at low temperature are found to be strongly influenced by supramolecular interactions. Moreover, taking into account the hydrogen-bond networks in the calculations allows to explain the orientation of the magnetic axes. This strongly suggests that hydrogen bonds play an important role in the modulation of the electrostatic environment around the DyIII center that governs the nature of its magnetic ground-state and the orientation of its anisotropy axes. We thus show here that SMM properties that rely on supramolecular organization may not be transferable into single-molecule devices.

Stigmergic construction and topochemical information shape ant nest architecture.

Science.gov (United States)

Khuong, Anaïs; Gautrais, Jacques; Perna, Andrea; Sbaï, Chaker; Combe, Maud; Kuntz, Pascale; Jost, Christian; Theraulaz, Guy

2016-02-02

The nests of social insects are not only impressive because of their sheer complexity but also because they are built from individuals whose work is not centrally coordinated. A key question is how groups of insects coordinate their building actions. Here, we use a combination of experimental and modeling approaches to investigate nest construction in the ant Lasius niger. We quantify the construction dynamics and the 3D structures built by ants. Then, we characterize individual behaviors and the interactions of ants with the structures they build. We show that two main interactions are involved in the coordination of building actions: (i) a stigmergic-based interaction that controls the amplification of depositions at some locations and is attributable to a pheromone added by ants to the building material; and (ii) a template-based interaction in which ants use their body size as a cue to control the height at which they start to build a roof from existing pillars. We then develop a 3D stochastic model based on these individual behaviors to analyze the effect of pheromone presence and strength on construction dynamics. We show that the model can quantitatively reproduce key features of construction dynamics, including a large-scale pattern of regularly spaced pillars, the formation and merging of caps over the pillars, and the remodeling of built structures. Finally, our model suggests that the lifetime of the pheromone is a highly influential parameter that controls the growth and form of nest architecture.

Reversible Guest Exchange Mechanisms in Supramolecular Host-GuestAssemblies

Energy Technology Data Exchange (ETDEWEB)

Pluth, Michael D.; Raymond, Kenneth N.

2006-09-01

Synthetic chemists have provided a wide array of supramolecular assemblies able to encapsulate guest molecules. The scope of this tutorial review focuses on supramolecular host molecules capable of reversibly encapsulating polyatomic guests. Much work has been done to determine the mechanism of guest encapsulation and guest release. This review covers common methods of monitoring and characterizing guest exchange such as NMR, UV-VIS, mass spectroscopy, electrochemistry, and calorimetry and also presents representative examples of guest exchange mechanisms. The guest exchange mechanisms of hemicarcerands, cucurbiturils, hydrogen-bonded assemblies, and metal-ligand assemblies are discussed. Special attention is given to systems which exhibit constrictive binding, a motif common in supramolecular guest exchange systems.

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

Directory of Open Access Journals (Sweden)

Joaquín Calbo

2018-01-01

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

Information processing in the CNS: a supramolecular chemistry?

Science.gov (United States)

Tozzi, Arturo

2015-10-01

How does central nervous system process information? Current theories are based on two tenets: (a) information is transmitted by action potentials, the language by which neurons communicate with each other-and (b) homogeneous neuronal assemblies of cortical circuits operate on these neuronal messages where the operations are characterized by the intrinsic connectivity among neuronal populations. In this view, the size and time course of any spike is stereotypic and the information is restricted to the temporal sequence of the spikes; namely, the "neural code". However, an increasing amount of novel data point towards an alternative hypothesis: (a) the role of neural code in information processing is overemphasized. Instead of simply passing messages, action potentials play a role in dynamic coordination at multiple spatial and temporal scales, establishing network interactions across several levels of a hierarchical modular architecture, modulating and regulating the propagation of neuronal messages. (b) Information is processed at all levels of neuronal infrastructure from macromolecules to population dynamics. For example, intra-neuronal (changes in protein conformation, concentration and synthesis) and extra-neuronal factors (extracellular proteolysis, substrate patterning, myelin plasticity, microbes, metabolic status) can have a profound effect on neuronal computations. This means molecular message passing may have cognitive connotations. This essay introduces the concept of "supramolecular chemistry", involving the storage of information at the molecular level and its retrieval, transfer and processing at the supramolecular level, through transitory non-covalent molecular processes that are self-organized, self-assembled and dynamic. Finally, we note that the cortex comprises extremely heterogeneous cells, with distinct regional variations, macromolecular assembly, receptor repertoire and intrinsic microcircuitry. This suggests that every neuron (or group of

The relationship between motivations of architectural designers and environmentally sustainable construction design

OpenAIRE

Murtagh, N. M.; Roberts, A.; Hind, R.

2016-01-01

Research on sustainability in construction design has tended to focus on technological, institutional and economic drivers but there has been little change in the industry. Social scientific approaches offer insights on the lack of progress. However, few previous studies have investigated psychological factors despite the pivotal role of the individual professional decision-maker. The aim was to understand what personal motivations drive architectural designers to pursue sustainable design in...

Macromolecular scaffolding: the relationship between nanoscale architecture and function in multichromophoric arrays for organic electronics.

Science.gov (United States)

Palermo, Vincenzo; Schwartz, Erik; Finlayson, Chris E; Liscio, Andrea; Otten, Matthijs B J; Trapani, Sara; Müllen, Klaus; Beljonne, David; Friend, Richard H; Nolte, Roeland J M; Rowan, Alan E; Samorì, Paolo

2010-02-23

The optimization of the electronic properties of molecular materials based on optically or electrically active organic building blocks requires a fine-tuning of their self-assembly properties at surfaces. Such a fine-tuning can be obtained on a scale up to 10 nm by mastering principles of supramolecular chemistry, i.e., by using suitably designed molecules interacting via pre-programmed noncovalent forces. The control and fine-tuning on a greater length scale is more difficult and challenging. This Research News highlights recent results we obtained on a new class of macromolecules that possess a very rigid backbone and side chains that point away from this backbone. Each side chain contains an organic semiconducting moiety, whose position and electronic interaction with neighboring moieties are dictated by the central macromolecular scaffold. A combined experimental and theoretical approach has made it possible to unravel the physical and chemical properties of this system across multiple length scales. The (opto)electronic properties of the new functional architectures have been explored by constructing prototypes of field-effect transistors and solar cells, thereby providing direct insight into the relationship between architecture and function.

Dynamic and bio-orthogonal protein assembly along a supramolecular polymer

NARCIS (Netherlands)

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

2013-01-01

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

Syntheses and structures of three supramolecular complexes based on 2-(pyridine-2-yl)-1H-imidazole-4,5-dicarboxylic acid

Science.gov (United States)

Yu, Xiao-Yang; Zhang, Xiao; Liu, Zhi-Gang; Cui, Xiao-Bing; Xu, Jia-Ning; Luo, Yu-Hui

2017-11-01

Three new supramolecular compounds, [Cu(o-HPIDC)(bpy)(H2O)]·2H2O 1, [Cu(o-H2PIDC)(phen)Cl]·[Cu(phen)2Cl]·10H2O·Cl 2 and {[Cd(o-H2PIDC)(H2O)2Cl]·H2O}23 (o-H3PIDC = 2-(pyridine-2-yl)-1H-imidazole-4,5-dicarboxylic acid, bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline), were hydrothermally synthesized and characterized. In compound 1, the adjacent two supramolecular layers are constructed from different types of helical chains with the same pitch. In compound 2, the adjacent 2D water-chloride layers, {[(H2O)10Cl]-}n, are pillared by [Cu(o-H2PIDC)(phen)Cl] units to form the overall 3D supramolecular network with 1D channels through Osbnd H⋯O hydrogen bond interactions. In compound 3, two Cd(II) are linked into a binuclear [Cd2(o-H2PIDC)2(H2O)4Cl2] with a ten-membered ring by two o-H2PIDC- ligands. The three compounds self-assemble into 3D supramolecular structures via hydrogen bond and π-π stacking interactions. The fluorescence properties of compound 3 was also investigated.

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

Science.gov (United States)

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

2015-02-20

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

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

Science.gov (United States)

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

2015-02-01

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

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

Science.gov (United States)

Albrecht, Markus

2007-12-01

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

A two-dimensional bilayered Cd(II) coordination polymer with a three-dimensional supramolecular architecture incorporating 1,2-bis(pyridin-4-yl)ethene and 2,2'-(diazenediyl)dibenzoic acid.

Science.gov (United States)

Liu, Lei-Lei; Zhou, Yan; Li, Ping; Tian, Jiang-Ya

2014-02-01

In poly[[μ2-1,2-bis(pyridin-4-yl)ethene-κ(2)N:N'][μ2-2,2'-(diazenediyl)dibenzoato-κ(3)O,O':O'']cadmium(II)], [Cd(C14H8N2O4)(C12H10N2)]n, the asymmetric unit contains one Cd(II) cation, one 2,2'-(diazenediyl)dibenzoate anion (denoted L(2-)) and one 1,2-bis(pyridin-4-yl)ethene ligand (denoted bpe). Each Cd(II) centre is six-coordinated by four O atoms of bridging/chelating carboxylate groups from three L(2-) ligands and by two N atoms from two bpe ligands, forming a distorted octahedron. The Cd(II) cations are bridged by L(2-) and bpe ligands to give a two-dimensional (4,4) layer. The layers are interlinked through bridging carboxylate O atoms from L(2-) ligands, generating a two-dimensional bilayered structure with a 3(6)4(13)6(2) topology. The bilayered structures are further extended to form a three-dimensional supramolecular architecture via a combination of hydrogen-bonding and aromatic stacking interactions.

Supramolecular "Trojan Horse" for Nuclear Delivery of Dual Anticancer Drugs.

Science.gov (United States)

Cai, Yanbin; Shen, Haosheng; Zhan, Jie; Lin, Mingliang; Dai, Liuhan; Ren, Chunhua; Shi, Yang; Liu, Jianfeng; Gao, Jie; Yang, Zhimou

2017-03-01

Nuclear delivery and accumulation are very important for many anticancer drugs that interact with DNA or its associated enzymes in the nucleus. However, it is very difficult for neutrally and negatively charged anticancer drugs such as 10-hydroxycamptothecine (HCPT). Here we report a simple strategy to construct supramolecular nanomedicines for nuclear delivery of dual synergistic anticancer drugs. Our strategy utilizes the coassembly of a negatively charged HCPT-peptide amphiphile and the positively charged cisplatin. The resulting nanomaterials behave as the "Trojan Horse" that transported soldiers (anticancer drugs) across the walls of the castle (cell and nucleus membranes). Therefore, they show improved inhibition capacity to cancer cells including the drug resistant cancer cell and promote the synergistic tumor suppression property in vivo. We envision that our strategy of constructing nanomaterials by metal chelation would offer new opportunities to develop nanomedicines for combination chemotherapy.

Supramolecular Nanoparticles for Molecular Diagnostics and Therapeutics

Science.gov (United States)

Chen, Kuan-Ju

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

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

DEFF Research Database (Denmark)

Gonzalez, Lidia; Yu, Liyun; Hvilsted, Søren

2014-01-01

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

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

NARCIS (Netherlands)

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

2015-01-01

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

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

International Nuclear Information System (INIS)

Shen Xinghai; Chen Qingde; Gao Hongcheng

2008-01-01

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

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

Science.gov (United States)

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

2018-04-01

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

[Special impact of supramolecular chemistry on Chinese medicine theories].

Science.gov (United States)

He, Fu-Yuan; Zhou, Yi-Qun; Deng, Kai-Wen; Deng, Jun-Lin; Shi, Ji-Lian; Liu, Wen-Long; Yang, Yan-Tao; Tang, Yu; Liu, Zhi-Gang

2014-04-01

The paper aimed to elucidate the specific impact of supramolecular chemistry on the Chinese medicine theories (CMT) in their modernization, after had summarized up the research status of supramolecular chemistry and analyzed the possible supramolecular forms of Chinese medicine (CM), as well as considered the problems in modernization of CM theories. On comparison of the classical chemistry that delt with chemical bonds among atoms, the supramolecular chemistry was rather concerned with varietes of weak noncovalent bonds intermolecules, and reflected the macro-apparent chemical properties of each molecules, and was the most appropriate chemical theories to explain the CMT and microcosmic materials. The molecules in the human body and Chinese material medica (CMM) formed supramolecules by way of self-assembly, self-organization, self-recognition and self-replication, with themselves or with complexation, composition, chelation, inclusion, neutralization etc. Meridian and Zang-fu viscera in CMT might be a space channel structure continuously consisted of unique molecules cavity that was imprinted with the supramolecularly template inside and outside of cells, through which the molecules in CMM interacted with the meridian and Zang-fu viscera. When small molecules in human body imprinted with macromolecules in meridian and Zang-fu viscera, in other words, they migrated along within imprinting channels of meridian and Zang-fu viscera on behavior of "Qi chromatography" impulsed by the heart beat, finally showed up on macroscopic the anisotropy of tissue and organ, as described namely as visceral manifestation in Chinese medical science. When small molecules in CMM interacted with imprinting channel on meridian and Zang-fu viscera, the natural properties and efficacy regularities of CMM was reflected on macroscopic. Therefore, the special representation forms of basic CMT is based on the macroscopic expression of "Qi chromatography" abided by imprinting effect

Intelligence in Construction between Contemporary and Traditional Architecture

Directory of Open Access Journals (Sweden)

Khalid abdul wahab

2016-10-01

Full Text Available The authentic traditional architecture proved that it is very convenient to the environmental and social regulations where it appeared and lasted for hundred of years. This traditional architecture got the intelligence in providing thermal comfort for their occupants by the intelligent usage of the building materials and the intelligent planning and designs which took in consideration the climatic condition and the aerodynamics of the whole city as one ecological system starting from the cold breeze passing through its narrow streets till it enters the dwelling units and glides out through the wind catchers. This architecture had been neglected and replaced by modern imported architecture which had collapsed within few decades not in our region only but all over the world. Now a days the increasing awareness of the global environmental crisis the green or sustainable architecture appeared as a new type of architecture by the eighties of the last century. Today these types of buildings began to enter Arab countries in general and Arabian Gulf countries especially like Masdar city, where smart building can be seen with inelegant treatments which will replace the modern high rise towers with its glass facades. This will lead to the general research problem which concerns the shortage of knowledge about the inelegance in design and planning used in the traditional architecture, and the special research problem concerning the shortage of knowledge concerning the ability to use the inelegant traditional architectural and planning concepts as a base for the future sustainable modern buildings and cites as the aim of this research.

Encoding complexity within supramolecular analogues of frustrated magnets

Science.gov (United States)

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

2016-05-01

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

Chemistry of supramolecular systems containing porphyrins and metal complexes

OpenAIRE

Araki, Koiti; Toma, Henrique Eisi

2002-01-01

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

Visualization of Stereoselective Supramolecular Polymers by Chirality-Controlled Energy Transfer.

Science.gov (United States)

Sarkar, Aritra; Dhiman, Shikha; Chalishazar, Aditya; George, Subi J

2017-10-23

Chirality-driven self-sorting is envisaged to efficiently control functional properties in supramolecular materials. However, the challenge arises because of a lack of analytical methods to directly monitor the enantioselectivity of the resulting supramolecular assemblies. Presented herein are two fluorescent core-substituted naphthalene-diimide-based donor and acceptor molecules with minimal structural mismatch and they comprise strong self-recognizing chiral motifs to determine the self-sorting process. As a consequence, stereoselective supramolecular polymerization with an unprecedented chirality control over energy transfer has been achieved. This chirality-controlled energy transfer has been further exploited as an efficient probe to visualize microscopically the chirality driven self-sorting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular architecture of metal-organic frameworks involving dinuclear copper paddle-wheel complexes.

Science.gov (United States)

Gomathi, Sundaramoorthy; Muthiah, Packianathan Thomas

2013-12-15

The two centrosymmetric dinuclear copper paddle-wheel complexes tetrakis(μ-4-hydroxybenzoato-κ(2)O:O')bis[aquacopper(II)] dimethylformamide disolvate dihydrate, [Cu2(C7H5O3)4(H2O)2]·2C3H7NO·2H2O, (I), and tetrakis(μ-4-methoxybenzoato-κ(2)O:O')bis[(dimethylformamide-κO)copper(II)], [Cu2(C8H7O3)4(C3H7NO)2], (II), crystallize with half of the dinuclear paddle-wheel cage unit in the asymmetric unit and, in addition, complex (I) has one dimethylformamide (DMF) and one water solvent molecule in the asymmetric unit. In both (I) and (II), two Cu(II) ions are bridged by four syn,syn-η(1):η(1):μ carboxylate groups, showing a paddle-wheel cage-type structure with a square-pyramidal coordination geometry. The equatorial positions of (I) and (II) are occupied by the carboxylate groups of 4-hydroxy- and 4-methoxybenzoate ligands, and the axial positions are occupied by aqua and DMF ligands, respectively. The three-dimensional supramolecular metal-organic framework of (I) consists of three different R2(2)(20) and an R4(4)(36) ring motif formed via O-H···O and OW-HW···O hydrogen bonds. Complex (II) simply packs as molecular species.

Reversible networks in supramolecular polymers

NARCIS (Netherlands)

Havermans - van Beek, D.J.M.

2007-01-01

Non–covalent interactions between low molecular weight polymers form the basis of supramolecular polymers. The material properties of such polymers are determined by the strength and lifetime of the non–covalent reversible interactions. Due to the reversibility of the interactions between the low

Design of molecule-based magnetic conductors

NARCIS (Netherlands)

Akhtar, Naureen; Blake, Graeme R.; Felici, Roberto; Amenitsch, Heinz; Palstra, Thomas T. M.; Rudolf, Petra

2014-01-01

Enabling the use of rationally designed thin films in technological devices is a recognized goal in materials science. However, constructing such thin films using highly ordered supramolecular architectures with well-controlled size and growth direction has remained an elusive target. Here, we

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

Science.gov (United States)

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

2018-06-01

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

Molecular Architectural Approach to Novel Electro-Optical Materials

Energy Technology Data Exchange (ETDEWEB)

Li, D.; Johal, M.S.; Smilowitz, L.B.; Robinson, J.M.

1999-06-29

This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The goal is to construct polar multilayers with nonlinear optical coefficients larger than classical inorganic crystals such as KDP or quartz. The strategy is to use various chemical interactions such as covalent bonds or hydrogen bonding to build polar structures. We have synthesized novel barbituric acid and melamine derivatives that will spontaneously self-assemble into a supramolecular ribbon according to their complementary H-bond motif. This supramolecular ribbon can then stack into a polar multilayer structure as verified by sum frequency generation (w{sub 1}+w{sub 2}) or second harmonic generation (when w{sub 1}=w{sub 2}). Second harmonic generation yields a value of d{sub 33}=3.2 pm/V for the self-assembled films and sum frequency generation shows a net polar orientation of the methyl groups in the multilayer along the surface normal. X-ray diffraction confirms the layered structure and produces the periodicity of {approximately}41 A, which corresponds well to the width of the supramolecular ribbons ({approximately}40 A).

Monosaccharides as Versatile Units for Water-Soluble Supramolecular Polymers.

Science.gov (United States)

Leenders, Christianus M A; Jansen, Gijs; Frissen, Martijn M M; Lafleur, René P M; Voets, Ilja K; Palmans, Anja R A; Meijer, E W

2016-03-18

We introduce monosaccharides as versatile water-soluble units to compatibilise supramolecular polymers based on the benzene-1,3,5-tricarboxamide (BTA) moiety with water. A library of monosaccharide-based BTAs is evaluated, varying the length of the alkyl chain (hexyl, octyl, decyl and dodecyl) separating the BTA and saccharide units, as well as the saccharide units (α-glucose, β-glucose, α-mannose and α-galactose). In all cases, the monosaccharides impart excellent water compatibility. The length of the alkyl chain is the determining factor to obtain either long, one-dimensional supramolecular polymers (dodecyl spacer), small aggregates (decyl spacer) or molecularly dissolved (octyl and hexyl) BTAs in water. For the BTAs comprising a dodecyl spacer, our results suggest that a cooperative self-assembly process is operative and that the introduction of different monosaccharides does not significantly change the self- assembly behaviour. Finally, we investigate the potential of post-assembly functionalisation of the formed supramolecular polymers by taking advantage of dynamic covalent bond formation between the monosaccharides and benzoxaboroles. We observe that the supramolecular polymers readily react with a fluorescent benzoxaborole derivative permitting imaging of these dynamic complexes by confocal fluorescence microscopy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular gel electrophoresis of large DNA fragments.

Science.gov (United States)

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

2017-10-01

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

Supra-amphiphiles: a new bridge between colloidal science and supramolecular chemistry.

Science.gov (United States)

Kang, Yuetong; Liu, Kai; Zhang, Xi

2014-06-03

In addition to conventional amphiphiles, an emerging research area is supra-amphiphiles, which are constructed on the basis of noncovalent interactions and dynamic covalent bonds. In this feature article, we have provided a general introduction to the concept, design principles, and topologies of supra-amphiphiles, starting from some rationally tailored building blocks. In addition, we highlight some progress in the functional assembly of supra-amphiphiles, such as responsive nanoscale carriers, antibacterial and antitumor agents, fluorescent-based chemical sensors, and enzyme mimics. The supra-amphiphile is a new bridge between colloidal science and supramolecular chemistry, and it is a field where we can make full use of our imaginative power.

Architecture of Institution & Home. Architecture as Cultural Medium

NARCIS (Netherlands)

Robinson, J.W.

2004-01-01

This dissertation addresses how architecture functions as a cultural medium. It does so by by investigating how the architecture of institution and home each construct and support different cultural practices. By studying the design of ordinary settings in terms of how qualitative differences in

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

Science.gov (United States)

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

2017-09-15

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

Selective Organic and Organometallic Reactions in Water-Soluble Host-Guest Supramolecular Systems

Energy Technology Data Exchange (ETDEWEB)

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

2008-02-16

Inspired by the efficiency and selectivity of enzymes, synthetic chemists have designed and prepared a wide range of host molecules that can bind smaller molecules with their cavities; this area has become known as 'supramolecular' or 'host-guest' chemistry. Pioneered by Lehn, Cram, Pedersen, and Breslow, and followed up by a large number of more recent investigators, it has been found that the chemical environment in each assembly - defined by the size, shape, charge, and functional group availability - greatly influences the guest-binding characteristics of these compounds. In contrast to the large number of binding studies that have been carried out in this area, the exploration of chemistry - especially catalytic chemistry - that can take place inside supramolecular host cavities is still in its infancy. For example, until the work described here was carried out, very few examples of organometallic reactivity inside supramolecular hosts were known, especially in water solution. For that reason, our group and the group directed by Kenneth Raymond decided to take advantage of our complementary expertise and attempt to carry out metal-mediated C-H bond activation reactions in water-soluble supramolecular systems. This article begins by providing background from the Raymond group in supramolecular coordination chemistry and the Bergman group in C-H bond activation. It goes on to report the results of our combined efforts in supramolecular C-H activation reactions, followed by extensions of this work into a wider range of intracavity transformations.

Supramolecular interactions of oxidative stress biomarker glutathione with fluorone black

Science.gov (United States)

Hepel, Maria; Stobiecka, Magdalena

2018-03-01

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

Supramolecular interactions of oxidative stress biomarker glutathione with fluorone black.

Science.gov (United States)

Hepel, Maria; Stobiecka, Magdalena

2018-03-05

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

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

NARCIS (Netherlands)

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

2015-01-01

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

Supramolecular protein immobilization on lipid bilayers

NARCIS (Netherlands)

Bosmans, R.P.G.; Hendriksen, W.E.; Verheijden, Mark Lloyd; Eelkema, R.; Jonkheijm, Pascal; van Esch, J.H.; Brunsveld, Luc

2015-01-01

Protein immobilization on surfaces, and on lipid bilayers specifically, has great potential in biomolecular and biotechnological research. Of current special interest is the immobilization of proteins using supramolecular noncovalent interactions. This allows for a reversible immobilization and

Supramolecular Complexes Formed in Systems Bile Salt-Bilirubin-Silica

Science.gov (United States)

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

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

Tectonic thinking in contemporary industrialized architecture

DEFF Research Database (Denmark)

Beim, Anne

2013-01-01

a creative force in building constructions, structural features and architectural design (construing) – helps to identify and refine technology transfer in contemporary industrialized building construction’. Through various references from the construction industry, business theory and architectural practice......This paper argues for a new critical approach to the ways architectural design strategies are developing. Contemporary construction industry appears to evolve into highly specialized and optimized processes driven by industrialized manufacturing, therefore the role of the architect...... and the understanding of the architectural design process ought to be revised. The paper is based on the following underlying hypothesis: ‘Tectonic thinking – defined as a central attention towards the nature, the properties, and the application of building materials (construction) and how this attention forms...

Nanoparticles functionalized with supramolecular host-guest systems for nanomedicine and healthcare.

Science.gov (United States)

Wu, Zilong; Song, Nan; Menz, Ryan; Pingali, Bharadwaj; Yang, Ying-Wei; Zheng, Yuebing

2015-05-01

Synthetic macrocyclic host compounds can interact with suitable guest molecules via noncovalent interactions to form functional supramolecular systems. With the synergistic integration of the response of molecules and the unique properties at the nanoscale, nanoparticles functionalized with the host-guest supramolecular systems have shown great potentials for a broad range of applications in the fields of nanoscience and nanotechnology. In this review article, we focus on the applications of the nanoparticles functionalized with supramolecular host-guest systems in nanomedicine and healthcare, including therapeutic delivery, imaging, sensing and removal of harmful substances. A large number of examples are included to elucidate the working mechanisms, advantages, limitations and future developments of the nanoparticle-supramolecule systems in these applications.

An impedimetric study of DNA hybridization on paper-supported inkjet-printed gold electrodes

International Nuclear Information System (INIS)

Ihalainen, Petri; Määttänen, Anni; Peltonen, Jouko; Pettersson, Fredrik; Pesonen, Markus; Österbacka, Ronald; Viitala, Tapani

2014-01-01

In this study, two different supramolecular recognition architectures for impedimetric detection of DNA hybridization have been formed on disposable paper-supported inkjet-printed gold electrodes. The gold electrodes were fabricated using a gold nanoparticle based ink. The first recognition architecture consists of subsequent layers of biotinylated self-assembly monolayer (SAM), streptavidin and biotinylated DNA probe. The other recognition architecture is constructed by immobilization of thiol-functionalized DNA probe (HS-DNA) and subsequent backfill with 11-mercapto-1-undecanol (MUOH) SAM. The binding capacity and selectivity of the recognition architectures were examined by surface plasmon resonance (SPR) measurements. SPR results showed that the HS-DNA/MUOH system had a higher binding capacity for the complementary DNA target. Electrochemical impedance spectroscopy (EIS) measurements showed that the hybridization can be detected with impedimetric spectroscopy in picomol range for both systems. EIS signal indicated a good selectivity for both recognition architectures, whereas SPR showed very high unspecific binding for the HS-DNA/MUOH system. The factors affecting the impedance signal were interpreted in terms of the complexity of the supramolecular architecture. The more complex architecture acts as a less ideal capacitive sensor and the impedance signal is dominated by the resistive elements. (paper)

Supramolecular chemistry - interdisciplinary branch of science

International Nuclear Information System (INIS)

Radecka-Paryzek, W.

1997-01-01

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

A Supramolecular Approach to Medicinal Chemistry: Medicine Beyond the Molecule

Science.gov (United States)

Smith, David K.

2005-03-01

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

From dendrimers to fractal polymers and beyond

Directory of Open Access Journals (Sweden)

Charles N. Moorefield

2013-01-01

Full Text Available The advent of dendritic chemistry has facilitated materials research by allowing precise control of functional component placement in macromolecular architecture. The iterative synthetic protocols used for dendrimer construction were developed based on the desire to craft highly branched, high molecular weight, molecules with exact mass and tailored functionality. Arborols, inspired by trees and precursors of the utilitarian macromolecules known as dendrimers today, were the first examples to employ predesigned, 1 → 3 C-branched, building blocks; physical characteristics of the arborols, including their globular shapes, excellent solubilities, and demonstrated aggregation, combined to reveal the inherent supramolecular potential (e.g., the unimolecular micelle of these unique species. The architecture that is a characteristic of dendritic materials also exhibits fractal qualities based on self-similar, repetitive, branched frameworks. Thus, the fractal design and supramolecular aspects of these constructs are suggestive of a larger field of fractal materials that incorporates repeating geometries and are derived by complementary building block recognition and assembly. Use of terpyridine-M2+-terpyridine (where, M = Ru, Zn, Fe, etc connectivity in concert with mathematical algorithms, such as forms the basis for the Seirpinski gasket, has allowed the beginning exploration of fractal materials construction. The propensity of the fractal molecules to self-assemble into higher order architectures adds another dimension to this new arena of materials and composite construction.

The experimental and theoretical landscape of a new antiplatelet drug ticagrelor: Insight into supramolecular architecture directed by Csbnd H⋯F, π⋯π and Csbnd H⋯π interactions

Science.gov (United States)

Bojarska, Joanna; Remko, Milan; Fruziński, Andrzej; Maniukiewicz, Waldemar

2018-02-01

The crystal and molecular structure landscape of a new drug ticagrelor has been investigated by using experimental and theoretical approach. The structures of this cyclopentyl-triazolo-pyrimidine derivative, (1) and its DMSO solvate (2), were determined by SC-XRD at 100 K. (1) crystallizes in the orthorhombic space group P21212 with four independent molecules, while (2) belongs to the monoclinic system with the space group C2, including two ticagrelor and 0.5 DMSO molecules in the asymmetric unit. Both crystals present diverse interactions, such as: Osbnd H⋯O, Nsbnd H⋯O and Csbnd H⋯X (X = O, N, F, S). H-bonds between Ntriazolopyrimidine and sbnd OH groups of cyclopentane-1,2-diol ring connect ticagrelor molecules into dimers forming three fused rings, encoded as R22(9) and R22(10) graph-set motifs, which are further linked by Chydroxyethoxy-H⋯Fsbnd C3,4difluorophenyl into a supramolecular chain. A comparative insight into the studies of all contacts in the crystal lattices of ticagrelors and other related adenosine derivatives from the CSD was provided using Hirshfeld surface analysis. It highlights a significant difference in terms of various substituents. Notably, F⋯H/H⋯F are more meaningful than O⋯H/H⋯O and N⋯H/H⋯N H-bonds. The π⋯π stacking and Csbnd H⋯π interactions participate in a cooperative way to stabilize the supramolecular architecture. The geometry of both ticagrelor forms was optimized in the gas-phase and solvated state, using the DFT method, at the Becke 3LYP/B97D level. The theoretical results show a good agreement with those obtained from the X-ray study. Moreover, structural elucidation of a new drug was extended by 1D 1H, 13C NMR, 2D 1H, 13C HSQC NMR, FT-IR and TG/DTG techniques.

Self-Assembly of Coordinative Supramolecular Polygons with Open Binding Sites.

Science.gov (United States)

Zheng, Yao-Rong; Wang, Ming; Kobayashi, Shiho; Stang, Peter J

2011-04-27

The design and synthesis of coordinative supramolecular polygons with open binding sites is described. Coordination-driven self-assembly of 2,6-bis(pyridin-4-ylethynyl)pyridine with 60° and 120° organoplatinum acceptors results in quantitative formation of a supramolecular rhomboid and hexagon, respectively, both bearing open pyridyl binding sites. The structures were determined by multinuclear ((31)P and (1)H) NMR spectroscopy and electrospray ionization (ESI) mass spectrometry, along with a computational study.

Intelligent Chiral Sensing Based on Supramolecular and Interfacial Concepts

Directory of Open Access Journals (Sweden)

Hironori Izawa

2010-07-01

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

Supramolecular fluorene based materials

OpenAIRE

Abbel, R.J.

2008-01-01

This thesis describes the use of noncovalent interactions in order to manipulate and control the self-assembly and morphology of electroactive fluorene-based materials. The supramolecular arrangement of p-conjugated polymers and oligomers can strongly influence their electronic and photophysical properties. Therefore, a detailed understanding of such organisation processes is essential for the optimisation of the performance of these materials as applied in optoelectronic devices. In order to...

Solid structures of the stepwise self-assembled copillar[5]arene-based supramolecular polymers

International Nuclear Information System (INIS)

Park, Yeon Sil; Hwang, Seong Min; Shin, Jae Yeon; Paek, Kyung Soo

2016-01-01

Development of supramolecular polymer has attracted much interest because of their interesting properties such as stimuli-responsiveness, recycling, self-healing and degradability, and their consequential applications. The essential feature of this class of polymers is the self-assembly of discrete monomeric subunits via non-covalent interactions or dynamic covalent bonds. Among the many monomeric subunits, pillar[n]arenes have been ideal building blocks for the fabrication of polymeric supramolecules because of their intrinsic characteristics. The ring-shaped morphologies in supramolecular polymer P are probably due to the tendency of the end-to-end connection in the solid state of long flexible supramolecular chains. The size increase of nano-rings as the stepwise addition increases might be due to the fact that the linear supramolecular polymer P in solution seems to be maintained until the nano-ring formation by solidification

Solid structures of the stepwise self-assembled copillar[5]arene-based supramolecular polymers

Energy Technology Data Exchange (ETDEWEB)

Park, Yeon Sil; Hwang, Seong Min; Shin, Jae Yeon; Paek, Kyung Soo [Dept. of Chemistry, Soongsil University, Seoul (Korea, Republic of)

2016-10-15

Development of supramolecular polymer has attracted much interest because of their interesting properties such as stimuli-responsiveness, recycling, self-healing and degradability, and their consequential applications. The essential feature of this class of polymers is the self-assembly of discrete monomeric subunits via non-covalent interactions or dynamic covalent bonds. Among the many monomeric subunits, pillar[n]arenes have been ideal building blocks for the fabrication of polymeric supramolecules because of their intrinsic characteristics. The ring-shaped morphologies in supramolecular polymer P are probably due to the tendency of the end-to-end connection in the solid state of long flexible supramolecular chains. The size increase of nano-rings as the stepwise addition increases might be due to the fact that the linear supramolecular polymer P in solution seems to be maintained until the nano-ring formation by solidification.

Side-Chain Supramolecular Polymers Employing Conformer Independent Triple Hydrogen Bonding Arrays

OpenAIRE

Gooch, Adam; Murphy, Natasha S.; Thomson, Neil H.; Wilson, Andrew J.

2013-01-01

Derivatives of thymine have been extensively used to promote supramolecular materials assembly. Such derivatives can be synthetically challenging to access and may be susceptible to degradation. The current article uses a conformer-independent acceptor-donor-acceptor array (ureidopyrimidine) which forms moderate affinity interactions with diamidopyridine derivatives to effect supramolecular blend formation between polystyrene and poly(methyl methacrylate) polymers obtained by RAFT which have ...

Supramolecular photocatalyst of RGO-cyclodextrin-TiO2

International Nuclear Information System (INIS)

Shen, Jianfeng; Li, Na; Ye, Mingxin

2013-01-01

Graphical abstract: Supramolecular photocatalyst of RGO-cyclodextrin-TiO 2 was achieved, which showed high photocatalytic activity and adsorption capacity. Highlights: •Supramolecular photocatalyst of RGO-cyclodextrin-TiO 2 was achieved. •β-CD molecules acted as linkers between RGO and monodisperse TiO 2 nanoparticles. •Reduction of GO and preparation of RGO-cyclodextrin-TiO 2 was simultaneous. •The prepared RGO-cyclodextrin-TiO 2 shows high photocatalytic activity and adsorption capacity. -- Abstract: Reduced graphene oxide (RGO)/β-cyclodextrin (β-CD)/titanium oxide (TiO 2 ) supramolecular photocatalyst was synthesized with a one-pot hydrothermal method. The reducing process was accomplished with the attaching of β-CD and generation of TiO 2 . β-CD acted as a linker between RGO and monodisperse TiO 2 nanoparticles. The structure and composition of the hybrid had been characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, thermal gravimetric analysis, X-ray diffraction and Transmission electron microscopy. The as-prepared RGO-CD-TiO 2 showed significant enhanced performance for phenol and Cr (VI) removal, due to the effective transfer of photo-generated electron from TiO2 to RGO and improved absorbance performance of the hybrid

Design of novel supramolecular self-assembly creating ...

Indian Academy of Sciences (India)

Administrator

Metal–organic composite materials with appropriate building blocks which can assemble into structures with specific and desired frameworks are challenging both for their solid state technology and for their chemical architecture. Of special interest is the construction of a microporous network that can exhibit reversible guest ...

Two Zn and Hg bromide salts based on 1-ethyl-3-methyl imidazolium ionic liquid: Ionothermal synthesis, structures and supramolecular organization

Directory of Open Access Journals (Sweden)

Xiu-Cheng Zhang

2012-12-01

Full Text Available Two Zn(II and Hg(II bromide salts, [EMI]2[ZnBr4] (1 and [EMI][HgBr3] (2, have been synthesized under ionothermal conditions using 1-ethyl-3-methyl imidazolium bromide ([EMI]Br as solvents. 1 consists of tetrahedral anion [ZnBr4]2− and 2 consists of 1D double chain locating in the cavities surrounded by [EMI]+ cations. Both compounds exhibit 3D supramolecular architectures organized by the C-H•••Br hydrogen bondings and alkyl-alkyl interactions.DOI: http://dx.doi.org/10.4314/bcse.v26i3.9

Supramolecular interactions in the solid state

Directory of Open Access Journals (Sweden)

Giuseppe Resnati

2015-11-01

Full Text Available In the last few decades, supramolecular chemistry has been at the forefront of chemical research, with the aim of understanding chemistry beyond the covalent bond. Since the long-range periodicity in crystals is a product of the directionally specific short-range intermolecular interactions that are responsible for molecular assembly, analysis of crystalline solids provides a primary means to investigate intermolecular interactions and recognition phenomena. This article discusses some areas of contemporary research involving supramolecular interactions in the solid state. The topics covered are: (1 an overview and historical review of halogen bonding; (2 exploring non-ambient conditions to investigate intermolecular interactions in crystals; (3 the role of intermolecular interactions in morphotropy, being the link between isostructurality and polymorphism; (4 strategic realisation of kinetic coordination polymers by exploiting multi-interactive linker molecules. The discussion touches upon many of the prerequisites for controlled preparation and characterization of crystalline materials.

Uses of neutron scattering in supramolecular chemistry

International Nuclear Information System (INIS)

Lindoy, L.F.

1998-01-01

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

Design and construction principles in nature and architecture

International Nuclear Information System (INIS)

Knippers, Jan; Speck, Thomas

2012-01-01

This paper will focus on how the emerging scientific discipline of biomimetics can bring new insights into the field of architecture. An analysis of both architectural and biological methodologies will show important aspects connecting these two. The foundation of this paper is a case study of convertible structures based on elastic plant movements.

Design and construction principles in nature and architecture.

Science.gov (United States)

Knippers, Jan; Speck, Thomas

2012-03-01

This paper will focus on how the emerging scientific discipline of biomimetics can bring new insights into the field of architecture. An analysis of both architectural and biological methodologies will show important aspects connecting these two. The foundation of this paper is a case study of convertible structures based on elastic plant movements.

Applications of supramolecular chemistry

CERN Document Server

Schneider, Hans-Jörg

2012-01-01

""The time is ripe for the present volume, which gathers thorough presentations of the numerous actually realized or potentially accessible applications of supramolecular chemistry by a number of the leading figures in the field. The variety of topics covered is witness to the diversity of the approaches and the areas of implementation…a broad and timely panorama of the field assembling an eminent roster of contributors.""-Jean-Marie Lehn, 1987 Noble Prize Winner in Chemistry

A supramolecular strategy for self-mobile adsorption sites in affinity membrane.

Science.gov (United States)

Lin, Ligang; Dong, Meimei; Liu, Chunyu; Wei, Chenjie; Wang, Yuanyuan; Sun, Hui; Ye, Hui

2014-09-01

Disclosed here is the design of a novel supramolecular membrane with self-mobile adsorption sites for biomolecules purification. In the 3D micropore channels of membrane matrix, the ligands are conjugated onto the cyclic compounds in polyrotaxanes for protein adsorption. During membrane filtration, the adsorption sites can rotate and/or slide along the axial chain, which results in the enhanced adsorption capacity. The excellent performance of supra-molecular membrane is related with the dynamic working manner of adsorption sites, which plays a crucial role on avoiding spatial mismatching and short-circuit effect. The supra-molecular strategy described here has general suggestions for the "sites" involved technologies such as catalysis, adsorption, and sensors, which is of broad interest. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-03-15

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

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

International Nuclear Information System (INIS)

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

2012-01-01

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

The Political Economy of Architectural Research : Dutch Architecture, Architects and the City, 2000-2012

NARCIS (Netherlands)

Djalali, A.

2016-01-01

The status of architectural research has not yet been clearly defined. Nevertheless, architectural research has surely become a core element in the profession of architecture. In fact, the tendency seem for architects to be less and less involved with building design and construction services, which

Re[valuating]-architecture

NARCIS (Netherlands)

Pereira Roders, A.R.; Post, J.M.; Erkelens, P.A.; Haugen, T.I.

2006-01-01

The architectural hierarchy of aims altered in the last decades. Quality and comfort have dethroned functionality! We are already familiar with the taxonomy – quality certification in the construction world; but in architectural designs, it is not common to evaluate scientifically, if the design has

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

International Nuclear Information System (INIS)

Halaszova, S.; Velic, D.

2013-01-01

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

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry.

Science.gov (United States)

Cremer, Paul S; Flood, Amar H; Gibb, Bruce C; Mobley, David L

2017-12-19

On planet Earth, water is everywhere: the majority of the surface is covered with it; it is a key component of all life; its vapour and droplets fill the lower atmosphere; and even rocks contain it and undergo geomorphological changes because of it. A community of physical scientists largely drives studies of the chemistry of water and aqueous solutions, with expertise in biochemistry, spectroscopy and computer modelling. More recently, however, supramolecular chemists - with their expertise in macrocyclic synthesis and measuring supramolecular interactions - have renewed their interest in water-mediated non-covalent interactions. These two groups offer complementary expertise that, if harnessed, offer to accelerate our understanding of aqueous supramolecular chemistry and water writ large. This Review summarizes the state-of-the-art of the two fields, and highlights where there is latent chemical space for collaborative exploration by the two groups.

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

Science.gov (United States)

Cremer, Paul S.; Flood, Amar H.; Gibb, Bruce C.; Mobley, David L.

2018-01-01

On planet Earth, water is everywhere: the majority of the surface is covered with it; it is a key component of all life; its vapour and droplets fill the lower atmosphere; and even rocks contain it and undergo geomorphological changes because of it. A community of physical scientists largely drives studies of the chemistry of water and aqueous solutions, with expertise in biochemistry, spectroscopy and computer modelling. More recently, however, supramolecular chemists -- with their expertise in macrocyclic synthesis and measuring supramolecular interactions -- have renewed their interest in water-mediated non-covalent interactions. These two groups offer complementary expertise that, if harnessed, offer to accelerate our understanding of aqueous supramolecular chemistry and water writ large. This Review summarizes the state-of-the-art of the two fields, and highlights where there is latent chemical space for collaborative exploration by the two groups.

Knowledge Management Practice in Two Australian Architecture-Engineering-Construction (AEC Companies

Directory of Open Access Journals (Sweden)

Patrick Zou

2012-11-01

Full Text Available Knowledge management (KM could be described as a management system that supports the creation, sharing and retrieving of valued information, expertise and insight within and across communities of people and related organizations using information and communication technologies and hence it is a combination of the effective application of information technlogy and management of human resources. KM is becoming a core competitive factor in construction operations. This paper presents the results of two case studies of KM practices in large AEC (architecture, engineering and construction companies through desk-top study and semi-structured interviews. The results indicate that implementing KM in AEC companies leads to competitive advantages and improved decision-making, problem solving and business performance. The results also indicateed that while technology plays an important role, top management commitment, total employee involvement, performance assessment and the culture of knowledge-learning and sharing must be considered when implementing KM. Therefore it is suggested that the implementation of KM should incorporate the company's vision, work processes, technology and culture, to improve the ability of knowledge creating, capturing, sharing, retrieving and ultimately, to improve the company's competitive advantage, decision making, problem solving and innovation.

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

Science.gov (United States)

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

2007-01-01

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

The role of supramolecular chemistry in stimuli responsive and hierarchically structured functional organic materials

NARCIS (Netherlands)

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

2014-01-01

ABSTRACT: In this review, we show the important role of supramolecular chemistry in the fabrication of stimuli responsive and hierarchically structured liquid crystalline polymer networks. Supramolecular interactions can be used to create three dimensional order or as molecular triggers in materials

Models in architectural design

OpenAIRE

Pauwels, Pieter

2017-01-01

Whereas architects and construction specialists used to rely mainly on sketches and physical models as representations of their own cognitive design models, they rely now more and more on computer models. Parametric models, generative models, as-built models, building information models (BIM), and so forth, they are used daily by any practitioner in architectural design and construction. Although processes of abstraction and the actual architectural model-based reasoning itself of course rema...

Syntheses, crystal structures and luminescent properties of two new 1D d 1 coordination polymers constructed from 2,2'-bibenzimidazole and 1,4-benzenedicarboxylate

International Nuclear Information System (INIS)

Wen Lili; Li Yizhi; Dang Dongbin; Tian Zhengfang; Ni Zhaoping; Meng Qingjin

2005-01-01

Two novel interesting d 1 metal coordination polymers, [Zn(H 2 bibzim)(BDC)] n (1) and [Cd(H 2 bibzim)(BDC)] n (2) [H 2 bibzim=2,2'-bibenzimidazole, BDC=1,4-benzenedicarboxylate] have been synthesized under solvothermal conditions and structurally characterized. Both 1 and 2 are constructed from infinite neutral zigzag-like one-dimensional (1D) chains. The π-π interactions and interchain hydrogen-bonding interactions further extend the 1D arrangement to generate a 3D supramolecular architecture for 1 and 2. Both complexes have high thermal stability and display strong blue fluorescent emissions in the solid state upon photo-excitation at 365 nm at room temperature. They are the first two examples that 2,2'-bibenzimidazole has been introduced into the d 1 coordination polymeric framework

Porphyrinic supramolecular daisy chains incorporating pillar[5]arene-viologen host-guest interactions

KAUST Repository

Fathalla, Maher; Strutt, Nathan; Srinivasan, Sampath; Katsiev, Khabiboulakh; Hartlieb, Karel J.; Bakr, Osman; Stoddart, J. Fraser

2015-01-01

A porphyrin functionalised with pillar[5]arene and a viologen at its 5- and 15-meso positions assembles in a head-to-tail manner, producing linear supramolecular daisy chains in dichloromethane. At high concentrations, it forms an organogel which has been investigated by electron microscopy and rheological measurements, paving the way for the preparation of other functional supramolecular assemblies which harness viologen"⊂" pillararene host-guest interactions.

Porphyrinic supramolecular daisy chains incorporating pillar[5]arene-viologen host-guest interactions

KAUST Repository

Fathalla, Maher

2015-05-18

A porphyrin functionalised with pillar[5]arene and a viologen at its 5- and 15-meso positions assembles in a head-to-tail manner, producing linear supramolecular daisy chains in dichloromethane. At high concentrations, it forms an organogel which has been investigated by electron microscopy and rheological measurements, paving the way for the preparation of other functional supramolecular assemblies which harness viologen"⊂" pillararene host-guest interactions.

Unexpected Rotamerism at the Origin of a Chessboard Supramolecular Assembly of Ruthenium Phthalocyanine.

Science.gov (United States)

Mattioli, Giuseppe; Larciprete, Rosanna; Alippi, Paola; Bonapasta, Aldo Amore; Filippone, Francesco; Lacovig, Paolo; Lizzit, Silvano; Paoletti, Anna Maria; Pennesi, Giovanna; Ronci, Fabio; Zanotti, Gloria; Colonna, Stefano

2017-11-16

We have investigated the formation and the properties of ultrathin films of ruthenium phthalocyanine (RuPc) 2 vacuum deposited on graphite by scanning tunneling microscopy and synchrotron photoemission spectroscopy measurements, interpreted in close conjunction with ab initio simulations. Thanks to its unique dimeric structure connected by a direct Ru-Ru bond, (RuPc) 2 can be found in two stable rotameric forms separated by a low-energy barrier. Such isomerism leads to a peculiar organization of the molecules in flat, horizontal layers on the graphite surface, characterized by a chessboard-like alternation of the two rotamers. Moreover, the molecules are vertically connected to form π-stacked columnar pillars of akin rotamers, compatible with the high conductivity measured in (RuPc) 2 powders. Such features yield an unprecedented supramolecular assembly of phthalocyanine films, which could open interesting perspectives toward the realization of new architectures of organic electronic devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A leadership-as-practice perspective on design in architecture, engineering and construction projects: interaction analysis of a collaborative workshop

NARCIS (Netherlands)

Zerjav, Vedran; Hartmann, Timo; van Amstel, Frederick

2014-01-01

This paper proposes an alternative perspective on the role of leadership in the context of collaborative practices in architecture, engineering and construction design. While most of current leadership literature is focused on outstanding individuals with abilities to influence others, the aim of

Strong and Reversible Monovalent Supramolecular Protein Immobilization

NARCIS (Netherlands)

Young, Jacqui F.; Nguyen, Hoang D.; Yang, Lanti; Huskens, Jurriaan; Jonkheijm, Pascal; Brunsveld, Luc

2010-01-01

Proteins with an iron clasp: Site-selective incorporation of a ferrocene molecule into a protein allows for easy, strong, and reversible supramolecular protein immobilization through a selective monovalent interaction of the ferrocene with a cucurbit[7]uril immobilized on a gold surface. The

From ring-in-ring to sphere-in-sphere: self-assembly of discrete 2D and 3D architectures with increasing stability.

Science.gov (United States)

Sun, Bin; Wang, Ming; Lou, Zhichao; Huang, Mingjun; Xu, Chenglong; Li, Xiaohong; Chen, Li-Jun; Yu, Yihua; Davis, Grant L; Xu, Bingqian; Yang, Hai-Bo; Li, Xiaopeng

2015-02-04

Directed by increasing the density of coordination sites (DOCS) to increase the stability of assemblies, discrete 2D ring-in-rings and 3D sphere-in-sphere were designed and self-assembled by one tetratopic pyridyl-based ligand with 180° diplatinum(II) acceptors and naked Pd(II), respectively. The high DOCS resulted by multitopic ligand provided more geometric constraints to form discrete structures with high stability. Compared to reported supramolecular hexagons and polyhedra by ditotpic ligands, the self-assembly of such giant architectures using multitopic ligands with all rigid backbone emphasized the structural integrity with precise preorganization of entire architecture, and required elaborate synthetic operations for ligand preparation. In-depth structural characterization was conducted to support desired structures, including multinuclear NMR ((1)H, (31)P, and (13)C) analysis, 2D NMR spectroscopy (COSY and NOESY), diffusion-ordered NMR spectroscopy (DOSY), multidimensional mass spectrometry, TEM and AFM. Furthermore, a quantitative definition of DOCS was proposed to compare 2D and 3D structures and correlate the DOCS and stability of assemblies in a quantitative manner. Finally, ring-in-rings in DMSO or DMF could undergo hierarchical self-assembly into the ordered nanostructures and generated translucent supramolecular metallogels.

Stoichiometry-Controlled Inversion of Supramolecular Chirality in Nanostructures Co-assembled with Bipyridines.

Science.gov (United States)

Wang, Fang; Feng, Chuan-Liang

2018-02-01

To control supramolecular chirality of the co-assembled nanostructures, one of the remaining issues is how stoichiometry of the different molecules involved in co-assembly influence chiral transformation. Through co-assembly of achiral 1,4-bis(pyrid-4-yl)benzene and chiral phenylalanine-glycine derivative hydrogelators, stoichiometry is found to be an effective tool for controlling supramolecular chirality inversion processes. This inversion is mainly mediated by a delicate balance between intermolecular hydrogen bonding interactions and π-π stacking of the two components, which may subtly change the stacking of the molecules, in turn, the self-assembled nanostructures. This study exemplifies a simplistic way to invert the handedness of chiral nanostructures and provide fundamental understanding of the inherent principles of supramolecular chirality. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular Rotor and Translator at Work: On-Surface Movement of Single Atoms.

Science.gov (United States)

Ohmann, Robin; Meyer, Jörg; Nickel, Anja; Echeverria, Jorge; Grisolia, Maricarmen; Joachim, Christian; Moresco, Francesca; Cuniberti, Gianaurelio

2015-08-25

A supramolecular nanostructure composed of four 4-acetylbiphenyl molecules and self-assembled on Au (111) was loaded with single Au adatoms and studied by scanning tunneling microscopy at low temperature. By applying voltage pulses to the supramolecular structure, the loaded Au atoms can be rotated and translated in a controlled manner. The manipulation of the gold adatoms is driven neither by mechanical interaction nor by direct electronic excitation. At the electronic resonance and driven by the tunneling current intensity, the supramolecular nanostructure performs a small amount of work of about 8 × 10(-21) J, while transporting the single Au atom from one adsorption site to the next. Using the measured average excitation time necessary to induce the movement, we determine the mechanical motive power of the device, yielding about 3 × 10(-21) W.

The signs of life in architecture.

Science.gov (United States)

Gruber, Petra

2008-06-01

Engineers, designers and architects often look to nature for inspiration. The research on 'natural constructions' is aiming at innovation and the improvement of architectural quality. The introduction of life sciences terminology in the context of architecture delivers new perspectives towards innovation in architecture and design. The investigation is focused on the analogies between nature and architecture. Apart from other principles that are found in living nature, an interpretation of the so-called 'signs of life', which characterize living systems, in architecture is presented. Selected architectural projects that have applied specific characteristics of life, whether on purpose or not, will show the state of development in this field and open up future challenges. The survey will include famous built architecture as well as students' design programs, which were carried out under supervision of the author at the Department of Design and Building Construction at the Vienna University of Technology.

Solution Construction of Multigeometry Nanoparticles and Multicompartment Superstructures from Block Copolymer Mixtures

Science.gov (United States)

Zhu, Jiahua; Zhang, Shiyi; Wooley, Karen; Pochan, Darrin

2013-03-01

Novel soft objects with both compositional and geometric complexity at nanoscale have been constructed through solution supramolecular assembly from block copolymer mixtures due to their non-ergodic character. The mixture is composed of two block copolymers with distinctive hydrophobic blocks but the same poly(acrylic acid) hydrophilic block. First, multigeometry nanoparticles, due to segregation of unlike block copolymer molecules into multiple subdomains trapped within the same micelle-like structures, have been assembled in tetrahydrofuran/water solution. Through carefully designed molecular architecture, mixing ratio and pathway kinetics, both size and shape of subdomains can be controlled to produce a novel class of multigeometry nanoparticles, including sphere-sphere, sphere-cylinder, cylinder-cylinder, cylinder-disk, and sphere-disk hybrid nanoparticles. Second, hierarchical multicompartment superstructures including particle chains, rings and other nano to micro cluster formations, have been built up from pre-formed multigeometry nanoparticles by taking advantage of their surface anisotropy and the controlled particle-particle association. The interparticle association can be achieved via either covalent or non-covalent bindings due to different post-polymerization chemical modifications with hydroxyethyl acrylate or crown ether functionalities, respectively.

Size-controlled and redox-responsive supramolecular nanoparticles

NARCIS (Netherlands)

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

2015-01-01

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

Design of Self-Healing Supramolecular Rubbers by Introducing Ionic Cross-Links into Natural Rubber via a Controlled Vulcanization.

Science.gov (United States)

Xu, Chuanhui; Cao, Liming; Lin, Baofeng; Liang, Xingquan; Chen, Yukun

2016-07-13

Introducing ionic associations is one of the most effective approaches to realize a self-healing behavior for rubbers. However, most of commercial rubbers are nonpolar rubbers without now available functional groups to be converted into ionic groups. In this paper, our strategy was based on a controlled peroxide-induced vulcanization to generate massive ionic cross-links via polymerization of zinc dimethacrylate (ZDMA) in natural rubber (NR) and exploited it as a potential self-healable material. We controlled vulcanization process to retard the formation of covalent cross-link network, and successfully generated a reversible supramolecular network mainly constructed by ionic cross-links. Without the restriction of covalent cross-linkings, the NR chains in ionic supramolecular network had good flexibility and mobility. The nature that the ionic cross-links was easily reconstructed and rearranged facilitating the self-healing behavior, thereby enabling a fully cut sample to rejoin and retain to its original properties after a suitable self-healing process at ambient temperature. This study thus demonstrates a feasible approach to impart an ionic association induced self-healing function to commercial rubbers without ionic functional groups.

Computation, architectural design and fabrication logic

DEFF Research Database (Denmark)

Larsen, Niels Martin

2016-01-01

Digital fabrication and digital form generation can change the way different professions interact in relation to the development and construction of architecture. The technologies can provide a more integrated design process and expand the architectural vocabulary. At Aarhus School of Architectur...

Enzymatic Dissolution of Biocomposite Solids Consisting of Phosphopeptides to Form Supramolecular Hydrogels

KAUST Repository

Shi, Junfeng; Yuan, Dan; Haburcak, Richard; Zhang, Qiang; Zhao, Chao; Zhang, Xixiang; Xu, Bing

2015-01-01

Enzyme-catalyzed dephosphorylation is essential for biomineralization and bone metabolism. Here we report the exploration of using enzymatic reaction to transform biocomposites of phosphopeptides and calcium (or strontium) ions to supramolecular hydrogels as a mimic of enzymatic dissolution of biominerals. 31P NMR shows that strong affinity between the phosphopeptides and alkaline metal ions (e.g., Ca2+ or Sr2+) induces the formation of biocomposites as precipitates. Electron microscopy reveals that the enzymatic reaction regulates the morphological transition from particles to nanofibers. Rheology confirms the formation of a rigid hydrogel. As the first example of enzyme-instructed dissolution of a solid to form supramolecular nanofibers/hydrogels, this work provides an approach to generate soft materials with desired properties, expands the application of supramolecular hydrogelators, and offers insights to control the demineralization of calcified soft tissues.

Enzymatic Dissolution of Biocomposite Solids Consisting of Phosphopeptides to Form Supramolecular Hydrogels

KAUST Repository

Shi, Junfeng

2015-10-14

Enzyme-catalyzed dephosphorylation is essential for biomineralization and bone metabolism. Here we report the exploration of using enzymatic reaction to transform biocomposites of phosphopeptides and calcium (or strontium) ions to supramolecular hydrogels as a mimic of enzymatic dissolution of biominerals. 31P NMR shows that strong affinity between the phosphopeptides and alkaline metal ions (e.g., Ca2+ or Sr2+) induces the formation of biocomposites as precipitates. Electron microscopy reveals that the enzymatic reaction regulates the morphological transition from particles to nanofibers. Rheology confirms the formation of a rigid hydrogel. As the first example of enzyme-instructed dissolution of a solid to form supramolecular nanofibers/hydrogels, this work provides an approach to generate soft materials with desired properties, expands the application of supramolecular hydrogelators, and offers insights to control the demineralization of calcified soft tissues.

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

Directory of Open Access Journals (Sweden)

Camillo La Mesa

2007-08-01

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

Cellular uptake: lessons from supramolecular organic chemistry.

Science.gov (United States)

Gasparini, Giulio; Bang, Eun-Kyoung; Montenegro, Javier; Matile, Stefan

2015-07-04

The objective of this Feature Article is to reflect on the importance of established and emerging principles of supramolecular organic chemistry to address one of the most persistent problems in life sciences. The main topic is dynamic covalent chemistry on cell surfaces, particularly disulfide exchange for thiol-mediated uptake. Examples of boronate and hydrazone exchange are added for contrast, comparison and completion. Of equal importance are the discussions of proximity effects in polyions and counterion hopping, and more recent highlights on ring tension and ion pair-π interactions. These lessons from supramolecular organic chemistry apply to cell-penetrating peptides, particularly the origin of "arginine magic" and the "pyrenebutyrate trick," and the currently emerging complementary "disulfide magic" with cell-penetrating poly(disulfide)s. They further extend to the voltage gating of neuronal potassium channels, gene transfection, and the delivery of siRNA. The collected examples illustrate that the input from conceptually innovative chemistry is essential to address the true challenges in biology beyond incremental progress and random screening.

Fabrication of Supramolecular Chirality from Achiral Molecules at the Liquid/Liquid Interface Studied by Second Harmonic Generation.

Science.gov (United States)

Lin, Lu; Zhang, Zhen; Guo, Yuan; Liu, Minghua

2018-01-09

We present the investigation into the supramolecular chirality of 5-octadecyloxy-2-(2-pyridylazo)phenol (PARC18) at water/1,2-dichloroethane interface by second harmonic generation (SHG). We observe that PARC18 molecules form supramolecular chirality through self-assembly at the liquid/liquid interface although they are achiral molecules. The bulk concentration of PARC18 in the organic phase has profound effects on the supramolecular chirality. By increasing bulk concentration, the enantiomeric excess at the interface first grows and then decreases until it eventually vanishes. Further analysis reveals that the enantiomeric excess is determined by the twist angle of PARC18 molecules at the interface rather than their orientational angle. At lower and higher bulk concentrations, the average twist angle of PARC18 molecules approaches zero, and the assemblies are achiral; whereas at medium bulk concentrations, the average twist angle is nonzero, so that the assemblies show supramolecular chirality. We also estimate the coverage of PARC18 molecules at the interface versus the bulk concentration and fit it to Langmuir adsorption model. The result indicates that PARC18 assemblies show strongest supramolecular chirality in a half-full monolayer. These findings highlight the opportunities for precise control of supramolecular chirality at liquid/liquid interfaces by manipulating the bulk concentration.

Minimalistic peptide supramolecular co-assembly: expanding the conformational space for nanotechnology.

Science.gov (United States)

Makam, Pandeeswar; Gazit, Ehud

2018-05-21

Molecular self-assembly is a ubiquitous process in nature and central to bottom-up nanotechnology. In particular, the organization of peptide building blocks into ordered supramolecular structures has gained much interest due to the unique properties of the products, including biocompatibility, chemical and structural diversity, robustness and ease of large-scale synthesis. In addition, peptides, as short as dipeptides, contain all the molecular information needed to spontaneously form well-ordered structures at both the nano- and the micro-scale. Therefore, peptide supramolecular assembly has been effectively utilized to produce novel materials with tailored properties for various applications in the fields of material science, engineering, medicine, and biology. To further expand the conformational space of peptide assemblies in terms of structural and functional complexity, multicomponent (two or more) peptide supramolecular co-assembly has recently evolved as a promising extended approach, similar to the structural diversity of natural sequence-defined biopolymers (proteins) as well as of synthetic covalent co-polymers. The use of this methodology was recently demonstrated in various applications, such as nanostructure physical dimension control, the creation of non-canonical complex topologies, mechanical strength modulation, the design of light harvesting soft materials, fabrication of electrically conducting devices, induced fluorescence, enzymatic catalysis and tissue engineering. In light of these significant advancements in the field of peptide supramolecular co-assembly in the last few years, in this tutorial review, we provide an updated overview and future prospects of this emerging subject.

Zwitterionic supramolecular nanoparticles: self-assembly and responsive properties

NARCIS (Netherlands)

Stoffelen, C.; Huskens, Jurriaan

2015-01-01

Supramolecular nanoparticles (SNPs) are of high interest in both nanoscience and molecular diagnostics and therapeutics, because of their reversible and designable properties. To ensure colloidal stabilization and biocompatibility, most reported strategies require the use of hydrophilic long-chain

Self-assemblage and post-radiation recovery of cell supramolecular structures

International Nuclear Information System (INIS)

Grodzinskij, D.M.; Kolomiets, K.D.

1979-01-01

The role of the molecular equation and self-assemblage in post-radiation chromatin recovery of meristematic cells of pea rootlets is shown. Found are the two repair types at the chromatin level by fractionating of the radiation dose. The first type comprises transient processes including DNA repair, the second type comprises processes including biosynthesis of the chromatin components and proteins, in the first place. The role of protein biosynthesis in the process of recovery of the chromatin supramolecular structure is shown. The improved radiostability of chromatin self-assemblage is characteristic for the level of its subunits. The supramolecular chromatin structure of the other levels has less radiostability

Supramolecular Allosteric Cofacial Porphyrin Complexes

International Nuclear Information System (INIS)

Oliveri, Christopher G.; Gianneschi, Nathan C.; Nguyen, Son Binh T.; Mirkin, Chad A.; Stern, Charlotte L.; Wawrzak, Zdzislaw; Pink, Maren

2008-01-01

Nature routinely uses cooperative interactions to regulate cellular activity. For years, chemists have designed synthetic systems that aim toward harnessing the reactivity common to natural biological systems. By learning how to control these interactions in situ, one begins to allow for the preparation of man-made biomimetic systems that can efficiently mimic the interactions found in Nature. To this end, we have designed a synthetic protocol for the preparation of flexible metal-directed supramolecular cofacial porphyrin complexes which are readily obtained in greater than 90% yield through the use of new hemilabile porphyrin ligands with bifunctional ether-phosphine or thioether-phosphine substituents at the 5 and 15 positions on the porphyrin ring. The resulting architectures contain two hemilabile ligand-metal domains (Rh I or Cu I sites) and two cofacially aligned porphyrins (Zn II sites), offering orthogonal functionalities and allowing these multimetallic complexes to exist in two states, 'condensed' or 'open'. Combining the ether-phosphine ligand with the appropriate Rh I or Cu I transition-metal precursors results in 'open' macrocyclic products. In contrast, reacting the thioether-phosphine ligand with RhI or CuI precursors yields condensed structures that can be converted into their 'open' macrocyclic forms via introduction of additional ancillary ligands. The change in cavity size that occurs allows these structures to function as allosteric catalysts for the acyl transfer reaction between X-pyridylcarbinol (where X = 2, 3, or 4) and 1-acetylimidazole. For 3- and 4-pyridylcarbinol, the 'open' macrocycle accelerates the acyl transfer reaction more than the condensed analogue and significantly more than the porphyrin monomer. In contrast, an allosteric effect was not observed for 2-pyridylcarbinol, which is expected to be a weaker binder and is unfavorably constrained inside the macrocyclic cavity.

Injectable self-healing carboxymethyl chitosan-zinc supramolecular hydrogels and their antibacterial activity.

Science.gov (United States)

Wahid, Fazli; Zhou, Ya-Ning; Wang, Hai-Song; Wan, Tong; Zhong, Cheng; Chu, Li-Qiang

2018-04-07

Injectable and self-healing hydrogels have found numerous applications in drug delivery, tissue engineering and 3D cell culture. Herein, we report an injectable self-healing carboxymethyl chitosan (CMCh) supramolecular hydrogels cross-linked by zinc ions (Zn 2+ ). Supramolecular hydrogels were obtained by simple addition of metal ions solution to CMCh solution at an appropriate pH value. The mechanical properties of these hydrogels were adjustable by the concentration of Zn 2+ . For example, the hydrogel with the highest concentration of Zn 2+ (CMCh-Zn4) showed strongest mechanical properties (storage modulus~11,000Pa) while hydrogel with the lowest concentration of Zn 2+ (CMCh-Zn1) showed weakest mechanical properties (storage modulus~220Pa). As observed visually and confirmed rheologically, the CMCh-Zn1 hydrogel with the lowest Zn 2+ concentration showed thixotropic property. CMCh-Zn1 hydrogel also presented injectable property. Moreover, the antibacterial properties of the prepared supramolecular hydrogels were studied against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) by agar well diffusion method. The results revealed Zn 2+ dependent antibacterial properties against both kinds of strains. The inhibition zones were ranging from ~11-24mm and ~10-22mm against S. aureus and E. coli, respectively. We believe that the prepared supramolecular hydrogels could be used as a potential candidate in biomedical fields. Copyright © 2018 Elsevier B.V. All rights reserved.

Model-centric software architecture reconstruction

NARCIS (Netherlands)

Stoermer, C.; Rowe, A.; O'Brien, L.; Verhoef, C.

2006-01-01

Much progress has been achieved in defining methods, techniques, and tools for software architecture reconstruction (SAR). However, less progress has been achieved in constructing reasoning frameworks from existing systems that support organizations in architecture analysis and design decisions.

Sustainable architecture approach in designing residential ...

African Journals Online (AJOL)

Sustainable architecture has been shaped with vernacular materials based on the vernacular architecture according to climatic conditions, saving energy and responding to needs and social and cultural conditions. In cold region architecture, the buildings are constructed as steps on the hills in the direction of sun and ...

Evaporation rate-based selection of supramolecular chirality.

Science.gov (United States)

Hattori, Shingo; Vandendriessche, Stefaan; Koeckelberghs, Guy; Verbiest, Thierry; Ishii, Kazuyuki

2017-03-09

We demonstrate the evaporation rate-based selection of supramolecular chirality for the first time. P-type aggregates prepared by fast evaporation, and M-type aggregates prepared by slow evaporation are kinetic and thermodynamic products under dynamic reaction conditions, respectively. These findings provide a novel solution reaction chemistry under the dynamic reaction conditions.

Fluorescent supramolecular micelles for imaging-guided cancer therapy

Science.gov (United States)

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

2016-02-01

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

Glucosamine-Based Supramolecular Nanotubes for Human Mesenchymal Cell Therapy.

Science.gov (United States)

Talloj, Satish Kumar; Cheng, Bill; Weng, Jen-Po; Lin, Hsin-Chieh

2018-04-23

Herein, we demonstrate an example of glucosamine-based supramolecular hydrogels that can be used for human mesenchymal cell therapy. We designed and synthesized a series of amino acid derivatives based on a strategy of capping d-glucosamine moiety at the C-terminus and fluorinated benzyl group at the N-terminus. From a systematic study on chemical structures, we discovered that the glucosamine-based supramolecular hydrogel [pentafluorobenzyl (PFB)-F-Glu] self-assembled with one-dimensional nanotubular structures at physiological pH. The self-assembly of a newly discovered PFB-F-Glu motif is attributed to the synergistic effect of π-π stacking and extensive intermolecular hydrogen bonding network in aqueous medium. Notably, PFB-F-Glu nanotubes are proven to be nontoxic to human mesenchymal stem cells (hMSCs) and have been shown to enhance hMSC proliferation while maintaining their pluripotency. Retaining of pluripotency capabilities provides potentially unlimited source of undifferentiated cells for the treatment of future cell therapies. Furthermore, hMSCs cultured on PFB-F-Glu are able to secrete paracrine factors that downregulate profibrotic gene expression in lipopolysaccharide-treated human skin fibroblasts, which demonstrates that PFB-F-Glu nanotubes have the potential to be used for wound healing applications. Overall, this article addresses the importance of chemical design to generate supramolecular biomaterials for stem cell therapy.

[Construction of 2-dimensional tumor microvascular architecture phenotype in non-small cell lung cancer].

Science.gov (United States)

Liu, Jin-kang; Wang, Xiao-yi; Xiong, Zeng; Zhou, Hui; Zhou, Jian-hua; Fu, Chun-yan; Li, Bo

2008-08-01

To construct a technological platform of 2-dimensional tumor microvascular architecture phenotype (2D-TAMP) expression. Thirty samples of non-small cell lung cancer (NSCLC) were collected after surgery. The corresponding sections of tumor tissue specimens to the slice of CT perfusion imaging were selected. Immunohistochemical staining,Gomori methenamine silver stain, and electron microscope observation were performed to build a technological platform of 2D-TMAP expression by detecting the morphology and the integrity of basement membrane of microvasculature, microvascular density, various microvascular subtype, the degree of the maturity and lumenization of microvasculature, and the characteristics of immunogenetics of microvasculature. The technological platform of 2D-TMAP expression was constructed successfully. There was heterogeneity in 2D-TMAP expression of non-small cell lung cancer. The microvascular of NSCLC had certain characteristics. 2D-TMAP is a key technology that can be used to observe the overall state of micro-environment in tumor growth.

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

Science.gov (United States)

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

2018-05-01

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

Supramolecular Derivation of Graphene Nanomaterials for Chemical Sensors

DEFF Research Database (Denmark)

Olsen, Gunnar

With properties such as high surface area, high conductivity, and low production cost with easy up-scaling, graphene-like materials provide a promising support for many applications, one of which is for chemical sensors. By functionalization with molecular receptors such as supramolecular moieties...... of 10−5 M. In the second approach Azido-RGO was prepared as a general platform for post reduction modification. GO was here functionalized with a short linker terminated in an alcohol. The intermediate material was then reduced effectively with NaBH4, followed by chemical transformation of the alcohol...... atoms or slightly more than one azide per nm2 of RGO-sheet. This Azido-RGO was used in successful functionalization with the large supramolecular receptor molecules TTF-calix[4]pyrrole which function as a sensor for Cl− and potentially for TNB. The coverage achieved was one molecule per 50 – 60 carbon...

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

Science.gov (United States)

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.

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

Science.gov (United States)

Wang, Fang; Feng, Chuan-Liang

2018-05-14

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

Double Dynamic Supramolecular Polymers of Covalent Oligo-Dynamers

NARCIS (Netherlands)

Schaeffer, Gaël; Buhler, Eric; Candau, Sauveur Jean; Lehn, Jean-Marie

2013-01-01

Double-dynamic polymers, incorporating both molecular and supramolecular dynamic features (“double dynamers”) have been generated, where these functions are present in a nonstoichiometric ratio in the main chain of the polymer. It has been achieved by (1) the formation of covalent oligo-dynamers in

Supramolecular oligothiophene microfibers spontaneously assembled on surfaces or coassembled with proteins inside live cells.

Science.gov (United States)

Barbarella, Giovanna; Di Maria, Francesca

2015-08-18

During the last few decades, multifunctional nano- and microfibers made of semiconducting π-conjugated oligomers and polymers have generated much interest because of a broad range of applications extending from sensing to bioelectronic devices and (opto)electronics. The simplest technique for the fabrication of these anisotropic supramolecular structures is to let the molecules do the work by spontaneous organization driven by the information encoded in their molecular structure. Oligothiophenes-semiconducting and fluorescent compounds that have been extensively investigated for applications in thin-film field-effect transistors and solar cells and to a lesser extent as dyes for fluorescent labeling of proteins, DNA, and live cells-are particularly suited as building blocks for supramolecular architectures because of the peculiar properties of the thiophene ring. Because of the great polarizability of sulfur outer-shell electrons and the consequent facile geometric deformability and adaptability of the ring to the environment, thiophene can generate multiple nonbonding interactions to promote non-covalent connections between blocks. Furthermore, sulfur can be hypervalent, i.e., it can accommodate more than the eight electrons normally associated with s and p shells. Hypervalent oligothiophene-S,S-dioxides whose oxygen atoms can be involved in hydrogen bonding have been synthesized. These compounds are amphiphilic, and some of them are able to spontaneously cross the membrane of live cells. Hypervalent nonbonding interactions of divalent sulfur, defined as weak coordination to a proximate nitrogen or oxygen, have also been invoked in the solid-state packing of many organic molecules and in the architecture of proteins. In this Account, we describe two different types of thiophene-based building blocks that can induce the spontaneous formation of nanostructured microfibers in very different environments. The first, based on the synthesis of "sulfur

JCSC_128_2_297-309_SI.doc

Indian Academy of Sciences (India)

Supramolecular architecture of the crystals 3d presented as packing of molecules and hedgehogs of intermolecular interactions. Figure S27. Supramolecular architecture of the crystals 3e presented as packing of molecules and hedgehogs of intermolecular interactions. Table TS1. Crystallographic data, parameters of ...

Supramolecular solubilization of fullerenes and radio-fullerenes in aqueous media

International Nuclear Information System (INIS)

Braun, T.

1999-01-01

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

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

DEFF Research Database (Denmark)

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

2005-01-01

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

Evaluation Research as a Mechanism for Critical Inquiry and Knowledge Construction in Architectural and Urban Education

Directory of Open Access Journals (Sweden)

Ashraf M. Salama

2012-12-01

Full Text Available This article responds to the misconceptions that continue to characterize the delivery of knowledge content in architectural courses. Based on reviewing the literature on pedagogy the paper explores the value and benefits of introducing evaluation research as a mechanism for critical inquiry and knowledge construction in theory courses in architecture and urbanism. A framework is developed and employed to demonstrate the way in which this type of learning can be incorporated.   The development and implementation of a series of in-class and off campus exercises in two different contexts reveal that structured actions and experiences help students to be in control over their learning while invigorating their understanding of the body of knowledge delivered in a typical lecture format. It firmly believed that this would offer students multiple learning opportunities while fostering their capabilities to shift from passive listeners to active learners and from knowledge consumers to knowledge producers.

Magnetic structure of two- and three-dimensional supramolecular compounds

Energy Technology Data Exchange (ETDEWEB)

Decurtins, S.; Schmalle, H.W.; Pellaux, R. [Zurich Univ. (Switzerland); Fischer, P.; Fauth, F. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Ouladdiaf, B. [Institut Max von Laue - Paul Langevin, 75 - Paris (France)

1997-09-01

Supramolecular chiral networks of oxalato-bridged transition metals show either two- or three-dimensional structural features. The magnetic structures of such compounds have been investigated by means of elastic neutron powder diffraction. (author) 2 figs., 2 refs.

Enumeration of virtual libraries of combinatorial modular macrocyclic (bracelet, necklace) architectures and their linear counterparts.

Science.gov (United States)

Taniguchi, Masahiko; Du, Hai; Lindsey, Jonathan S

2013-09-23

A wide variety of cyclic molecular architectures are built of modular subunits and can be formed combinatorially. The mathematics for enumeration of such objects is well-developed yet lacks key features of importance in chemistry, such as specifying (i) the structures of individual members among a set of isomers, (ii) the distribution (i.e., relative amounts) of products, and (iii) the effect of nonequal ratios of reacting monomers on the product distribution. Here, a software program (Cyclaplex) has been developed to determine the number, identity (including isomers), and relative amounts of linear and cyclic architectures from a given number and ratio of reacting monomers. The program includes both mathematical formulas and generative algorithms for enumeration; the latter go beyond the former to provide desired molecular-relevant information and data-mining features. The program is equipped to enumerate four types of architectures: (i) linear architectures with directionality (macroscopic equivalent = electrical extension cords), (ii) linear architectures without directionality (batons), (iii) cyclic architectures with directionality (necklaces), and (iv) cyclic architectures without directionality (bracelets). The program can be applied to cyclic peptides, cycloveratrylenes, cyclens, calixarenes, cyclodextrins, crown ethers, cucurbiturils, annulenes, expanded meso-substituted porphyrin(ogen)s, and diverse supramolecular (e.g., protein) assemblies. The size of accessible architectures encompasses up to 12 modular subunits derived from 12 reacting monomers or larger architectures (e.g. 13-17 subunits) from fewer types of monomers (e.g. 2-4). A particular application concerns understanding the possible heterogeneity of (natural or biohybrid) photosynthetic light-harvesting oligomers (cyclic, linear) formed from distinct peptide subunits.

Supramolecular polymeric materials via cyclodextrin-guest interactions.

Science.gov (United States)

Harada, Akira; Takashima, Yoshinori; Nakahata, Masaki

2014-07-15

CONSPECTUS: Cyclodextrins (CDs) have many attractive functions, including molecular recognition, hydrolysis, catalysis, and polymerization. One of the most important uses of CDs is for the molecular recognition of hydrophobic organic guest molecules in aqueous solutions. CDs are desirable host molecules because they are environmentally benign and offer diverse functions. This Account demonstrates some of the great advances in the development of supramolecular materials through host-guest interactions within the last 10 years. In 1990, we developed topological supramolecular complexes with CDs, polyrotaxane, and CD tubes, and these preparation methods take advantage of self-organization between the CDs and the polymers. The combination of polyrotaxane with αCD forms a hydrogel through the interaction of αCDs with the OH groups on poly(ethylene glycol). We categorized these polyrotaxane chemistries within main chain type complexes. At the same time, we studied the interactions of side chain type supramolecular complexes with CDs. In these systems the guest molecules modified the polymers and selectively formed inclusion complexes with CDs. The systems that used low molecular weight compounds did not show such selectivity with CDs. The multivalency available within the complex cooperatively enhances the selective binding of CD with guest molecules via the polymer side chains, a phenomenon that is analogous to binding patterns observed in antigen-antibody complexes. To incorporate the molecular recognition properties of CDs within the polymer side chains, we first prepared stimuli-responsive sol-gel switching materials through host-guest interactions. We chose azobenzene derivatives for their response to light and ferrocene derivatives for their response to redox conditions. The supramolecular materials were both redox-responsive and self-healing, and these properties resulted from host-guest interactions. These sol-gels with built in switches gave us insight for

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

International Nuclear Information System (INIS)

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

2014-01-01

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

[Study on meridian tropism of medicinal property theory for Chines medicines by supramolecular chemistry (I)].

Science.gov (United States)

He, Fu-yuan; Deng, Kai-wen; Yang, Yan-tao; Zhou, Yi-qun; Shi, Ji-lian; Liu, Wen-long; Tang, Yu

2015-04-01

In this paper, based on the special influence of supramolecular chemistry on the basic theory of Chinese medicines ( CM) , the authors further analyzed the history of meridian tropism and natural origins of CM organisms and explained CM ingredients and the universal regularity of the automatic action of the supramolecular "imprinting templates" hole channel structure. After entering human bodies, CMs, as the aggregation of supramolecular "imprinting templates" , automatically seek supramolecular subjects that are matched with their "imprinting templates" in human meridians and organs for the purpose of self-recognition, self-organization, self-assembly and self-replication, so as to generate specific efficacy in meridians and organs, which is reflected as the meridian tropism phenomena at macro level. This regularity can be studied by in vitro and in vivo experimental studies. In vitro methods are mostly supra molecular structure analysis and kinetic and thermodynamic parameter calculation; Whereas in vivo methods are dominated by the analysis on object component distribution, chromatopharmacodynamic parameters and network chromatopharmacodynamic parameters; Particularly, the acupoint-medicine method can simplify to study the supramolecular subject-object relations. Consequently, CM's'meridian tropism reveals the universal regularity for interactions of macromolecular and micromolecular "imprinting templates" of subjects and objects in natural organisms. As the first barrier for the material base of the CM theory and breakthrough in the modernization of the basic CM theory, meridian tropism plays an important role in studies on basic theories of the basic CM theory.

The use of supramolecular chemistry in dye delivery systems

International Nuclear Information System (INIS)

Merckel, Daniel Andrew Sturton

2002-01-01

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

The architectural design of networks of protein domain architectures.

Science.gov (United States)

Hsu, Chia-Hsin; Chen, Chien-Kuo; Hwang, Ming-Jing

2013-08-23

Protein domain architectures (PDAs), in which single domains are linked to form multiple-domain proteins, are a major molecular form used by evolution for the diversification of protein functions. However, the design principles of PDAs remain largely uninvestigated. In this study, we constructed networks to connect domain architectures that had grown out from the same single domain for every single domain in the Pfam-A database and found that there are three main distinctive types of these networks, which suggests that evolution can exploit PDAs in three different ways. Further analysis showed that these three different types of PDA networks are each adopted by different types of protein domains, although many networks exhibit the characteristics of more than one of the three types. Our results shed light on nature's blueprint for protein architecture and provide a framework for understanding architectural design from a network perspective.

Supramolecular nanofibers of triamcinolone acetonide for uveitis therapy

Science.gov (United States)

Li, Xingyi; Wang, Yuqin; Yang, Chengbiao; Shi, Shuai; Jin, Ling; Luo, Zichao; Yu, Jing; Zhang, Zhaoliang; Yang, Zhimou; Chen, Hao

2014-11-01

Supramolecular nanofibers of prodrugs hold advantages for drug release due to their high drug payload, sustained and constant drug release behavior, and stimuli responsiveness. In this study, we report on a supramolecular hydrogel mainly formed by a clinically used drug triamcinolone acetonide (TA). Such a hydrogel could only be prepared via an ester bond hydrolysis process from its prodrug of succinated triamcinolone acetonide (STA). The resulting hydrogel could constantly release TA in the in vitro release experiment. The TA hydrogel possessed an excellent transscleral penetration ability, as evaluated by the in vitro transscleral transport study. The developed TA hydrogel also exhibited a great ocular compatibility in rats, as indicated by the optical coherence tomography (OCT) images, HE observation, and glial fibrillary acidic protein (GFAP) and vimentin immuno-staining assays of the retinas. Our TA hydrogel showed a decreased efficacy to inhibit ocular inflammation in the rat's experiment autoimmune uveitis (EAU) model compared to the commercial TA suspension (Transton®), but without causing complications such as high intraocular pressure and cataracts. These promising properties of the hydrogel indicated its great potential for the treatment of eye diseases.Supramolecular nanofibers of prodrugs hold advantages for drug release due to their high drug payload, sustained and constant drug release behavior, and stimuli responsiveness. In this study, we report on a supramolecular hydrogel mainly formed by a clinically used drug triamcinolone acetonide (TA). Such a hydrogel could only be prepared via an ester bond hydrolysis process from its prodrug of succinated triamcinolone acetonide (STA). The resulting hydrogel could constantly release TA in the in vitro release experiment. The TA hydrogel possessed an excellent transscleral penetration ability, as evaluated by the in vitro transscleral transport study. The developed TA hydrogel also exhibited a great ocular

Radiology Architecture Project Primer.

Science.gov (United States)

Sze, Raymond W; Hogan, Laurie; Teshima, Satoshi; Davidson, Scott

2017-12-19

The rapid pace of technologic advancement and increasing expectations for patient- and family-friendly environments make it common for radiology leaders to be involved in imaging remodel and construction projects. Most radiologists and business directors lack formal training in architectural and construction processes but are expected to play significant and often leading roles in all phases of an imaging construction project. Avoidable mistakes can result in significant increased costs and scheduling delays; knowledgeable participation and communication can result in a final product that enhances staff workflow and morale and improves patient care and experience. This article presents practical guidelines for preparing for and leading a new imaging architectural and construction project. We share principles derived from the radiology and nonradiology literature and our own experience over the past decade completely remodeling a large pediatric radiology department and building a full-service outpatient imaging center. Copyright © 2017 American College of Radiology. Published by Elsevier Inc. All rights reserved.

Reversible optical transcription of supramolecular chirality into molecular chirality

NARCIS (Netherlands)

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

2004-01-01

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

Switchable charge injection barrier in an organic supramolecular semiconductor

NARCIS (Netherlands)

Gorbunov, A.V.; Haedler, A.T.; Putzeys, T.; Zha, R.H.; Schmidt, H.W.; Kivala, M.; Urbanavičiutec, I.; Wübbenhorst, M.; Meijer, E.W.; Kemerink, M.

2016-01-01

We disclose a supramolecular material that combines semiconducting and dipolar functionalities. The material consists of a discotic semiconducting carbonyl-bridged triarylamine core, which is surrounded by three dipolar amide groups. In thin films, the material self-organizes in a hexagonal columnar

Rotation of a single molecule within a supramolecular bearing

DEFF Research Database (Denmark)

Gimzewski, J.K.; Joachim, C.; Schlittler, R.R.

1998-01-01

Experimental visualization and verification of a single-molecule rotor operating within a supramolecular bearing is reported. Using a scanning tunneling microscope, single molecules were observed to exist in one of two spatially defined states Laterally separated by 0.26 nanometers. One...

A redox responsive, fluorescent supramolecular metallohydrogel consists of nanofibers with single-molecule width

KAUST Repository

Zhang, Ye

2013-04-03

The integration of a tripeptide derivative, which is a versatile self-assembly motif, with a ruthenium(II)tris(bipyridine) complex affords the first supramolecular metallo-hydrogelator that not only self assembles in water to form a hydrogel but also exhibits gel-sol transition upon oxidation of the metal center. Surprisingly, the incorporation of the metal complex in the hydrogelator results in the nanofibers, formed by the self-assembly of the hydrogelator in water, to have the width of a single molecule of the hydrogelator. These results illustrate that metal complexes, besides being able to impart rich optical, electronic, redox, or magnetic properties to supramolecular hydrogels, also offer a unique geometrical control to prearrange the self-assembly motif prior to self-assembling. The use of metal complexes to modulate the dimensionality of intermolecular interactions may also help elucidate the interactions of the molecular nanofibers with other molecules, thus facilitating the development of supramolecular hydrogel materials for a wide range of applications. © 2013 American Chemical Society.

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

Science.gov (United States)

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

2010-05-17

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

Thermo-reversible supramolecular hydrogels of trehalose-type diblock methylcellulose analogues.

Science.gov (United States)

Yamagami, Mao; Kamitakahara, Hiroshi; Yoshinaga, Arata; Takano, Toshiyuki

2018-03-01

This paper describes the design and synthesis of new trehalose-type diblock methylcellulose analogues with nonionic, cationic, and anionic cellobiosyl segments, namely 1-(tri-O-methyl-cellulosyl)-4-[β-d-glucopyranosyl-(1→4)-β-d-glucopyranosyloxymethyl]-1H-1,2,3-triazole (1), 1-(tri-O-methyl-cellulosyl)-4-[(6-amino-6-deoxy-β-d-glucopyranosyl)-(1→4)- 6-amino-6-deoxy-β-d-glucopyranosyloxymethyl]-1H-1,2,3-triazole (2), and 4-(tri-O-methyl-cellulosyloxymethyl)-1-[β-d-glucopyranuronosyl-(1→4)-β-d-glucopyranuronosyl]-1H-1,2,3-triazole (3), respectively. Aqueous solutions of all of the 1,2,3-triazole-linked diblock methylcellulose analogues possessed higher surface activities than that of industrially produced methylcellulose and exhibited lower critical solution temperatures, that allowed the formation of thermoresponsive supramolecular hydrogels at close to human body temperature. Supramolecular structures of thermo-reversible hydrogels based on compounds 1, 2, and 3 were investigated by means of scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Detailed structure-property-function relationships of compounds 1, 2, and 3 were discussed. Not only nonionic hydrophilic segment but also ionic hydrophilic segments of diblock methylcellulose analogues were valid for the formation of thermo-reversible supramolecular hydrogels based on end-functionalized methylcellulose. Copyright © 2017 Elsevier Ltd. All rights reserved.

3D-models in landscape architecture

NARCIS (Netherlands)

Nijhuis, S.; Stellingwerff, M.C.

2011-01-01

Landscape architecture consists of a basic attitude that involves four principles of study and practice. These are: anamnesis (palimpsest), process, three-dimensional space and scale-continuum (relational context). The core of landscape architecture as a design discipline is the construction and

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

Science.gov (United States)

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

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

Directory of Open Access Journals (Sweden)

Victor R. de la Rosa

2015-04-01

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

CONTEMPORARY SLOVENIAN TIMBER ARCHITECTURE INTERNATIONAL RECOGNIZED

Directory of Open Access Journals (Sweden)

Manja Kitek Kuzman

2014-12-01

Full Text Available The book presents Slovenia' s contemporary timber architecture. Thanks to its abundant forests, Slovenia has preserved the tradition of wood construction. As much as 60% of its surface is covered by forests. Slovenia is also the third most forested country in Europe. The high share of forest-covered surface allows for a sustainable production of high-quality wood. In the past, wood was used primarily in the construction of farm buildings, but now timber architecture is used for everything from residences and office buildings to public buildings such as community centres and schools. Timber construction is becoming increasingly popular. Apart from larger companies taking this approach, a great number of wooden houses have sprung up, built either on personal initiative or with the support of carpenter workshops. Slovenian timber architecture has taken a new approach to environmental and energy-efficiency problems and received great international recognition. The book discusses over fifty projects built over a ten-year period, and includes descriptions, photographs, and plans. The projects include residential areas, administration, and office, as well as tourist, educational, and industrial buildings. Timber architecture is presented as an integral part of the Slovenian landscape. The monograph will be useful to designers and future experts in their planning of optimal timber buildings and will highlight the main benefits of using timber construction.

Report to the Board of Regents State University System of Florida. Review of Programs: Architecture, Architectural Technology, Landscape Architecture, Interior Design, Construction and Construction Technology, Building Construction, Urban and Regional Planning.

Science.gov (United States)

McMinn, William G.

An evaluation and report was done on the status of programs in architecture and related fields in the Florida State University System as a follow-up to a 1983 evaluation. The evaluation involved self-studies prepared by each program and a series of site visits to each of seven campuses and two centers with programs under review. These institutions…

Artificial cognition architectures

CERN Document Server

Crowder, James A; Friess, Shelli A

2013-01-01

The goal of this book is to establish the foundation, principles, theory, and concepts that are the backbone of real, autonomous Artificial Intelligence. Presented here are some basic human intelligence concepts framed for Artificial Intelligence systems. These include concepts like Metacognition and Metamemory, along with architectural constructs for Artificial Intelligence versions of human brain functions like the prefrontal cortex. Also presented are possible hardware and software architectures that lend themselves to learning, reasoning, and self-evolution

3D Printing of Biocompatible Supramolecular Polymers and their Composites.

Science.gov (United States)

Hart, Lewis R; Li, Siwei; Sturgess, Craig; Wildman, Ricky; Jones, Julian R; Hayes, Wayne

2016-02-10

A series of polymers capable of self-assembling into infinite networks via supramolecular interactions have been designed, synthesized, and characterized for use in 3D printing applications. The biocompatible polymers and their composites with silica nanoparticles were successfully utilized to deposit both simple cubic structures, as well as a more complex twisted pyramidal feature. The polymers were found to be not toxic to a chondrogenic cell line, according to ISO 10993-5 and 10993-12 standard tests and the cells attached to the supramolecular polymers as demonstrated by confocal microscopy. Silica nanoparticles were then dispersed within the polymer matrix, yielding a composite material which was optimized for inkjet printing. The hybrid material showed promise in preliminary tests to facilitate the 3D deposition of a more complex structure.

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

Directory of Open Access Journals (Sweden)

Delphine Paolantoni

2015-02-01

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

Self-assembly of cationic multidomain peptide hydrogels: supramolecular nanostructure and rheological properties dictate antimicrobial activity

Science.gov (United States)

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

From metal-organic squares to porous zeolite-like supramolecular assemblies

KAUST Repository

Wang, Shuang; Zhao, Tingting; Li, Guanghua; Wojtas, Łukasz; Huo, Qisheng; Eddaoudi, Mohamed; Liu, Yunling

2010-01-01

We report the synthesis, structure, and characterization of two novel porous zeolite-like supramolecular assemblies, ZSA-1 and ZSA-2, having zeolite gis and rho topologies, respectively. The two compounds were assembled from functional metal

Supramolecular Cocrystals of Gliclazide: Synthesis, Characterization and Evaluation.

Science.gov (United States)

Chadha, Renu; Rani, Dimpy; Goyal, Parnika

2017-03-01

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

Phthalocyanine-nanocarbon ensembles: from discrete molecular and supramolecular systems to hybrid nanomaterials.

Science.gov (United States)

Bottari, Giovanni; de la Torre, Gema; Torres, Tomas

2015-04-21

Phthalocyanines (Pcs) are macrocyclic and aromatic compounds that present unique electronic features such as high molar absorption coefficients, rich redox chemistry, and photoinduced energy/electron transfer abilities that can be modulated as a function of the electronic character of their counterparts in donor-acceptor (D-A) ensembles. In this context, carbon nanostructures such as fullerenes, carbon nanotubes (CNTs), and, more recently, graphene are among the most suitable Pc "companions". Pc-C60 ensembles have been for a long time the main actors in this field, due to the commercial availability of C60 and the well-established synthetic methods for its functionalization. As a result, many Pc-C60 architectures have been prepared, featuring different connectivities (covalent or supramolecular), intermolecular interactions (self-organized or molecularly dispersed species), and Pc HOMO/LUMO levels. All these elements provide a versatile toolbox for tuning the photophysical properties in terms of the type of process (photoinduced energy/electron transfer), the nature of the interactions between the electroactive units (through bond or space), and the kinetics of the formation/decay of the photogenerated species. Some recent trends in this field include the preparation of stimuli-responsive multicomponent systems with tunable photophysical properties and highly ordered nanoarchitectures and surface-supported systems showing high charge mobilities. A breakthrough in the Pc-nanocarbon field was the appearance of CNTs and graphene, which opened a new avenue for the preparation of intriguing photoresponsive hybrid ensembles showing light-stimulated charge separation. The scarce solubility of these 1-D and 2-D nanocarbons, together with their lower reactivity with respect to C60 stemming from their less strained sp(2) carbon networks, has not meant an unsurmountable limitation for the preparation of variety of Pc-based hybrids. These systems, which show improved

Epoxy resin-inspired reconfigurable supramolecular networks

OpenAIRE

Balkenende Diederik; Olson Rebecca; Balog Sandor; Weder Christoph; Montero de Espinosa Lucas

2016-01-01

With the goal to push the mechanical properties of reconfigurable supramolecular polymers toward those of thermoset resins we prepared and investigated a new family of hydrogen bonded polymer networks that are assembled from isophthalic acid terminated oligo(bisphenol A co epichlorohydrin) and different bipyridines. These materials display high storage moduli of up to 3.9 GPa can be disassembled upon heating to form melts with a viscosity of as low as 2.1 Pa·s and fully reassemble upon coolin...

Supramolecular Structure and Function 9

CERN Document Server

Pifat-Mrzljak, Greta

2007-01-01

The book is based on International Summer Schools on Biophysics held in Croatia which, contrary to other workshops centered mainly on one topic or technique, has very broad scope providing advanced training in areas related to biophysics. This volume is presenting papers in the field of biophysics for studying biological phenomena by using physical methods (NMR, EPR, FTIR, Mass Spectrometry, etc.) and/or concepts (predictions of protein-protein interactions, virtual ligand screening etc.). The interrelationship of supramolecular structures and there functions is enlightened by applications of principals of these physical methods in the biophysical and molecular biology context.

Irreversible Conversion of a Water-Ethanol Solution into an Organized Two-Dimensional Network of Alternating Supramolecular Units in a Hydrophobic Zeolite under Pressure.

Science.gov (United States)

Arletti, Rossella; Fois, Ettore; Gigli, Lara; Vezzalini, Giovanna; Quartieri, Simona; Tabacchi, Gloria

2017-02-13

Turning disorder into organization is a key issue in science. By making use of X-ray powder diffraction and modeling studies, we show herein that high pressures in combination with the shape and space constraints of the hydrophobic all-silica zeolite ferrierite separate an ethanol-water liquid mixture into ethanol dimer wires and water tetramer squares. The confined supramolecular blocks alternate in a binary two-dimensional (2D) architecture that remains stable upon complete pressure release. These results support the combined use of high pressures and porous networks as a viable strategy for driving the organization of molecules or nano-objects towards complex, pre-defined patterns relevant for the realization of novel functional nanocomposites. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supra-molecular hydrogen-bonding patterns in the N(9)-H protonated and N(7)-H tautomeric form of an N(6) -benzoyl-adenine salt: N (6)-benzoyl-adeninium nitrate.

Science.gov (United States)

Karthikeyan, Ammasai; Jeeva Jasmine, Nithianantham; Thomas Muthiah, Packianathan; Perdih, Franc

2016-02-01

In the title molecular salt, C12H10N5O(+)·NO3 (-), the adenine unit has an N (9)-protonated N(7)-H tautomeric form with non-protonated N(1) and N(3) atoms. The dihedral angle between the adenine ring system and the phenyl ring is 51.10 (10)°. The typical intra-molecular N(7)-H⋯O hydrogen bond with an S(7) graph-set motif is also present. The benzoyl-adeninium cations also form base pairs through N-H⋯O and C-H⋯N hydrogen bonds involving the Watson-Crick face of the adenine ring and the C and O atoms of the benzoyl ring of an adjacent cation, forming a supra-molecular ribbon with R 2 (2)(9) rings. Benzoyl-adeninum cations are also bridged by one of the oxygen atoms of the nitrate anion, which acts as a double acceptor, forming a pair of N-H⋯O hydrogen bonds to generate a second ribbon motif. These ribbons together with π-π stacking inter-actions between the phenyl ring and the five- and six-membered adenine rings of adjacent mol-ecules generate a three-dimensional supra-molecular architecture.

Autodesk Revit Architecture 2014 fundamentals metric

CERN Document Server

ASCENT center for technical knowledge

2014-01-01

The Autodesk® Revit® Architecture software is a powerful Building Information Modeling (BIM) program that works the way Architects think. From Preliminary Design through Design Development, and into Construction Documents, the program streamlines the design process with a central 3D model. Changes made in one view update across all views and on the printable sheets. This training guide is designed to teach you the Autodesk Revit functionality as you would work with it in the design process. You begin by learning about the user interface and the Autodesk Revit commands for design development followed by those available for construction documentation. Since building projects themselves tend to be extremely complex, the Autodesk Revit Architecture software is also complex. The objective of the Autodesk Revit Architecture 2014 Fundamentals training guide is to enable students to create full 3D architectural project models and set them up in working drawings. This training guide focuses on basic tools that the ...

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

Science.gov (United States)

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

2018-06-01

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

Synthesis and characterization of maltose-based amphiphiles as supramolecular hydrogelators.

Science.gov (United States)

Clemente, María J; Fitremann, Juliette; Mauzac, Monique; Serrano, José L; Oriol, Luis

2011-12-20

Low molecular mass amphiphilic glycolipids have been prepared by linking a maltose polar head and a hydrophobic linear chain either by amidation or copper(I)-catalyzed azide-alkyne [3 + 2] cycloaddition. The liquid crystalline properties of these amphiphilic materials have been characterized. The influence of the chemical structure of these glycolipids on the gelation properties in water has also been studied. Glycolipids obtained by the click coupling of the two components give rise to stable hydrogels at room temperature. The fibrillar structure of supramolecular hydrogels obtained by the self-assembly of these gelators have been characterized by electron microscopy. Fibers showed some torsion, which could be related with a chiral supramolecular arrangement of amphiphiles, as confirmed by circular dichroism (CD). The sol-gel transition temperature was also determined by differential scanning calorimetry (DSC) and NMR. © 2011 American Chemical Society

Predicting supramolecular self-assembly on reconstructed metal surfaces

Science.gov (United States)

Roussel, Thomas J.; Barrena, Esther; Ocal, Carmen; Faraudo, Jordi

2014-06-01

The prediction of supramolecular self-assembly onto solid surfaces is still challenging in many situations of interest for nanoscience. In particular, no previous simulation approach has been capable to simulate large self-assembly patterns of organic molecules over reconstructed surfaces (which have periodicities over large distances) due to the large number of surface atoms and adsorbing molecules involved. Using a novel simulation technique, we report here large scale simulations of the self-assembly patterns of an organic molecule (DIP) over different reconstructions of the Au(111) surface. We show that on particular reconstructions, the molecule-molecule interactions are enhanced in a way that long-range order is promoted. Also, the presence of a distortion in a reconstructed surface pattern not only induces the presence of long-range order but also is able to drive the organization of DIP into two coexisting homochiral domains, in quantitative agreement with STM experiments. On the other hand, only short range order is obtained in other reconstructions of the Au(111) surface. The simulation strategy opens interesting perspectives to tune the supramolecular structure by simulation design and surface engineering if choosing the right molecular building blocks and stabilising the chosen reconstruction pattern.The prediction of supramolecular self-assembly onto solid surfaces is still challenging in many situations of interest for nanoscience. In particular, no previous simulation approach has been capable to simulate large self-assembly patterns of organic molecules over reconstructed surfaces (which have periodicities over large distances) due to the large number of surface atoms and adsorbing molecules involved. Using a novel simulation technique, we report here large scale simulations of the self-assembly patterns of an organic molecule (DIP) over different reconstructions of the Au(111) surface. We show that on particular reconstructions, the molecule

Space and Architecture's Current Line of Research? A Lunar Architecture Workshop With An Architectural Agenda.

Science.gov (United States)

Solomon, D.; van Dijk, A.

space context that will be useful on Earth on a conceptual and practical level? * In what ways could architecture's field of reference offer building on the Moon (and other celestial bodies) a paradigm shift? 1 In addition to their models and designs, workshop participants will begin authoring a design recommendation for the building of (infra-) structures and habitats on celestial bodies in particular the Moon and Mars. The design recommendation, a substantiated aesthetic code of conduct (not legally binding) will address long term planning and incorporate issues of sustainability, durability, bio-diversity, infrastructure, CHANGE, and techniques that lend themselves to Earth-bound applications. It will also address the cultural implications of architectural design might have within the context of space exploration. The design recommendation will ultimately be presented for peer review to both the space and architecture communities. What would the endorsement from the architectural community of such a document mean to the space community? The Lunar Architecture Workshop is conceptualised, produced and organised by(in alphabetical order): Alexander van Dijk, Art Race in Space, Barbara Imhof; ES- CAPE*spHERE, Vienna, University of Technology, Institute for Design and Building Construction, Vienna, Bernard Foing; ESA SMART1 Project Scientist, Susmita Mo- hanty; MoonFront, LLC, Hans Schartner' Vienna University of Technology, Institute for Design and Building Construction, Debra Solomon; Art Race in Space, Dutch Art Institute, Paul van Susante; Lunar Explorers Society. Workshop locations: ESTEC, Noordwijk, NL and V2_Lab, Rotterdam, NL Workshop dates: June 3-16, 2002 (a Call for Participation will be made in March -April 2002.) 2

Hierarchical self-assembly of a bow-shaped molecule bearing self-complementary hydrogen bonding sites into extended supramolecular assemblies.

Science.gov (United States)

Ikeda, Masato; Nobori, Tadahito; Schmutz, Marc; Lehn, Jean-Marie

2005-01-07

The bow-shaped molecule 1 bearing a self-complementary DAAD-ADDA (D=donor A=acceptor) hydrogen-bonding array generates, in hydrocarbon solvents, highly ordered supramolecular sheet aggregates that subsequently give rise to gels by formation of an entangled network. The process of hierarchical self-assembly of compound 1 was investigated by the concentration and temperature dependence of UV-visible and (1)H NMR spectra, fluorescence spectra, and electron microscopy data. The temperature dependence of the UV-visible spectra indicates a highly cooperative process for the self-assembly of compound 1 in decaline. The electron micrograph of the decaline solution of compound 1 (1.0 mM) revealed supramolecular sheet aggregates forming an entangled network. The selected area electronic diffraction patterns of the supramolecular sheet aggregates were typical for single crystals, indicative of a highly ordered assembly. The results exemplify the generation, by hierarchical self-assembly, of highly organized supramolecular materials presenting novel collective properties at each level of organization.

Neural Architectures for Control

Science.gov (United States)

Peterson, James K.

1991-01-01

The cerebellar model articulated controller (CMAC) neural architectures are shown to be viable for the purposes of real-time learning and control. Software tools for the exploration of CMAC performance are developed for three hardware platforms, the MacIntosh, the IBM PC, and the SUN workstation. All algorithm development was done using the C programming language. These software tools were then used to implement an adaptive critic neuro-control design that learns in real-time how to back up a trailer truck. The truck backer-upper experiment is a standard performance measure in the neural network literature, but previously the training of the controllers was done off-line. With the CMAC neural architectures, it was possible to train the neuro-controllers on-line in real-time on a MS-DOS PC 386. CMAC neural architectures are also used in conjunction with a hierarchical planning approach to find collision-free paths over 2-D analog valued obstacle fields. The method constructs a coarse resolution version of the original problem and then finds the corresponding coarse optimal path using multipass dynamic programming. CMAC artificial neural architectures are used to estimate the analog transition costs that dynamic programming requires. The CMAC architectures are trained in real-time for each obstacle field presented. The coarse optimal path is then used as a baseline for the construction of a fine scale optimal path through the original obstacle array. These results are a very good indication of the potential power of the neural architectures in control design. In order to reach as wide an audience as possible, we have run a seminar on neuro-control that has met once per week since 20 May 1991. This seminar has thoroughly discussed the CMAC architecture, relevant portions of classical control, back propagation through time, and adaptive critic designs.

Relational Architecture

DEFF Research Database (Denmark)

Reeh, Henrik

2018-01-01

in a scholarly institution (element #3), as well as the certified PhD scholar (element #4) and the architectural profession, notably its labour market (element #5). This first layer outlines the contemporary context which allows architectural research to take place in a dynamic relationship to doctoral education...... a human and institutional development going on since around 1990 when the present PhD institution was first implemented in Denmark. To be sure, the model is centred around the PhD dissertation (element #1). But it involves four more components: the PhD candidate (element #2), his or her supervisor...... and interrelated fields in which history, place, and sound come to emphasize architecture’s relational qualities rather than the apparent three-dimensional solidity of constructed space. A third layer of relational architecture is at stake in the professional experiences after the defence of the authors...

Supramolecular assembly of organic bicapped Keggin polyoxometalate

International Nuclear Information System (INIS)

Han Zhangang; Zhao Yulong; Peng Jun; Ma Huiyuan; Liu Qun; Wang Enbo; Hu Ninghai

2004-01-01

Two novel supramolecular assemblies of organic bicapped Keggin polyoxometalates (pbpy) 8 H 3 [PW 12 O 40 ]·2H 2 O (1) and (pbpy) 4 H[PMo 12 O 40 (VO)] (2) (pbpy=5-phenyl-2-(4-pyridinyl)pyridine) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Crystallographic data for compound (1), C 128 H 103 N 16 O 42 PW 12 , triclinic, space group P1-bar: a=13.4759(8) A, b=14.6395(11) A, c=16.5743(10) A, α=95.764(2) deg., β=102.166(2) deg., γ=92.9870(10) deg., Z=1, V=3171.1(4) A 3 ; for compound (2), C 64 H 49 N 8 O 41 PMo 12 V, triclinic, space group P1-bar: a=11.5377(11) A, b=12.7552(8) A, c=14.9599(10) A, α=72.270(4) deg., β=88.916(2) deg., γ=67.865(4) deg., Z=1, V=1931.0(3) A 3 . X-ray analyses show that both 1 and 2 represent rare organic bicapped Keggin structures and are supported by supramolecular interactions to extend into a 3D framework. In particular, the unusual structure feature of compound 2 contains a simultaneously organic and inorganic capped structure

Autoamplification of molecular chirality through the induction of supramolecular chirality

NARCIS (Netherlands)

van Dijken, Derk Jan; Beierle, John M.; Stuart, Marc C. A.; Szymanski, Wiktor; Browne, Wesley R.; Feringa, Ben L.

2014-01-01

The novel concept for the autoamplification of molecular chirality, wherein the amplification proceeds through the induction of supramolecular chirality, is presented. A solution of prochiral, ring-open diarylethenes is doped with a small amount of their chiral, ring-closed counterpart. The

Move-tecture: A Conceptual Framework for Designing Movement in Architecture

Science.gov (United States)

Yilmaz, Irem

2017-10-01

Along with the technological improvements in our age, it is now possible for the movement to become one of the basic components of the architectural space. Accordingly, architectural construction of movement changes both our architectural production practices and our understanding of architectural space. However, existing design concepts and approaches are insufficient to discuss and understand this change. In this respect, this study aims to form a conceptual framework on the relationship of architecture and movement. In this sense, the conceptualization of move-tecture is developed to research on the architectural construction of movement and the potentials of spatial creation through architecturally constructed movement. Move-tecture, is a conceptualization that treats movement as a basic component of spatial creation. It presents the framework of a qualitative categorization on the design of moving architectural structures. However, this categorization is a flexible one that can evolve in the direction of the expanding possibilities of the architectural design and the changing living conditions. With this understanding, six categories have been defined within the context of the article: Topological Organization, Choreographic Formation, Kinetic Structuring, Corporeal Constitution, Technological Configuration and Interactional Patterning. In line with these categories, a multifaceted perspective on the moving architectural structures is promoted. It is aimed that such an understanding constitutes a new initiative in the design practices carried out in this area and provides a conceptual basis for the discussions to be developed.

Supramolecular curcumin-barium prodrugs for formulating with ceramic particles.

Science.gov (United States)

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

Control over Structure and Function of Peptide Amphiphile Supramolecular Assemblies through Molecular Design and Energy Landscapes

Science.gov (United States)

Tantakitti, Faifan

a controlled local release of the soluble growth factor bone morphogenetic protein 4 (BMP-4) was realized from the particle's core composed of cross-linked alginate. The alginate-core and PA-shell microparticles were found to allow independent tuning of the bioactivity of a PA and a release of the growth factor for specific signaling to cells. Using microcarriers which encapsulated BMP-4 and coated with RGDS PA nanofibers, it was shown that a control over spatial distribution, proliferation, and osteogenic differentiation of premyoblastic cells on the surface of microcarriers can be effectively achieved. Finally, in drastic contrast to the traditional approach to material development based on altering molecular structure, chapter 4 presents the energy landscapes in which supramolecular assemblies of unique architecture exist in different thermodynamic wells. Experimental results and calculations revealed that the energy landscapes are rooted in competing interactions between PA monomers, namely beta-sheet hydrogen bonds and repulsion among charged groups. Switching off or on the repulsive electrostatic interactions by changing the ionic strength promoted or suppressed the dominant ?-sheet hydrogen bonding interactions respectively. However, the dominant forces can prevail if the assemblies are above a certain size and thereby can exist in a kinetically trapped state. Preparative pathways involving dilution, annealing, and addition of salt were investigated in which the structures belonging to different energy states could be accessed and demonstrated that these energy landscapes involving competitive interactions was applicable not only to PA systems but also to a non-peptide supramolecular system based on pi-orbital overlaps as the dominant attraction among molecules and electrostatic repulsion. In chapter 5, structure and biological function relationships of long or short PA nanofibers are reported, and such fibers were prepared from identical monomers based on

Differences in Cellulosic Supramolecular Structure of Compositionally Similar Rice Straw Affect Biomass Metabolism by Paddy Soil Microbiota.

Directory of Open Access Journals (Sweden)

Tatsuki Ogura

Full Text Available Because they are strong and stable, lignocellulosic supramolecular structures in plant cell walls are resistant to decomposition. However, they can be degraded and recycled by soil microbiota. Little is known about the biomass degradation profiles of complex microbiota based on differences in cellulosic supramolecular structures without compositional variations. Here, we characterized and evaluated the cellulosic supramolecular structures and composition of rice straw biomass processed under different milling conditions. We used a range of techniques including solid- and solution-state nuclear magnetic resonance (NMR and Fourier transform infrared spectroscopy followed by thermodynamic and microbial degradability characterization using thermogravimetric analysis, solution-state NMR, and denaturing gradient gel electrophoresis. These measured data were further analyzed using an "ECOMICS" web-based toolkit. From the results, we found that physical pretreatment of rice straw alters the lignocellulosic supramolecular structure by cleaving significant molecular lignocellulose bonds. The transformation from crystalline to amorphous cellulose shifted the thermal degradation profiles to lower temperatures. In addition, pretreated rice straw samples developed different microbiota profiles with different metabolic dynamics during the biomass degradation process. This is the first report to comprehensively characterize the structure, composition, and thermal degradation and microbiota profiles using the ECOMICS toolkit. By revealing differences between lignocellulosic supramolecular structures of biomass processed under different milling conditions, our analysis revealed how the characteristic compositions of microbiota profiles develop in addition to their metabolic profiles and dynamics during biomass degradation.

Synthesis and crystal structure of a wheel-shaped supramolecular ...

Indian Academy of Sciences (India)

41-218/2012 (SR)), India for financial support. DG and BS thank the Council of Scientific and Indus- trial Research (CSIR) for Senior Research Fellowship. We are grateful to Perkin-Elmer for ESI-Mass analysis. References. 1. (a) Lehn J M 1995 In Supramolecular Chem- istry, Concepts and Perspectives (Weinheim: VCH);.

Synthesis and strong photooxidation power of a supramolecular hybrid comprising a polyoxometalate and Ru(II) polypyridyl complex with zinc(II).

Science.gov (United States)

Ohashi, Kenji; Takeda, Hiroyuki; Koike, Kazuhide; Ishitani, Osamu

2015-01-01

A novel method for constructing supramolecular hybrids composed of polyoxometalates and photofunctional metal complexes was developed. A Ru(II) complex with phosphonate groups (RuP) strongly interacted with Zn(II) to afford a 2 : 1 trinuclear metal complex ([(RuP)2Zn](3+)). In dimethylsulfoxide, [(RuP)2Zn](3+) strongly interacted with a Keggin-type heteropolyoxometalate (Si-WPOM) to form a 1 : 1 hybrid ([(RuP)2Zn]-POM). Irradiation of [(RuP)2Zn]-POM in the presence of diethanolamine caused rapid accumulation of the one-electron reduced hybrid with a quantum yield of 0.99.

Synthesis, spectroscopy, thermal studies and supramolecular ...

Indian Academy of Sciences (India)

TECS

Synthesis, spectroscopy, thermal studies and supramolecular structures of two .... J = 9 Hz), 8∙13 (d, 2H, J = 9 Hz), 7∙69 (s, 1H), 7∙04. (s, 2H). ... 1H NMR (D2O): δ (in ppm); 8∙05 (d, 2H, ..... 86∙33 (2). 86∙92(1). 87∙08(2). V (Ε3). 553∙1(6). 573∙71(5). 561∙56(14). 557∙5(3) .... Mn, Co and Ni complexes.28–30 The observed inter-.

Structure-directing star-shaped block copolymers: supramolecular vesicles for the delivery of anticancer drugs.

Science.gov (United States)

Yang, Chuan; Liu, Shao Qiong; Venkataraman, Shrinivas; Gao, Shu Jun; Ke, Xiyu; Chia, Xin Tian; Hedrick, James L; Yang, Yi Yan

2015-06-28

Amphiphilic polycarbonate/PEG copolymer with a star-like architecture was designed to facilitate a unique supramolecular transformation of micelles to vesicles in aqueous solution for the efficient delivery of anticancer drugs. The star-shaped amphipilic block copolymer was synthesized by initiating the ring-opening polymerization of trimethylene carbonate (TMC) from methyl cholate through a combination of metal-free organo-catalytic living ring-opening polymerization and post-polymerization chain-end derivatization strategies. Subsequently, the self-assembly of the star-like polymer in aqueous solution into nanosized vesicles for anti-cancer drug delivery was studied. DOX was physically encapsulated into vesicles by dialysis and drug loading level was significant (22.5% in weight) for DOX. Importantly, DOX-loaded nanoparticles self-assembled from the star-like copolymer exhibited greater kinetic stability and higher DOX loading capacity than micelles prepared from cholesterol-initiated diblock analogue. The advantageous disparity is believed to be due to the transformation of micelles (diblock copolymer) to vesicles (star-like block copolymer) that possess greater core space for drug loading as well as the ability of such supramolecular structures to encapsulate DOX. DOX-loaded vesicles effectively inhibited the proliferation of 4T1, MDA-MB-231 and BT-474 cells, with IC50 values of 10, 1.5 and 1.0mg/L, respectively. DOX-loaded vesicles injected into 4T1 tumor-bearing mice exhibited enhanced accumulation in tumor tissue due to the enhanced permeation and retention (EPR) effect. Importantly, DOX-loaded vesicles demonstrated greater tumor growth inhibition than free DOX without causing significant body weight loss or cardiotoxicity. The unique ability of the star-like copolymer emanating from the methyl cholate core provided the requisite modification in the block copolymer interfacial curvature to generate vesicles of high loading capacity for DOX with significant

Flexible weapons architecture design

Science.gov (United States)

Pyant, William C., III

Present day air-delivered weapons are of a closed architecture, with little to no ability to tailor the weapon for the individual engagement. The closed architectures require weaponeers to make the target fit the weapon instead of fitting the individual weapons to a target. The concept of a flexible weapons aims to modularize weapons design using an open architecture shell into which different modules are inserted to achieve the desired target fractional damage while reducing cost and civilian casualties. This thesis shows that the architecture design factors of damage mechanism, fusing, weapons weight, guidance, and propulsion are significant in enhancing weapon performance objectives, and would benefit from modularization. Additionally, this thesis constructs an algorithm that can be used to design a weapon set for a particular target class based on these modular components.

Self-assembly of supramolecular triarylamine nanowires in mesoporous silica and biocompatible electrodes thereof

Science.gov (United States)

Licsandru, Erol-Dan; Schneider, Susanne; Tingry, Sophie; Ellis, Thomas; Moulin, Emilie; Maaloum, Mounir; Lehn, Jean-Marie; Barboiu, Mihail; Giuseppone, Nicolas

2016-03-01

Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting electronic pathways crossing the silica layer. They allow very efficient charge transfer from the redox species in solution to the gold surface. We demonstrate the potential of these hybrid constitutional materials by implementing them as biocathodes and by measuring laccase activity that reduces dioxygen to produce water.Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting

Supramolecular effects as driving force of dipyrrin based functional materials engineering

Science.gov (United States)

Banakova, E.; Bobrov, A.; Kazak, A.; Marfin, Yu; Merkushev, D.; Molchanov, E.; Rumyantsev, E.; Shipalova, M.; Usoltsev, S.; Vodyanova, O.

2018-01-01

Dipyrrin based luminophores are of major interest in different areas of chemistry, material science and molecular biology. Vast variety of the structures with dipyrrin motif were synthesized and investigated up to date. Modern trend in the dipyrrin chemistry is the aimed functionalization of the ligand or complex structure allowing to gain the mechanism based on supramolecular interactions for controlling spectral and photophysical characteristics of compounds for tuning practically valuable properties for specific tasks. Presented paper summarize the results of our research group, working in the field of dipyrrin complexes with p-elements: synthesis, spectral characteristics evaluation and possibilities of practical application investigation. Discussion is focused on the opportunities of molecules preorganization for achieving the supramolecular interactions causing the tuning of fluorescence of the compounds in solutions, polymeric matrices and thin films.

Solvent Clathrate Driven Dynamic Stereomutation of a Supramolecular Polymer with Molecular Pockets.

Science.gov (United States)

Kulkarni, Chidambar; Korevaar, Peter A; Bejagam, Karteek K; Palmans, Anja R A; Meijer, E W; George, Subi J

2017-10-04

Control over the helical organization of synthetic supramolecular systems is intensively pursued to manifest chirality in a wide range of applications ranging from electron spin filters to artificial enzymes. Typically, switching the helicity of supramolecular assemblies involves external stimuli or kinetic traps. However, efforts to achieve helix reversal under thermodynamic control and to understand the phenomena at a molecular level are scarce. Here we present a unique example of helix reversal (stereomutation) under thermodynamic control in the self-assembly of a coronene bisimide that has a 3,5-dialkoxy substitution on the imide phenyl groups (CBI-35CH), leading to "molecular pockets" in the assembly. The stereomutation was observed only if the CBI monomer possesses molecular pockets. Detailed chiroptical studies performed in alkane solvents with different molecular structures reveal that solvent molecules intercalate or form clathrates within the molecular pockets of CBI-35CH at low temperature (263 K), thereby triggering the stereomutation. The interplay among the helical assembly, molecular pockets, and solvent molecules is further unraveled by explicit solvent molecular dynamics simulations. Our results demonstrate how the molecular design of self-assembling building blocks can orchestrate the organization of surrounding solvent molecules, which in turn dictates the helical organization of the resulting supramolecular assembly.

Thermoresponsive Supramolecular Chemotherapy by "V"-Shaped Armed β-Cyclodextrin Star Polymer to Overcome Drug Resistance.

Science.gov (United States)

Fan, Xiaoshan; Cheng, Hongwei; Wang, Xiaoyuan; Ye, Enyi; Loh, Xian Jun; Wu, Yun-Long; Li, Zibiao

2018-04-01

Pump mediated drug efflux is the key reason to result in the failure of chemotherapy. Herein, a novel star polymer β-CD-v-(PEG-β-PNIPAAm) 7 consisting of a β-CD core, grafted with thermo-responsive poly(N-isopropylacrylamide) (PNIPAAm) and biocompatible poly(ethylene glycol) (PEG) in the multiple "V"-shaped arms is designed and further fabricated into supramolecular nanocarriers for drug resistant cancer therapy. The star polymer could encapsulate chemotherapeutics between β-cyclodextrin and anti-cancer drug via inclusion complex (IC). Furthermore, the temperature induced chain association of PNIPAAm segments facilitated the IC to form supramolecular nanoparticles at 37 °C, whereas the presence of PEG impart great stability to the self-assemblies. When incubated with MDR-1 membrane pump regulated drug resistant tumor cells, much higher and faster cellular uptake of the supramolecular nanoparticles were detected, and the enhanced intracellular retention of drugs could lead to significant inhibition of cell growth. Further in vivo evaluation showed high therapeutic efficacy in suppressing drug resistant tumor growth without a significant impact on the normal functions of main organs. This work signifies thermo-responsive supramolecular chemotherapy is promising in combating pump mediated drug resistance in both in vitro and in vivo models, which may be encouraging for the advanced drug delivery platform design to overcome drug resistant cancer. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Architectural and Environmental Refurbishment of Industrialised Residential Construction. The example of the Selva Cafaro Quarter in Naples

Directory of Open Access Journals (Sweden)

Massimo Perriccioli

2012-10-01

Full Text Available This essay presents the experimental research conducted over the past years by the CHED (Concept House and Environmental Design Research Unit at the “Eduardo Vittoria” School of Architecture and Design in Ascoli Piceno, focused on the theme of Social Housing. The CHED is a temporary research team that proposes a union between diverse know-how, cultures, skills and specialisations, working towards a method of theoretical and conceptual investigation and design and building experiments in the field of innovative construction for sustainable dwelling. In particular, the experience outlined in this text relates to a design experiment completed between 2010 and 2011 and outside the borders of the Marche region, in agreement with the City of Naples' Assessorato all’Edilizia e al Centro Storico (Department of Building and the Historical Centre and focused on the architectural and environmental refurbishment of the residential quarter of Selva Cafaro in San Pietro a Patierno (Naples.

Architecture - re-Construction - Geometry: a knowledge path applied to the study of Plantery's vaults in Turin

Directory of Open Access Journals (Sweden)

Roberta Spallone

2012-06-01

Full Text Available Plantery's vaults, by the name of the architect working in Turin since first years of '700, are composed by a main vault intersected by some axial and angular secondary vaults. Plantery's vaults allow to roof over unitary spaces obtaining effects of lightness also by small rises. Their diffusion, up to the '80s of the century, in boardrooms as palaces halls, and the richness of variations on the theme, justifies a research, that makes use of survey and digital modeling. This research is focused on the relationships between geometric models and built architecture, connected by use of materials, construction techniques and decorative styles.

Two novel alkaline earth coordination polymers constructed from cinnamic acid and 1,10-phenanthroline: synthesis and structural and thermal properties.

Science.gov (United States)

Bendjellal, Nassima; Trifa, Chahrazed; Bouacida, Sofiane; Boudaren, Chaouki; Boudraa, Mhamed; Merazig, Hocine

2018-02-01

In coordination chemistry and crystal engineering, many factors influence the construction of coordination polymers and the final frameworks depend greatly on the organic ligands used. The diverse coordination modes of N-donor ligands have been employed to assemble metal-organic frameworks. Carboxylic acid ligands can deprotonate completely or partially when bonding to metal ions and can also act as donors or acceptors of hydrogen bonds; they are thus good candidates for the construction of supramolecular architectures. We synthesized under reflux or hydrothermal conditions two new alkaline earth(II) complexes, namely poly[(1,10-phenanthroline-κ 2 N,N')bis(μ-3-phenylprop-2-enoato-κ 3 O,O':O)calcium(II)], [Ca(C 10 H 7 O 2 ) 2 (C 10 H 8 N 2 )] n , (1), and poly[(1,10-phenanthroline-κ 2 N,N')(μ 3 -3-phenylprop-2-enoato-κ 4 O:O,O':O')(μ-3-phenylprop-2-enoato-κ 3 O,O':O)barium(II)], [Ba(C 10 H 7 O 2 ) 2 (C 10 H 8 N 2 )] n , (2), and characterized them by FT-IR and UV-Vis spectroscopies, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction analysis, as well as by powder X-ray diffraction (PXRD) analysis. Complex (1) features a chain topology of type 2,4 C4, where the Ca atoms are connected by O and N atoms, forming a distorted bicapped trigonal prismatic geometry. Complex (2) displays chains of topology type 2,3,5 C4, where the Ba atom is nine-coordinated by seven O atoms of bridging/chelating carboxylate groups from two cinnamate ligands and by two N atoms from one phenanthroline ligand, forming a distorted tricapped prismatic arrangement. Weak C-H...O hydrogen bonds and π-π stacking interactions between phenanthroline ligands are responsible to the formation of a supramolecular three-dimensional network. The thermal decompositions of (1) and (2) in the temperature range 297-1173 K revealed that they both decompose in three steps and transform to the corresponding metal oxide.

Paper relief architecture

NARCIS (Netherlands)

Latka, J.F.

2014-01-01

The article presents two contemporary projects of paper structures relief architecture designed and built by Shigeru Ban Architects and Voluntary Architect Network. Author of the article took part in design and construction process of one of the projects. The project of Yaan Nursery School, which

From steroids to aqueous supramolecular chemistry: an autobiographical career review.

Science.gov (United States)

Gibb, Bruce C

2016-01-01

The focus of my group's research is aqueous supramolecular chemistry; we try to understand how chemical entities interact with water and consequently how they interact with each other. This personal history recounts my career experiences that led to his involvement with this fascinating area of science.

Look and Do Ancient Greece. Teacher's Manual: Primary Program, Greek Art & Architecture [and] Workbook: The Art and Architecture of Ancient Greece [and] K-4 Videotape. History through Art and Architecture.

Science.gov (United States)

Luce, Ann Campbell

This resource, containing a teacher's manual, reproducible student workbook, and a color teaching poster, is designed to accompany a 21-minute videotape program, but may be adapted for independent use. Part 1 of the program, "Greek Architecture," looks at elements of architectural construction as applied to Greek structures, and…

Strong and Robust Polyaniline-Based Supramolecular Hydrogels for Flexible Supercapacitors.

Science.gov (United States)

Li, Wanwan; Gao, Fengxian; Wang, Xiaoqian; Zhang, Ning; Ma, Mingming

2016-08-01

We report a supramolecular strategy to prepare conductive hydrogels with outstanding mechanical and electrochemical properties, which are utilized for flexible solid-state supercapacitors (SCs) with high performance. The supramolecular assembly of polyaniline and polyvinyl alcohol through dynamic boronate bond yields the polyaniline-polyvinyl alcohol hydrogel (PPH), which shows remarkable tensile strength (5.3 MPa) and electrochemical capacitance (928 F g(-1) ). The flexible solid-state supercapacitor based on PPH provides a large capacitance (306 mF cm(-2) and 153 F g(-1) ) and a high energy density of 13.6 Wh kg(-1) , superior to other flexible supercapacitors. The robustness of the PPH-based supercapacitor is demonstrated by the 100 % capacitance retention after 1000 mechanical folding cycles, and the 90 % capacitance retention after 1000 galvanostatic charge-discharge cycles. The high activity and robustness enable the PPH-based supercapacitor as a promising power device for flexible electronics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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.

Fabrication of supramolecular frameworks by tuning the binding site ...

Indian Academy of Sciences (India)

Administrator

Fabrication of supramolecular frameworks by tuning the binding site of a tripodal ligand with d. 10 metal ions 803. Table 1. Crystal data and structure refinement parameters for 1 and 2. 1 .... e-mail: deposit@ccdc.cam.ac.uk web: http://www. ccdc. cam.ac.uk/deposit]. Supplementary figures and tables can be found in website ...

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

Science.gov (United States)

Sambrook, M R; Notman, S

2013-12-21

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

Assembly of three organic–inorganic hybrid supramolecular materials based on reduced molybdenum(V) phosphates

Energy Technology Data Exchange (ETDEWEB)

Zhang, He [Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025 (China); Key Laboratory of Synthesis of Functional Materials and Green Catalysis, Colleges of Heilongjiang Province, Harbin Normal University, Harbin 150025 (China); Yu, Kai, E-mail: hlyukai188@163.com [Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025 (China); Key Laboratory of Synthesis of Functional Materials and Green Catalysis, Colleges of Heilongjiang Province, Harbin Normal University, Harbin 150025 (China); Lv, Jing-Hua; Wang, Chun-Mei; Wang, Chun-Xiao [Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025 (China); Key Laboratory of Synthesis of Functional Materials and Green Catalysis, Colleges of Heilongjiang Province, Harbin Normal University, Harbin 150025 (China); Zhou, Bai-Bin, E-mail: zhou_bai_bin@163.com [Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025 (China); Key Laboratory of Synthesis of Functional Materials and Green Catalysis, Colleges of Heilongjiang Province, Harbin Normal University, Harbin 150025 (China)

2014-09-15

Three supramolecular materials based on (P{sub 4}Mo{sub 6}) polyoxoanions, (Hbbi){sub 2}(H{sub 2}bbi)[Cu{sub 3}Mo{sub 12}{sup V}O{sub 24}(OH){sub 6}(H{sub 2}O){sub 6}(HPO{sub 4}){sub 4}(H{sub 2}PO{sub 4}){sub 2}(PO{sub 4}){sub 2}]·3H{sub 2}O (1), (Hbbi){sub 2}(H{sub 2}bbi)[Ni{sub 3}Mo{sub 12}{sup V}O{sub 24}(OH){sub 6}(H{sub 2}O){sub 2}(HPO{sub 4}){sub 4}(H{sub 2}PO{sub 4}){sub 2}(PO{sub 4}){sub 2}]·9H{sub 2}O (2), (Hbpy)(bpy){sub 3}[Ni{sub 2}(H{sub 2}O){sub 10}Na(PCA){sub 2}][NiMo{sub 12}{sup V}O{sub 24}(OH){sub 6}(H{sub 2}PO{sub 4}){sub 6}(PO{sub 4}){sub 2}]·6H{sub 2}O (3) (bbi=1,1′-(1,4-butanediyl)bis(imidazole), bpy=4,4′-bipyridine, PCA=pyridine-4-carboxylic acid), have been hydrothermally synthesized and structurally characterized by the elemental analysis, TG, IR, UV–vis, PXRD and the single-crystal X-ray diffraction. Compounds 1 and 2 exhibit covalent 1-D chains constructed from M[P{sub 4}Mo{sub 6}]{sub 2} dimeric cluster and (M(H{sub 2}O){sub n}) (M=Cu, n=3 for 1 and M=Ni, n=1 for 2) linker. Compound 3 possesses an unusual POMMOF supramolecular layers based on [Ni(P{sub 4}Mo{sub 6})]{sub 2} dimeric units and 1-D metal–organic strings [Ni(H{sub 2}O){sub 5}Na(PCA)]{sub n}, in which an in situ ligand of PCA from 1,3-bis(4-pyridyl)propane (bpp) precursor was observed. Furthermore, the electrochemical behavior of 1–3-CPE and magnetic properties of 1–3 have been investigated in detail. - Graphical abstract: As new linking unit, Cu(H{sub 2}O){sub 3}, Ni(H{sub 2}O), and (Ni{sub 2}(H{sub 2}O){sub 10}Na(PCA){sub 2}) are introduced into (TM(P{sub 4}Mo{sub 6}){sub 2}) reaction systems to assemble three supramolecular materials under hydrothermal conditions via changing organic ligand and transition metal. - Highlights: • Tree new supramolecular hybrids based on (P{sub 4}Mo{sub 6}) cluster are reported. • Cu(H{sub 2}O){sub 3} and Ni(H{sub 2}O) as linker are introduced into the (TM(P{sub 4}Mo{sub 6}){sub 2}) systems. • 3 shows unusual layers based on

Dielectric electroactive polymers comprising an ionic supramolecular structure

DEFF Research Database (Denmark)

2014-01-01

The present invention relates to an ionic interpenetrating polymer network comprising at least one elastomer and an ionic supramolecular structure comprising the reaction product of at least two chemical compounds wherein each of said compounds has at least two functional groups and wherein said ...... compounds are able to undergo Lewis acid-base reactions. The interpenetrating polymer network may be used as dielectric electroactive polymers (DEAPs) having a high dielectric permittivity....

Supramolecular Assembly of Complementary Cyanine Salt J-Aggregates

KAUST Repository

Li, Zhong’ an; Mukhopadhyay, Sukrit; Jang, Sei-Hum; Bredas, Jean-Luc; Jen, Alex K.-Y.

2015-01-01

An understanding of structure–property relationships in cyanine dyes is critical for their design and application. Anionic and cationic cyanines can be organized into complementary cyanine salts, offering potential building blocks to modulate their intra/intermolecular interactions in the solid state. Here, we demonstrate how the structures of these complementary salts can be tuned to achieve highly ordered J-type supramolecular aggregate structures of heptamethine dyes in crystalline solids.

Supramolecular Assembly of Complementary Cyanine Salt J-Aggregates

KAUST Repository

Li, Zhong’an

2015-09-09

An understanding of structure–property relationships in cyanine dyes is critical for their design and application. Anionic and cationic cyanines can be organized into complementary cyanine salts, offering potential building blocks to modulate their intra/intermolecular interactions in the solid state. Here, we demonstrate how the structures of these complementary salts can be tuned to achieve highly ordered J-type supramolecular aggregate structures of heptamethine dyes in crystalline solids.

Reframing textiles into architectural systems : Construction of a membrane shell by patchwork

NARCIS (Netherlands)

Vrouwe, I.; Feijen, M.; Houtnam, R.; Borgart, A.

2011-01-01

In this paper different qualities of architectural textile techniques and tectonics are explored. By using a reframing strategy micro techniques and tectonics as used in fashion and textile design are evolved into an architectural scale. To reveal the quality of this reframing procedure a case

Architectural Thermal Forms II: Brick Envelope

DEFF Research Database (Denmark)

Foged, Isak Worre

2013-01-01

The paper presents an architectural concept and design method that investigates the use of dynamic factors in evolutionary form finding processes. The architectural construct, phenotype, is based on a brick assembly and how this can be organized based upon material properties and environmental...... aspects selected from the factors used in the Fanger equations to determine perceived comfort. The work finds that the developed method can be applied as performance oriented driver, while at the same time allowing diversity and variation in the architectural design space....

The influence of architectural designers on construction ergonomics ...

African Journals Online (AJOL)

, the construction process generates a disproportionate number of fatalities, injuries and disease and both the direct and indirect costs contribute to the cumulative cost of construction. Designers influence construction ergonomics directly and ...

Constructing Business Models around Identity : Tensions in Architectural Firms

NARCIS (Netherlands)

Bos-De Vos, M.; Volker, L.; Chan, Paul W; Neilson, Christopher J.

2017-01-01

Architectural firms experience difficulties to establish healthy and sustainable business models as they have to reconcile the often-competing value systems that they are based upon. Organizational members continuously negotiate professional values and beliefs with the firm's commercial goals,

Terpyridine modified poly(vinyl chloride) : possibilities for supramolecular grafting and crosslinking

NARCIS (Netherlands)

Meier, M.A.R.; Schubert, U.S.

2003-01-01

Commercially available poly(vinyl chloride) (PVC) was covalently modified with terpyridine supramolecular binding units in a two-step reaction. First, PVC was modified with aromatic thiols to introduce OH functionalities into the polymer backbone, which were subsequently reacted with an

Materials science and architecture

Science.gov (United States)

Bechthold, Martin; Weaver, James C.

2017-12-01

Materiality — the use of various materials in architecture — has been fundamental to the design and construction of buildings, and materials science has traditionally responded to needs formulated by design, engineering and construction professionals. Material properties and processes are shaping buildings and influencing how they perform. The advent of technologies such as digital fabrication, robotics and 3D printing have not only accelerated the development of new construction solutions, but have also led to a renewed interest in materials as a catalyst for novel architectural design. In parallel, materials science has transformed from a field that explains materials to one that designs materials from the bottom up. The conflation of these two trends is giving rise to materials-based design research in which architects, engineers and materials scientists work as partners in the conception of new materials systems and their applications. This Review surveys this development for different material classes (wood, ceramics, metals, concrete, glass, synthetic composites and polymers), with an emphasis on recent trends and innovations.

Studio Constructing an Archive - Modelkabinettet

DEFF Research Database (Denmark)

2012-01-01

. This has, among other subjects, included an analysis of the architectural exhibition "OMA Progress" at the Barbican Arts Centre in London as well as OMA's architecture, design strategy and media usage. The study has been based on discussions of archives, collections and architecture exhibitions as cultural...... products, historiography, media and architectural representation. Based on the above studies, the students have developed their own projects, which reflect in a critical manner on exhibitions, archives and collections. In Studio Constructing an Archive we focus on architectural representation and its...... significance and influence on the development of architecture and our understanding of architecture. During the spring semester, we have, in particular, been discussing the model and its media characteristics....

Coherent states field theory in supramolecular polymer physics

Science.gov (United States)

Fredrickson, Glenn H.; Delaney, Kris T.

2018-05-01

In 1970, Edwards and Freed presented an elegant representation of interacting branched polymers that resembles the coherent states (CS) formulation of second-quantized field theory. This CS polymer field theory has been largely overlooked during the intervening period in favor of more conventional "auxiliary field" (AF) interacting polymer representations that form the basis of modern self-consistent field theory (SCFT) and field-theoretic simulation approaches. Here we argue that the CS representation provides a simpler and computationally more efficient framework than the AF approach for broad classes of reversibly bonding polymers encountered in supramolecular polymer science. The CS formalism is reviewed, initially for a simple homopolymer solution, and then extended to supramolecular polymers capable of forming reversible linkages and networks. In the context of the Edwards model of a non-reacting homopolymer solution and one and two-component models of telechelic reacting polymers, we discuss the structure of CS mean-field theory, including the equivalence to SCFT, and show how weak-amplitude expansions (random phase approximations) can be readily developed without explicit enumeration of all reaction products in a mixture. We further illustrate how to analyze CS field theories beyond SCFT at the level of Gaussian field fluctuations and provide a perspective on direct numerical simulations using a recently developed complex Langevin technique.

Supramolecular nano-sniffers for ultrasensitive detection of formaldehyde.

Science.gov (United States)

Akshath, Uchangi Satyaprasad; Bhatt, Praveena

2018-02-15

Supramolecular nanoparticle hybrids for biosensing of analytes have been a major focus due to their tunable optical and surface properties. Quantum dots-Gold nanoparticle (QDs-GNP) based FRET probes involving turn on/off principles have gained immense interest due to their specificity and sensitivity. Recent focus is on applying these supramolecular hybrids for enzyme operated biosensors that can specifically turn-on fluorescence induced by co-factor or product formed from enzymatic reaction. The present study focuses on locking and unlocking the interaction between QD-GNP pair leading to differential fluorescent properties. Cationic GNPs efficiently quenched the anionic QD fluorescence by forming nanoparticle hybrid. Quenching interaction between QD-GNP pair was unlocked by NADH leading to QD fluorescence turn-on. This phenomenon was applied for the successful detection of formaldehyde using NAD + dependent formaldehyde dehydrogenase. The proposed nano-sniffer could successfully detect formaldehyde from 0.001 to 100000ng/mL (R 2 = 0.9339) by the turn off-turn on principle. It could also detect formaldehyde in fruit juice and wine samples indicating its stability and sensitivity in real samples. The proposed nanoprobe can have wide applications in developing enzyme biosensors in future. Copyright © 2017 Elsevier B.V. All rights reserved.

Between architecture and model: Strategies for cognitive control

NARCIS (Netherlands)

Taatgen, Niels

One major limitation of current cognitive architectures is that models are typically constructed in an “empty” architecture, and that the knowledge specifications (typically production rules) are specific to the particular task. This means that general cognitive control strategies have to be

Meccano: the building game, the architecture of commerce

Directory of Open Access Journals (Sweden)

Raúl Castellanos Gómez

2015-12-01

Full Text Available Between 1968 and 1970 Georges Candilis worked on a project for the construction of two shopping centres in the Le Barcarès-Leucate tourist train station located on the Languedoc-Roussillon region of the French coast. This article studies the project as an exemplary intervention in terms of the construction being inserted as a stem in the urban storyline, the organisation of the commercial programme in a mat-building style, and the diverse applications of the meccano construction set. This article analyses, through architectural writings, the character in which consumer society lends itself to the commercial architecture, which itself is finally turned into a consumer object.

Dynamic logic architecture based on piecewise-linear systems

International Nuclear Information System (INIS)

Peng Haipeng; Liu Fei; Li Lixiang; Yang Yixian; Wang Xue

2010-01-01

This Letter explores piecewise-linear systems to construct dynamic logic architecture. The proposed schemes can discriminate the two input signals and obtain 16 kinds of logic operations by different combinations of parameters and conditions for determining the output. Each logic cell performs more flexibly, that makes it possible to achieve complex logic operations more simply and construct computing architecture with less logic cells. We also analyze the various performances of our schemes under different conditions and the characteristics of these schemes.

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

Science.gov (United States)

Chui, Tin Ki

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

Comparison of Cellulose Supramolecular Structures Between Nanocrystals of Different Origins

Science.gov (United States)

Umesh P. Agarwal; Richard S. Reiner; Christopher G. Hunt; Jeffery Catchmark; E. Johan Foster; Akira Isogai

2015-01-01

In this study, morphologies and supramolecular structures of CNCs from wood-pulp, cotton, bacteria, tunicate, and cladophora were investigated. TEM was used to study the morphological aspects of the nanocrystals whereas Raman spectroscopy provided information on the cellulose molecular structure and its organization within a CNC. Dimensional differences between the...

Physical vapor deposited films of a perylene derivative: supramolecular arrangement and thermal stability

Energy Technology Data Exchange (ETDEWEB)

Fernandes, Jose Diego; Alessio, Priscila; Silva, Matheus Rodrigues Medeiros; Aroca, Ricardo Flavio; Souza, Agda Eunice de; Constantino, Carlos Jose Leopoldo, E-mail: case@fct.unesp.br [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Presidente Prudente, SP (Brazil). Dept. de Fisica

2017-07-15

The analysis of supramolecular arrangement is essential to understand the role of this key factor on the optical and electrical properties of organic thin films. In this work, thin solid films of bis(phenethylimido) perylene (PhPTCD) fabricated using physical vapor deposition (PVD) technique (thermal evaporation), deposited simultaneously onto different substrates (Ag mirror, Ge, and quartz plates) contingent on the characterization technique. The main objective is to study the PhPTCD supramolecular arrangement and the thermal stability of this arrangement in PVD films. The ultraviolet-visible absorption reveals a controlled growth of the PVD films, and the micro-Raman scattering data show that the PhPTCD molecule is not thermally degraded in the conditions of these experiments. The microscopy also shows a homogeneous morphological surface of the PVD film at macro and micro scales, with molecular aggregates at nanoscale. Besides, the PVD film roughness does not follow substrate roughness. The X-ray diffraction indicates a crystalline structure for PhPTCD powder and an amorphous form for PhPTCD PVD film. The infrared absorption spectroscopy points to a preferential flat-on organization of the molecules in the PVD films. In addition, the annealing process (200 deg C for 20 minutes) does not affect the supramolecular arrangement of the PhPTCD PVD films. (author)

Physical vapor deposited films of a perylene derivative: supramolecular arrangement and thermal stability

International Nuclear Information System (INIS)

Fernandes, Jose Diego; Alessio, Priscila; Silva, Matheus Rodrigues Medeiros; Aroca, Ricardo Flavio; Souza, Agda Eunice de; Constantino, Carlos Jose Leopoldo

2017-01-01

The analysis of supramolecular arrangement is essential to understand the role of this key factor on the optical and electrical properties of organic thin films. In this work, thin solid films of bis(phenethylimido) perylene (PhPTCD) fabricated using physical vapor deposition (PVD) technique (thermal evaporation), deposited simultaneously onto different substrates (Ag mirror, Ge, and quartz plates) contingent on the characterization technique. The main objective is to study the PhPTCD supramolecular arrangement and the thermal stability of this arrangement in PVD films. The ultraviolet-visible absorption reveals a controlled growth of the PVD films, and the micro-Raman scattering data show that the PhPTCD molecule is not thermally degraded in the conditions of these experiments. The microscopy also shows a homogeneous morphological surface of the PVD film at macro and micro scales, with molecular aggregates at nanoscale. Besides, the PVD film roughness does not follow substrate roughness. The X-ray diffraction indicates a crystalline structure for PhPTCD powder and an amorphous form for PhPTCD PVD film. The infrared absorption spectroscopy points to a preferential flat-on organization of the molecules in the PVD films. In addition, the annealing process (200 deg C for 20 minutes) does not affect the supramolecular arrangement of the PhPTCD PVD films. (author)

Sunken garden: remarkable example of Iranian sustainable architecture

Energy Technology Data Exchange (ETDEWEB)

Rezaei, Davood; Toufani, Sargol; Sadegh Falahat, Mohammad [Zanjan University (Iran, Islamic Republic of)], email: d_rezaei@znu.ac.ir, email: sargol2fun@gmail.com, email: safalahat@yahoo.com

2011-07-01

The energy crisis and climate change give new importance to sustainable architecture which reduces the negative impacts that buildings can have on the environment. In ancient times, architects did not have access to modern equipment and had to use natural energies to provide pleasant indoor conditions. Iran has various climatic zones and Iranian traditional architecture relied on a variety of solutions to provide for human comfort. The aim of this study is to present those solutions used in traditional Iranian architecture. This paper presents the use of the energy of the earth depth and other methods such as Syzan, a cellar, Shvadan, pool house, Zmhryr in addition to the sunken garden, which taps geothermal energy by constructing a courtyard lower than street level. This document showed that traditional Iranian architectural strategies are efficient in providing sustainable buildings and could be applied in the design of new construction.

[Architecture and movement].

Science.gov (United States)

Rivallan, Armel

2012-01-01

Leading an architectural project means accompanying the movement which it induces within the teams. Between questioning, uncertainty and fear, the organisational changes inherent to the new facility must be subject to constructive and ongoing exchanges. Ethics, safety and training are revised and the unit projects are sometimes modified.

Layered architecture for quantum computing

OpenAIRE

Jones, N. Cody; Van Meter, Rodney; Fowler, Austin G.; McMahon, Peter L.; Kim, Jungsang; Ladd, Thaddeus D.; Yamamoto, Yoshihisa

2010-01-01

We develop a layered quantum-computer architecture, which is a systematic framework for tackling the individual challenges of developing a quantum computer while constructing a cohesive device design. We discuss many of the prominent techniques for implementing circuit-model quantum computing and introduce several new methods, with an emphasis on employing surface-code quantum error correction. In doing so, we propose a new quantum-computer architecture based on optical control of quantum dot...

Amplification of chirality in helical supramolecular polymers: the majority-rules principle.

NARCIS (Netherlands)

Gestel, van J.A.M.

2004-01-01

Amplification of chirality, being a strongly nonlinear response of the optical activity of helical polymers to a small (net) amount of optically active material, has recently been discovered in supramolecular copolymers. Apart from the sergeants-and-soldiers type we discussed in earlier work,

Solvent-assisted multistage nonequilibrium electron transfer in rigid supramolecular systems: Diabatic free energy surfaces and algorithms for numerical simulations

Science.gov (United States)

Feskov, Serguei V.; Ivanov, Anatoly I.

2018-03-01

An approach to the construction of diabatic free energy surfaces (FESs) for ultrafast electron transfer (ET) in a supramolecule with an arbitrary number of electron localization centers (redox sites) is developed, supposing that the reorganization energies for the charge transfers and shifts between all these centers are known. Dimensionality of the coordinate space required for the description of multistage ET in this supramolecular system is shown to be equal to N - 1, where N is the number of the molecular centers involved in the reaction. The proposed algorithm of FES construction employs metric properties of the coordinate space, namely, relation between the solvent reorganization energy and the distance between the two FES minima. In this space, the ET reaction coordinate zn n' associated with electron transfer between the nth and n'th centers is calculated through the projection to the direction, connecting the FES minima. The energy-gap reaction coordinates zn n' corresponding to different ET processes are not in general orthogonal so that ET between two molecular centers can create nonequilibrium distribution, not only along its own reaction coordinate but along other reaction coordinates too. This results in the influence of the preceding ET steps on the kinetics of the ensuing ET. It is important for the ensuing reaction to be ultrafast to proceed in parallel with relaxation along the ET reaction coordinates. Efficient algorithms for numerical simulation of multistage ET within the stochastic point-transition model are developed. The algorithms are based on the Brownian simulation technique with the recrossing-event detection procedure. The main advantages of the numerical method are (i) its computational complexity is linear with respect to the number of electronic states involved and (ii) calculations can be naturally parallelized up to the level of individual trajectories. The efficiency of the proposed approach is demonstrated for a model

Synthetic Approach to biomolecular science by cyborg supramolecular chemistry.

Science.gov (United States)

Kurihara, Kensuke; Matsuo, Muneyuki; Yamaguchi, Takumi; Sato, Sota

2018-02-01

To imitate the essence of living systems via synthetic chemistry approaches has been attempted. With the progress in supramolecular chemistry, it has become possible to synthesize molecules of a size and complexity close to those of biomacromolecules. Recently, the combination of precisely designed supramolecules with biomolecules has generated structural platforms for designing and creating unique molecular systems. Bridging between synthetic chemistry and biomolecular science is also developing methodologies for the creation of artificial cellular systems. This paper provides an overview of the recently expanding interdisciplinary research to fuse artificial molecules with biomolecules, that can deepen our understanding of the dynamical ordering of biomolecules. Using bottom-up approaches based on the precise chemical design, synthesis and hybridization of artificial molecules with biological materials have been realizing the construction of sophisticated platforms having the fundamental functions of living systems. The effective hybrid, molecular cyborg, approaches enable not only the establishment of dynamic systems mimicking nature and thus well-defined models for biophysical understanding, but also the creation of those with highly advanced, integrated functions. This article is part of a Special Issue entitled "Biophysical Exploration of Dynamical Ordering of Biomolecular Systems" edited by Dr. Koichi Kato. Copyright © 2017 Elsevier B.V. All rights reserved.

Self-Healing Natural Rubber with Tailorable Mechanical Properties Based on Ionic Supramolecular Hybrid Network.

Science.gov (United States)

Xu, Chuanhui; Cao, Liming; Huang, Xunhui; Chen, Yukun; Lin, Baofeng; Fu, Lihua

2017-08-30

In most cases, the strength of self-healing supramolecular rubber based on noncovalent bonds is in the order of KPa, which is a challenge for their further applications. Incorporation of conventional fillers can effectively enhance the strength of rubbers, but usually accompanied by a sacrifice of self-healing capability due to that the filler system is independent of the reversible supramolecular network. In the present work, in situ reaction of methacrylic acid (MAA) and excess zinc oxide (ZnO) was realized in natural rubber (NR). Ionic cross-links in NR matrix were obtained by limiting the covalent cross-linking of NR molecules and allowing the in situ polymerization of MAA/ZnO. Because of the natural affinity between Zn 2+ ion-rich domains and ZnO, the residual nano ZnO participated in formation of a reversible ionic supramolecular hybrid network, thus having little obstructions on the reconstruction of ionic cross-links. Meanwhile, the well dispersed residual ZnO could tailor the mechanical properties of NR by changing the MAA/ZnO molar ratios. The present study thus provides a simple method to fabricate a new self-healing NR with tailorable mechanical properties that may have more potential applications.

PEG-bis phosphonic acid based ionic supramolecular structures

DEFF Research Database (Denmark)

Gonzalez, Lidia; Skov, Anne Ladegaard; Hvilsted, Søren

2014-01-01

. The resulting ionic assemblies are very comprehensively characterized by ATR-FTIR, proton, and carbon-13 NMR spectroscopy that unequivocally demonstrate the ionic network formation through ammonium phophonates. The resulting salt and ionic networks are additionally analyzed by differential scanning calorimetry...... and thermogravimetric analysis. The conclusion is that mixing the virgin components at room temperature spontaneously form either a salt or ionic supramolecular networks. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim....

Molecular self-assembly approaches for supramolecular electronic and organic electronic devices

Science.gov (United States)

Yip, Hin-Lap

Molecular self-assembly represents an efficient bottom-up strategy to generate structurally well-defined aggregates of semiconducting pi-conjugated materials. The capability of tuning the chemical structures, intermolecular interactions and nanostructures through molecular engineering and novel materials processing renders it possible to tailor a large number of unprecedented properties such as charge transport, energy transfer and light harvesting. This approach does not only benefit traditional electronic devices based on bulk materials, but also generate a new research area so called "supramolecular electronics" in which electronic devices are built up with individual supramolecular nanostructures with size in the sub-hundred nanometers range. My work combined molecular self-assembly together with several novel materials processing techniques to control the nucleation and growth of organic semiconducting nanostructures from different type of pi-conjugated materials. By tailoring the interactions between the molecules using hydrogen bonds and pi-pi stacking, semiconducting nanoplatelets and nanowires with tunable sizes can be fabricated in solution. These supramolecular nanostructures were further patterned and aligned on solid substrates through printing and chemical templating methods. The capability to control the different hierarchies of organization on surface provides an important platform to study their structural-induced electronic properties. In addition to using molecular self-assembly to create different organic nanostructures, functional self-assembled monolayer (SAM) formed by spontaneous chemisorption on surfaces was used to tune the interfacial property in organic solar cells. Devices showed dramatically improved performance when appropriate SAMs were applied to optimize the contact property for efficiency charge collection.

Insight into the chiral induction in supramolecular stacks through preferential chiral salvation

NARCIS (Netherlands)

George, S.J.; Tomovic, Z.; Schenning, A.P.H.J.; Meijer, E.W.

2011-01-01

Preferred handedness in the supramolecular chirality of self-assembled achiral oligo(p-phenylenevinylene) (OPV) derivatives is induced by chiral solvents and spectroscopic probing provides insight into the mechanistic aspects of this chiral induction through chiral solvation

A series of coordination polymers constructed from R-isophthalic acid (R=-SO3H, -NO2, and -OH) and N-donor ligands: Syntheses, structures and fluorescence properties

Science.gov (United States)

Zhou, Yong-Hong; Zhou, Xu-Wan; Zhou, Su-Rong; Tian, Yu-Peng; Wu, Jie-Ying

2017-01-01

Six novel Zn(II), Cd(II), and Cu(II) mixed-ligand coordination complexes, namely, [Zn2Na(sip)2(bpp)3(Hbpp)(H2O)2]·8H2O (1), [Cd3(sip)2(nbi)6(H2O)2]·7H2O (2), [Zn(sip)(nbi)2(H2O)]·Hnbi·3H2O (3), [Cd(hip)(nbi)2(H2O)]·nbi·5H2O (4), [Cd2(nip)2(nbi)2(H2O)2]·DMF (5), and [Cu(nip)(nbi)(H2O)2]·H2O (6) (H3sip=5-sulfoisophthalic acid, H2hip=5-hydroxylisophthalic acid, H2nip=5-nitroisophthalic acid, bpp=1,3-bis(4-pyridyl)propane, and nbi=6-nitrobenzimidazole) have been synthesized hydrothermally by the self-assembly of R-isophthalic acid (R=-SO3H, -NO2, and -OH) and N-donor ligands. Single crystal X-ray analyses reveal that two Zn(II) ions and one Na(I) ion of complex 1 are linked through O atoms to generate a 1D linear chain. Then the 2D supramolecular architectures are constructed via intermolecular interactions. In complex 2, the Cd1 ions are connected by bridging carboxyl groups from sip3- anions to form 1D double chain, which are further connected by Cd2 ions to afford 2D layer structure. The adjacent 2D layers are further linked via hydrogen-bonding interactions to give 3D supramolecular network. Compounds 3-5 show 1D chain structures, which are assembled into 2D or 3D supramolecular frameworks via weak interactions. In compound 6, the Cu(II) ions are bridged by the nip2- ligands to form 48-membered ring, which is assembled into 1Dchain via the π-π stacking interaction. In addition, the thermal stabilities and fluorescence properties of these compounds have also been studied.

Photoluminescence Spectra of Self-Assembling Helical Supramolecular Assemblies: A Theoretical Study

NARCIS (Netherlands)

van Dijk, Leon; Kersten, Sander P.; Jonkheijm, Pascal; van der Schoot, Paul; Bobbert, Peter A.

2008-01-01

The reversible assembly of helical supramolecular polymers of chiral molecular building blocks is known to be governed by the interplay between mass action and the competition between weakly and strongly bound states of these building blocks. The highly co-operative transition from free monomers at

Programming Recognition Arrays through Double Chalcogen-Bonding Interactions.

Science.gov (United States)

Biot, Nicolas; Bonifazi, Davide

2018-04-11

In this work, we have programmed and synthesized a recognition motif constructed around a chalcogenazolo-pyridine scaffold (CGP) that, through the formation of frontal double chalcogen-bonding interactions, associates into dimeric EX-type complexes. The reliability of the double chalcogen-bonding interaction has been shown at the solid-state by X-ray analysis, depicting the strongest recognition persistence for a Te-congener. The high recognition fidelity, chemical and thermal stability and easy derivatization at the 2-position makes CGP a convenient motif for constructing supramolecular architectures through programmed chalcogen-bonding interactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mesoscopic Self-Assembly: A Shift to Complexity

Directory of Open Access Journals (Sweden)

Massimo eMastrangeli

2015-06-01

Full Text Available By focusing on the construction of thermodynamically stable structures, the self-assembly of mesoscopic systems has proven capable of formidable achievements in the bottom-up engineering of micro- and nanosystems. Yet, inspired by an analogous evolution in supramolecular chemistry, synthetic mesoscopic self-assembly may have a lot more ahead, within reach of a shift toward fully three-dimensional architectures, collective interactions of building blocks and kinetic control. All over these challenging fronts, complexity holds the key.

Noncovalent assembly. A rational strategy for the realization of chain-growth supramolecular polymerization.

Science.gov (United States)

Kang, Jiheong; Miyajima, Daigo; Mori, Tadashi; Inoue, Yoshihisa; Itoh, Yoshimitsu; Aida, Takuzo

2015-02-06

Over the past decade, major progress in supramolecular polymerization has had a substantial effect on the design of functional soft materials. However, despite recent advances, most studies are still based on a preconceived notion that supramolecular polymerization follows a step-growth mechanism, which precludes control over chain length, sequence, and stereochemical structure. Here we report the realization of chain-growth polymerization by designing metastable monomers with a shape-promoted intramolecular hydrogen-bonding network. The monomers are conformationally restricted from spontaneous polymerization at ambient temperatures but begin to polymerize with characteristics typical of a living mechanism upon mixing with tailored initiators. The chain growth occurs stereoselectively and therefore enables optical resolution of a racemic monomer. Copyright © 2015, American Association for the Advancement of Science.

Supramolecular Lego assembly towards three-dimensional multi-responsive hydrogels.

Science.gov (United States)

Ma, Chunxin; Li, Tiefeng; Zhao, Qian; Yang, Xuxu; Wu, Jingjun; Luo, Yingwu; Xie, Tao

2014-08-27

Inspired by the assembly of Lego toys, hydrogel building blocks with heterogeneous responsiveness are assembled utilizing macroscopic supramolecular recognition as the adhesion force. The Lego hydrogel provides 3D transformation upon pH variation. After disassembly of the building blocks by changing the oxidation state, they can be re-assembled into a completely new shape. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular architecture of 5-bromo-7-methoxy-1-methyl-1H-benzoimidazole.3H2O: Synthesis, spectroscopic investigations, DFT computation, MD simulations and docking studies

Science.gov (United States)

Murthy, P. Krishna; Smitha, M.; Sheena Mary, Y.; Armaković, Stevan; Armaković, Sanja J.; Rao, R. Sreenivasa; Suchetan, P. A.; Giri, L.; Pavithran, Rani; Van Alsenoy, C.

2017-12-01

Crystal and molecular structure of newly synthesized compound 5-bromo-7-methoxy-1-methyl-1H-benzoimidazole (BMMBI) has been authenticated by single crystal X-ray diffraction, FT-IR, FT-Raman, 1H NMR, 13C NMR and UV-Visible spectroscopic techniques; compile both experimental and theoretical results which are performed by DFT/B3LYP/6-311++G(d,p) method at ground state in gas phase. Visualize nature and type of intermolecular interactions and crucial role of these interactions in supra-molecular architecture has been investigated by use of a set of graphical tools 3D-Hirshfeld surfaces and 2D-fingerprint plots analysis. The title compound stabilized by strong intermolecular hydrogen bonds N⋯Hsbnd O and O⋯Hsbnd O, which are envisaged by dark red spots on dnorm mapped surfaces and weak Br⋯Br contacts envisaged by red spot on dnorm mapped surface. The detailed fundamental vibrational assignments of wavenumbers were aid by with help of Potential Energy distribution (PED) analysis by using GAR2PED program and shows good agreement with experimental values. Besides frontier orbitals analysis, global reactivity descriptors, natural bond orbitals and Mullikan charges analysis were performed by same basic set at ground state in gas phase. Potential reactive sites of the title compound have been identified by ALIE, Fukui functions and MEP, which are mapped to the electron density surfaces. Stability of BMMBI have been investigated from autoxidation process and pronounced interaction with water (hydrolysis) by using bond dissociation energies (BDE) and radial distribution functions (RDF), respectively after MD simulations. In order to identify molecule's most important reactive spots we have used a combination of DFT calculations and MD simulations. Reactivity study encompassed calculations of a set of quantities such as: HOMO-LUMO gap, MEP and ALIE surfaces, Fukui functions, bond dissociation energies and radial distribution functions. To confirm the potential

Supramolecular architectures constructed through self-assembly of a chalcone and substituted diazo-β-diketones

Science.gov (United States)

Prajapati, R.; Mishra, L.; Grabowski, S. J.; Govil, G.; Dubey, S. K.

2008-05-01

Organic compounds namely pyridyl chalcone viz. 3-[4-(3-oxo-3-pyridin-2-yl-propenyl)-phenyl]-1-pyridin-2-yl-propenone (L 1), p-cholorophenyldiazopentane-2,4-dione (L 2) and p-methyl phenyldiazopentane-2,4-dione (L 3) have been characterized by their single-crystal X-ray crystallographic studies. Several structural motifs resulting upon their self-association through probable non-covalent interactions have been discussed. The studies of related motifs found in Cambridge Structural Database are performed and the results are related to the structural data obtained for crystal structures reported here in.

Supramolecular network through Nsbnd H…O, Osbnd H…O and Csbnd H…O hydrogen bonding interaction and density functional theory studies of 4-methylanilinium-3-carboxy-4-hydroxybenzenesulphonate crystal

Science.gov (United States)

Rajkumar, M.; Muthuraja, P.; Dhandapani, M.; Chandramohan, A.

2018-02-01

By utilizing the hydrogen bonding strategy, 4-methylanilinium-3-hydroxy-4-corboxy-benzenesulphonate (4MABS), an organic proton transfer molecular salt was synthesized and single crystals of it were successfully grown by slow solvent evaporation solution growth technique at ambient temperature. The 1H and 13C NMR spectra were recorded to establish the molecular structure of the title salt. The single crystal XRD analysis reveals that the title salt crystallizes in monoclinic crystal system with centrosymmetric space group, P21/n. Further, the title salt involves extensive intermolecular Nsbnd H…O, Osbnd H…O and Csbnd H…O as well as intramolecular Osbnd H…O hydrogen bonding interactions to construct supramolecular architecture. All quantum chemical calculations were performed at the level of density functional theory (DFT) with B3LYP functional using 6-311G (d,p) basis atomic set. The photoluminescence spectrum was recorded to explore the emission property of the title crystal. The presence of the various vibrational modes and functional groups in the synthesized salt was confirmed by FT-IR studies. The thermal behaviour of title crystal was established employing TG/DTA analyses. The mechanical properties of the grown crystal were determined by Vicker's microhardness studies. Dielectric measurements were carried out on the grown crystal at a different temperature to evaluate electrical properties.

Methodology for studying molecular and supramolecular structures of coals and carbonaceous materials

Energy Technology Data Exchange (ETDEWEB)

G.B. Skripchenko [Russian Academy of Sciences, Moscow (Russian Federation). Russia Institute for Fossil Fuels - Science and Technology Center for Complex Processing of Solid Fossil Fuels

2009-07-01

Those studying coals have to account for petrographic nonuniformity (the optical structural level), different types of chemical bonding between structural fragments, the existence of aromatic clusters in the organic matter, the appearance of a supramolecular order between aromatic clusters, and further orientation ordering of crystallites under the action of the geological pressure. Combinations of conventional chemical strategies with advanced physicochemical methods, such as IR, NMR, EPR, and X-ray spectroscopy; X-ray diffraction; electronic and scanning microscopy; and some others, are pertinent for structure determination. The appearance of supramolecular structures is a manifestation of molecular-level structural rearrangements, which are characteristic of coals, cokes, pitches, and various pyrolytic carbons. This necessitates the use of optical, electronic, and scanning microscopy along with other chemical methods. The occurrence of mineral components in coals can appreciably limit the resolution of IR spectroscopy and X-ray crystallography.

Water-soluble building blocks for terpyridine-containing supramolecular polymers : synthesis, complexation, and pH stability studies of poly(ethylene oxide) moieties

NARCIS (Netherlands)

Lohmeijer, B.G.G.; Schubert, U.S.

2003-01-01

Poly(ethylene oxide) of various molecular weights ([bar M ]n = 3 000, 5 200, 10 000, 16 500 g · mol-1) has been modified with terpyridine end groups as building blocks for water-soluble metallo-supramolecular polymers. Metallo-supramolecular A-A homopolymers have been prepared and characterized by

Is Supramolecular Filament Chirality the Underlying Cause of Major Morphology Differences in Amyloid Fibrils?

Science.gov (United States)

2015-01-01

The unique enhanced sensitivity of vibrational circular dichroism (VCD) to the formation and development of amyloid fibrils in solution is extended to four additional fibril-forming proteins or peptides where it is shown that the sign of the fibril VCD pattern correlates with the sense of supramolecular filament chirality and, without exception, to the dominant fibril morphology as observed in AFM or SEM images. Previously for insulin, it has been demonstrated that the sign of the VCD band pattern from filament chirality can be controlled by adjusting the pH of the incubating solution, above pH 2 for “normal” left-hand-helical filaments and below pH 2 for “reversed” right-hand-helical filaments. From AFM or SEM images, left-helical filaments form multifilament braids of left-twisted fibrils while the right-helical filaments form parallel filament rows of fibrils with a flat tape-like morphology, the two major classes of fibril morphology that from deep UV resonance Raman scattering exhibit the same cross-β-core secondary structure. Here we investigate whether fibril supramolecular chirality is the underlying cause of the major morphology differences in all amyloid fibrils by showing that the morphology (twisted versus flat) of fibrils of lysozyme, apo-α-lactalbumin, HET-s (218–289) prion, and a short polypeptide fragment of transthyretin, TTR (105–115), directly correlates to their supramolecular chirality as revealed by VCD. The result is strong evidence that the chiral supramolecular organization of filaments is the principal underlying cause of the morphological heterogeneity of amyloid fibrils. Because fibril morphology is linked to cell toxicity, the chirality of amyloid aggregates should be explored in the widely used in vitro models of amyloid-associated diseases. PMID:24484302

Is supramolecular filament chirality the underlying cause of major morphology differences in amyloid fibrils?

Science.gov (United States)

Kurouski, Dmitry; Lu, Xuefang; Popova, Ludmila; Wan, William; Shanmugasundaram, Maruda; Stubbs, Gerald; Dukor, Rina K; Lednev, Igor K; Nafie, Laurence A

2014-02-12

The unique enhanced sensitivity of vibrational circular dichroism (VCD) to the formation and development of amyloid fibrils in solution is extended to four additional fibril-forming proteins or peptides where it is shown that the sign of the fibril VCD pattern correlates with the sense of supramolecular filament chirality and, without exception, to the dominant fibril morphology as observed in AFM or SEM images. Previously for insulin, it has been demonstrated that the sign of the VCD band pattern from filament chirality can be controlled by adjusting the pH of the incubating solution, above pH 2 for "normal" left-hand-helical filaments and below pH 2 for "reversed" right-hand-helical filaments. From AFM or SEM images, left-helical filaments form multifilament braids of left-twisted fibrils while the right-helical filaments form parallel filament rows of fibrils with a flat tape-like morphology, the two major classes of fibril morphology that from deep UV resonance Raman scattering exhibit the same cross-β-core secondary structure. Here we investigate whether fibril supramolecular chirality is the underlying cause of the major morphology differences in all amyloid fibrils by showing that the morphology (twisted versus flat) of fibrils of lysozyme, apo-α-lactalbumin, HET-s (218-289) prion, and a short polypeptide fragment of transthyretin, TTR (105-115), directly correlates to their supramolecular chirality as revealed by VCD. The result is strong evidence that the chiral supramolecular organization of filaments is the principal underlying cause of the morphological heterogeneity of amyloid fibrils. Because fibril morphology is linked to cell toxicity, the chirality of amyloid aggregates should be explored in the widely used in vitro models of amyloid-associated diseases.

"Intelligent" design of molecular materials: Understanding the concepts of design in supramolecular synthesis of network solids

Science.gov (United States)

Moulton, Brian D.

This work endeavors to delineate modern paradigms for crystal engineering, i.e. the design and supramolecular synthesis of functional molecular materials. Paradigms predicated on an understanding of the geometry of polygons and polyhedra are developed. The primary focus is on structural determination by single crystal X-ray crystallography, structural interpretation using a suite of graphical visualization and molecular modeling software, and on the importance of proper graphical representation in the presentation and explanation of crystal structures. A detailed analysis of a selected series of crystal structures is presented. The reduction of these molecular networks to schematic representations that illustrate their fundamental connectivity facilitates the understanding of otherwise complex supramolecular solids. Circuit symbols and Schlafli notation are used to describe the network topologies, which enables networks of different composition and metrics to be easily compared. This reveals that molecular orientations in the crystals and networks are commensurate with networks that can be derived from spherical close packed lattices. The development of a logical design strategy for a new class of materials based on our understanding of the chemical composition and topology of these networks is described. The synthesis and crystal structure of a series of new materials generated by exploitation of this design strategy is presented, in addition to a detailed analysis of the topology of these materials and their relationship to a 'parent' structure. In summary, this dissertation demonstrates that molecular polygons can self-assemble at their vertexes to produce molecular architectures and crystal structures that are consistent with long established geometric dogma. The design strategy represents a potentially broad ranging approach to the design of nanoporous structures from a wide range of chemical components that are based on molecular shape rather than chemical

Extensive Evaluation of Using a Game Project in a Software Architecture Course

Science.gov (United States)

Wang, Alf Inge

2011-01-01

This article describes an extensive evaluation of introducing a game project to a software architecture course. In this project, university students have to construct and design a type of software architecture, evaluate the architecture, implement an application based on the architecture, and test this implementation. In previous years, the domain…

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

NARCIS (Netherlands)

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

2013-01-01

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

Heparin-binding peptide amphiphile supramolecular architectures as platforms for angiogenesis and drug delivery

Science.gov (United States)

Chow, Lesleyann W.

A fascinating phenomenon in nature is the self-assembly of molecules into a functional, hierarchical structure. In the past decade, the Stupp Laboratory has developed several classes of self-assembling biomaterials, one of which is the synthetic peptide amphiphile (PA). Self-assembling PAs are attractive and versatile biomolecules that can be customized for specific applications in regenerative medicine. In particular, a heparin-binding peptide amphiphile (HBPA) containing a specific heparin-binding peptide sequence was used here to induce angiogenesis and serve as a delivery vehicle for growth factors and small hydrophobic molecules. Throughout this dissertation, the HBPA/heparin system is used in different architectures for a variety of regenerative medicine applications. In one aspect of this work, hybrid scaffolds made from HBPA/heparin gelled on a poly(L-lactic acid) (PLLA) fiber mesh were used to promote angiogenesis to facilitate pancreatic islet transplantation for the treatment of type 1 diabetes. Delivery of growth factors with HBPA/PLLA scafflolds increased vessel density in vivo and correlated with improved transplant outcomes in a streptozotocin-induced diabetic mouse model. Soluble HBPA nanofiber architectures were also useful for islet transplantation applications. These nanofibers were used at concentrations below gelation to deliver growth factors into the dense islet cell aggregate, promoting cell survival and angiogenesis in vitro. The nanostructures infiltrated the islets and promoted the retention of heparin and growth factors within the islet. Another interesting growth factor release system discussed here is the HBPA membrane structure. HBPA was found to self-assemble with hyaluronic acid, a large biopolymer found in the body, into macroscopic, hierarchically-ordered membranes. Heparin was incorporated into these membranes and affected the membrane's mechanical properties and growth factor release. Human mesenchymal stem cells were also shown

Revolution of Chinese architectural design at the new-type urbanization stage

Directory of Open Access Journals (Sweden)

Jianguo Wang

2015-09-01

Full Text Available Witnessing more than three decades of sustained and rapid economic growth, China has become a nation that enjoys the fastest rate of urbanization; the largest quantities of civil construction; the most obvious urban development to be “newer”, “bigger” and “higher”; and the most prosperous architectural design market worldwide. In terms of the construction industry, housing construction totals 31.3 billion square meters, occupying more than 70% of the floor area of the existing stock houses. It is safe to say that the construction industry significantly boosts GDP growth, expands the number of jobs, and improves the living conditions of the masses. Related to this is the need to end the architectural guidelines of the planned economy era economizing on food and clothing and instead step into a new historic stage allowing bold pursuit of architectural aesthetics and individuality. A group of architects who have social ideals, adhere faithfully to professional standards and pledge to pursue architectural innovation are active in China. Instead of simply converting the overwhelming opportunities brought to carry economic benefits, they dare to embrace the challenges imposed on enhancing architectural connotation and create a batch of high-level work that lives up to expectations of the era, marking the achievement of reform and rapid urbanization in China. Yet, as time goes on, the promotion of national development concepts, ideas of social consumption and the masses’ cultural level establishes new requirements for the architectural design industry, architects and architectural design works. An appeal is thus made against Chinese architects for a summary, reflection and proactive anticipation to respond to the new requirements of the era.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

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

Diagnosis of Transformation in Architecture and Construction of the Housing Stock in the Years 1848-2013 in Selected Cities Of Upper Silesia

Science.gov (United States)

Cibis, Jerzy; Nowogońska, Beata

2017-10-01

Despite extensive and valuable literature and a series of activities over the past several years of scientific studies, there’s lack of work presenting a comprehensive inventory of housing shaped over the centuries in terms of the assessment of the users’ needs based on suitability and real modernisation. Such coverage of the subject, based largely on research methods using statistical reports on the changes carried out in the substance subject to research, would enable the assessment - as close to the reality as possible - of the housing stock and the potential associated with its further use. The subject of the work is the state of residential architecture resources of the period 1848-2013 in selected cities of Upper Silesia, changes carried out in the architecture and construction. Changes to the architecture and construction carried out in the housing stock subject to research constitute an important means of evaluation of the housing resources by their users. The changes occur three aspects: technical, functional and aesthetic. The main objective of the work is the presentation of a detailed assessment and comprehensive picture of the state of the housing stock of selected cities in Upper Silesia, based on statistical tests, numerous spatial solutions in terms of the evolutionary development of forms of residential architecture in Upper Silesia. The premise of the work is on the one hand, the expansion of knowledge of housing resources in Upper Silesian cities. On the other hand, it is an attempt to formulate a method of the comprehensive assessment of the housing stock in general, using the elements of statistics, analysis of spatial solutions and macrosocial determinants that shape human residential space. For greater clarity and precision of the obtained information, the performed assessment is connected with a direct private space of a dwelling place. It discusses to a limited extent the modernisation and transformation of the neighbourhood or the so

Linear Viscoelastic and Dielectric Relaxation Response of Unentangled UPy-Based Supramolecular Networks

DEFF Research Database (Denmark)

Shabbir, Aamir; Javakhishvili, Irakli; Cerveny, Silvina

2016-01-01

Supramolecular polymers possess versatile mechanical properties and a unique ability to respond to external stimuli. Understanding the rich dynamics of such associative polymers is essential for tailoring user-defined properties in many products. Linear copolymers of 2-methoxyethyl acrylate (MEA)...

Macromolecules containing bipyridine and terpyridine metal complexes: towards metallo-supramolecular polymers

NARCIS (Netherlands)

Schubert, U.S.; Eschbaumer, C.

2002-01-01

The ability of a broad range of N-heterocycles to act as very effective and stable complexation agents for several transition metal ions, such as cobalt(II), copper(II), nickel(II), and ruthenium(II), has long been known in analytical chemistry. This behavior was later utilized in supramolecular

The brand architecture of grocery retailers

DEFF Research Database (Denmark)

Bech-Larsen, Tino; Esbjerg, Lars

2009-01-01

This article discusses how the brand architecture of grocery retailers set material and symbolic boundaries for consumer choice, thus limiting consumer sovereignty. The article first discusses previous work on store atmospherics, servicescapes and brand architecture. It is argued that work based...... on these concepts has taken an internal management perspective on how retailers can manipulate aspects of the retail setting to serve their own interests. Then, we develop an alternative conceptualisation of retailer brand architecture that takes into account that consumers (and other constituents) are active co......- constructors of material and symbolic aspects of retail settings. It is discussed how consumers participate in constructing retailer brand architecture and how this concept differs from previous research. Implications for both research and practice are discussed....

Transfer and Dynamic Inversion of Coassembled Supramolecular Chirality through 2D-Sheet to Rolled-Up Tubular Structure.

Science.gov (United States)

Choi, Heekyoung; Cho, Kang Jin; Seo, Hyowon; Ahn, Junho; Liu, Jinying; Lee, Shim Sung; Kim, Hyungjun; Feng, Chuanliang; Jung, Jong Hwa

2017-12-13

Transfer and inversion of supramolecular chirality from chiral calix[4]arene analogs (3D and 3L) with an alanine moiety to an achiral bipyridine derivative (1) with glycine moieties in a coassembled hydrogel are demonstrated. Molecular chirality of 3D and 3L could transfer supramolecular chirality to an achiral bipyridine derivative 1. Moreover, addition of 0.6 equiv of 3D or 3L to 1 induced supramolecular chirality inversion of 1. More interestingly, the 2D-sheet structure of the coassembled hydrogels formed with 0.2 equiv of 3D or 3L changed to a rolled-up tubular structure in the presence of 0.6 equiv of 3D or 3L. The chirality inversion and morphology change are mainly mediated by intermolecular hydrogen-bonding interactions between the achiral and chiral molecules, which might be induced by reorientations of the assembled molecules, confirmed by density functional theory calculations.

Self-organization of a self-assembled supramolecular rectangle, square, and three-dimensional cage on Au111 surfaces.

Science.gov (United States)

Yuan, Qun-Hui; Wan, Li-Jun; Jude, Hershel; Stang, Peter J

2005-11-23

The structure and conformation of three self-assembled supramolecular species, a rectangle, a square, and a three-dimensional cage, on Au111 surfaces were investigated by scanning tunneling microscopy. These supramolecular assemblies adsorb on Au111 surfaces and self-organize to form highly ordered adlayers with distinct conformations that are consistent with their chemical structures. The faces of the supramolecular rectangle and square lie flat on the surface, preserving their rectangle and square conformations, respectively. The three-dimensional cage also forms well-ordered adlayers on the gold surface, forming regular molecular rows of assemblies. When the rectangle and cage were mixed together, the assemblies separated into individual domains, and no mixed adlayers were observed. These results provide direct evidence of the noncrystalline solid-state structures of these assemblies and information about how they self-organize on Au111 surfaces, which is of importance in the potential manufacturing of functional nanostructures and devices.

Conceptual service architecture for adaptive mobile location services

DEFF Research Database (Denmark)

Schou, Saowanee

2008-01-01

This paper presents a conceptual service architecture for adaptive mobile location services designed to be used on the next generation wireless network. The developed service architecture consists of a set of concepts, principles, rules and guidelines for constructing, deploying, and operating...... the mobile location services. The service architecture identifies the components required to build the mobile location services and describes how these components are combined and how they should interact. As a means of exploring the developed conceptual service architecture, an illustrative case study...... of a new-concept tracking service is chosen to demonstrate the applicability of the architecture. Through the case study, the service request and response processes will be illustrated. New possible service functions provided by the developed service architecture will be examined and discussed...

Geometrical objects architecture and the mathematical sciences 1400-1800

CERN Document Server

2014-01-01

This volume explores the mathematical character of architectural practice in diverse pre- and early modern contexts. It takes an explicitly interdisciplinary approach, which unites scholarship in early modern architecture with recent work in the history of science, in particular, on the role of practice in the scientific revolution. As a contribution to architectural history, the volume contextualizes design and construction in terms of contemporary mathematical knowledge, attendant forms of mathematical practice, and relevant social distinctions between the mathematical professions. As a contribution to the history of science, the volume presents a series of micro-historical studies that highlight issues of process, materiality, and knowledge production in specific, situated, practical contexts. Our approach sees the designer’s studio, the stone-yard, the drawing floor, and construction site not merely as places where the architectural object takes shape, but where mathematical knowledge itself is depl...

Metal-organic and supramolecular architectures based on mechanically interlocked molecules

Science.gov (United States)

Fernando, Isurika Rosini

The focus of this work is on mechanically interlocked molecules (MIMs), which have unusual physicochemical and mechanical properties with potential applications in nano-scale/molecular devices and high strength materials. Rotaxanes, for example, consist of an axle-like molecule threaded through a wheel-like molecule, with bulky groups at the two ends of the axle preventing the wheel from dissociating. The position of the wheel along the axle can be switched in a controllable and reversible manner by applying external stimuli, a feature that might lead to the next generation of computers. Molecularly woven materials (MWMs), another example of molecules with mechanically interlocked features, are predicted to be unprecedentedly strong while being lightweight and flexible. With the ultimate goal of achieving control over the functioning of molecular devices in the solid state, a variety of pseudorotaxane building blocks were prepared and characterized, including a novel, rare blue-colored motif. The temperature-dependent assembly/disassembly of pseudorotaxanes was exploited for the construction of single-wavelength colorimetric temperature sensors over a 100 °C window. Pseudorotaxanes based on aromatic crown ether wheels and disubstituted 4,4'-bipyridinium axles were converted into rotaxanes upon binding to metal complexes (zinc, cadmium, mercury, copper, cobalt), and the formation of ordered crystalline arrays was studied in the solid state. The columnar organization of pseudorotaxanes by Hg2X6 2-- complexes (X = Cl, Br, I), leading to unprecedented dichroic (blue/red) rotaxane crystals, was demonstrated for the first time. From the crystal structures studied it became apparent that negatively charged metal complexes are needed for successful assembly with the positively charged pseudorotaxane units. To be able to use the more common, positively charged metal ions for rotaxane framework construction, neutral and negatively charged pseudorotaxanes were synthesized

Development of a Room Temperature SAW Methane Gas Sensor Incorporating a Supramolecular Cryptophane A Coating

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Wen Wang

2016-01-01

Full Text Available A new room temperature supra-molecular cryptophane A (CrypA-coated surface acoustic wave (SAW sensor for sensing methane gas is presented. The sensor is composed of differential resonator-oscillators, a supra-molecular CrypA coated along the acoustic propagation path, and a frequency signal acquisition module (FSAM. A two-port SAW resonator configuration with low insertion loss, single resonation mode, and high quality factor was designed on a temperature-compensated ST-X quartz substrate, and as the feedback of the differntial oscillators. Prior to development, the coupling of modes (COM simulation was conducted to predict the device performance. The supramolecular CrypA was synthesized from vanillyl alcohol using a double trimerisation method and deposited onto the SAW propagation path of the sensing resonators via different film deposition methods. Experiential results indicate the CrypA-coated sensor made using a dropping method exhibits higher sensor response compared to the unit prepared by the spinning approach because of the obviously larger surface roughness. Fast response and excellent repeatability were observed in gas sensing experiments, and the estimated detection limit and measured sensitivity are ~0.05% and ~204 Hz/%, respectively.

Architectural fragments

DEFF Research Database (Denmark)

Bang, Jacob Sebastian

2018-01-01

I have created a large collection of plaster models: a collection of Obstructions, errors and opportunities that may develop into architecture. The models are fragments of different complex shapes as well as more simple circular models with different profiling and diameters. In this contect I have....... I try to invent the ways of drawing the models - that decode and unfold them into architectural fragments- into future buildings or constructions in the landscape. [1] Luigi Moretti: Italian architect, 1907 - 1973 [2] Man Ray: American artist, 1890 - 1976. in 2015, I saw the wonderful exhibition...... "Man Ray - Human Equations" at the Glyptotek in Copenhagen, organized by the Philips Collection in Washington D.C. and the Israel Museum in Jerusalem (in 2013). See also: "Man Ray - Human Equations" catalogue published by Hatje Cantz Verlag, Germany, 2014....

Biomedical laboratories: architecture and radioprotection principles

International Nuclear Information System (INIS)

Lapa, Renata

2005-01-01

In institutions where biological research are made and some technologies make use of radioisotope, the radiation protection is an issue of biosecurity for conceptual reasons. In the process of architectural design of Biomedical Laboratories, engineering and architecture reveal interfaces with other areas of knowledge and specific concepts. Exploring the role of architectural design in favor of personal and environmental protection in biological containment laboratories that handle non-sealed sources in research, the work discusses the triad that compose the principle of containment in health environments: best practices, protective equipment, physical facilities, with greater emphasis on the latter component. The shortcomings of the design process are reflected in construction and in use-operation and maintenance of these buildings, with direct consequences on the occupational health and safety, environmental and credibility of work processes. In this context, the importance of adoption of alternatives to improve the design process is confirmed, taking into account the early consideration of several variables involved and providing subsidies to the related laboratories . The research, conducted at FIOCRUZ - a Brazilian health institution, developed from the analysis of the participants in the architectural project, aiming at the formulation of design guidelines which could contribute to the rationalisation of this kind of building construction

Statics of historic masonry constructions

CERN Document Server

Como, Mario

2016-01-01

This successful book, which is now appearing in its second edition, presents a comprehensive new Statics of Masonry Constructions. Masonry constructions are the great majority of the buildings in Europe’s historic centres and the most important monuments in its architectural heritage. Given the age of these constructions, the demand for safety assessments and restoration projects is pressing and constant. The book you hold in hands contributes to fill this demand. The second edition integrates the original text of the first edition with new developments, widening and revisions, due to recent research studies achievements. The result is a book that gives a complete picture of the behaviour of the Masonry Constructions. First of all, it gives the fundamentals of its Statics, based on the no-tension assumption, and then it develops the Limit Analysis for the Masonry Constructions. In this framework, through an interdisciplinary approach combining Engineering and Architecture, the book also investigates the sta...

Preserving urban objects of historicaland architectural heritage

Directory of Open Access Journals (Sweden)

Bal'zannikova Ekaterina Mikhailovna

2014-01-01

Full Text Available Large cities of central Russia were built under the influence of the factors that played an important role in protecting their population; natural resources and opportunities for trading were also essential. The industrial development and construction of large industrial facilities were significant for the formation of urban environment. As a result architectural monuments of great historical value that have a significant influence on the formation of the modern city image were preserved.Nowadays, a great number of buildings of historical and architectural heritage turned out to be in poor condition. Funding and its efficient use are rational means of saving the most valuable objects of historical and cultural heritage. In order to do this it is necessary to solve the problems of developing complex and effective measures for preserving these objectsThe existing method of preserving urban objects does not focus on urban architectural objects of historical and architectural value. It does not cover the study of urban development features in architectural and town-planning environment surrounding this object, it does not determine the historical and architectural value of the object and it does not identify the relationship of the object and the surrounding objects as well as architectural frame of the total area. That is why the existing method cannot be considered an appropriate system for preserving the objects of historical and architectural heritage.In order to avoid the disadvantages mentioned above and to increase tourist interest to the architecturally valuable buildings in urban areas, the author has proposed a complex approach to improve the method of reconstructing urban objects of great historical and architectural significance.The existing method of preserving historical objects includes the preparatory period of studying the degree of historical and architectural heritage wear and decay, developing the techniques for strengthening

Toward a Fault Tolerant Architecture for Vital Medical-Based Wearable Computing.

Science.gov (United States)

Abdali-Mohammadi, Fardin; Bajalan, Vahid; Fathi, Abdolhossein

2015-12-01

Advancements in computers and electronic technologies have led to the emergence of a new generation of efficient small intelligent systems. The products of such technologies might include Smartphones and wearable devices, which have attracted the attention of medical applications. These products are used less in critical medical applications because of their resource constraint and failure sensitivity. This is due to the fact that without safety considerations, small-integrated hardware will endanger patients' lives. Therefore, proposing some principals is required to construct wearable systems in healthcare so that the existing concerns are dealt with. Accordingly, this paper proposes an architecture for constructing wearable systems in critical medical applications. The proposed architecture is a three-tier one, supporting data flow from body sensors to cloud. The tiers of this architecture include wearable computers, mobile computing, and mobile cloud computing. One of the features of this architecture is its high possible fault tolerance due to the nature of its components. Moreover, the required protocols are presented to coordinate the components of this architecture. Finally, the reliability of this architecture is assessed by simulating the architecture and its components, and other aspects of the proposed architecture are discussed.

Energy and architecture. [Denmark]; Energi + arkitektur

Energy Technology Data Exchange (ETDEWEB)

Lehrskov, H. [Ingenioerhoejskolen i Aarhus, Aarhus (Denmark); Oehlenschlaeger, R. [AplusB, Aarhus (Denmark); Kappel, K. [Solar City Copenhagen, Copenhagen (Denmark); Kleis, B. [Arkitekturformidling.dk, Vanloese (Denmark); Klint, J. [Kuben Management, Aarhus (Denmark); Vejsig Pedersen, P. [Cenergia, Herlev (Denmark)

2011-07-01

The book presents the best examples of Danish energy-oriented architecture with a focus on architectural and energy measures in the integrated design process, resulting in architectural quality. The book consists of two parts and consists first of an introduction to the challenges and tools within low-energy buildings, and then a catalog of a wide range of building projects in the categories of housing, business, education, institutions and sports. The book contains examples of new buildings that as a minimum meet the requirements of the building codes LE1, BR08. The book also contains suggestions for renovation projects that meet LE2 BR08, as the energy optimization of the existing building stock is an imminent task with great constructional and aesthetic challenges. The selected projects are designed and built in the period 2009 to 2011 and include both everyday architecture, created under highly competitive economic environment, as more exclusive development projects. The objectives of the projects are often higher than required by the building code, and in many projects measurements were made to find out what works. These examples show that the stricter energy requirements can serve as inspiration for a holistic architecture and contribute to a paradigm shift in the cooperation process between the project parties. But it is also clear that it requires a focused commitment of all players in the construction industry - clients, consultants, contractors and building product manufacturers - to reduce energy consumption significantly. (LN)

A Ferrocene-Based Catecholamide Ligand: the Consequences of Ligand Swivel for Directed Supramolecular Self-Assembly

Energy Technology Data Exchange (ETDEWEB)

Mugridge, Jeffrey; Fiedler, Dorothea; Raymond, Kenneth

2010-02-04

A ferrocene-based biscatecholamide ligand was prepared and investigated for the formation of metal-ligand supramolecular assemblies with different metals. Reaction with Ge(IV) resulted in the formation of a variety of Ge{sub n}L{sub m} coordination complexes, including [Ge{sub 2}L{sub 3}]{sup 4-} and [Ge{sub 2}L{sub 2}({mu}-OMe){sub 2}]{sup 2-}. The ligand's ability to swivel about the ferrocenyl linker and adopt different conformations accounts for formation of many different Ge{sub n}L{sub m} species. This study demonstrates why conformational ligand rigidity is essential in the rational design and directed self-assembly of supramolecular complexes.

The Supramolecular Organization of a Peptide-Based Nanocarrier at High Molecular Detail

NARCIS (Netherlands)

Rad-Malekshahi, Mazda; Visscher, Koen M.; Rodrigues, João P.G.L.M.; De Vries, Renko; Hennink, Wim E.; Baldus, Marc; Bonvin, Alexandre M.J.J.; Mastrobattista, Enrico; Weingarth, Markus

2015-01-01

Nanovesicles self-assembled from amphiphilic peptides are promising candidates for applications in drug delivery. However, complete high-resolution data on the local and supramolecular organization of such materials has been elusive thus far, which is a substantial obstacle to their rational design.

Democratic management and architecture school

Directory of Open Access Journals (Sweden)

Silvana Aparecida de Souza

2011-10-01

Full Text Available It is a conceptual and theoretical research on school organization and its democratization, focusing on one aspect of an objective nature: its architecture. The study was based on the academic literature on democratization and theoretical contribution of Michel Foucault, with regard to the analysis of space as a resourcecontrol, surveillance and training, going through a historical review of the modelconstruction of school buildings in Brazil. It is therefore a sociological analysis of the school environment, in relation to the democratization process of basic education, understood as ensuring that the conditions of access and permanence to a universalquality education, and conceived and gestated from collective interests of its users.We conclude that the architecture of public schools in Brazil do not provides democratic management, either by format controller of buildings constructed in the republican period, either by the current economic priority for the construction of public school buildings, which includes little or no space for collective activities. The character of the buildings remains controller, no more for its architecture, but made possible by technological development, which allows monitoring by video cameras, which is made with the permission and support of community.

Rapid fabrication of hierarchically structured supramolecular nanocomposite thin films in one minute

Energy Technology Data Exchange (ETDEWEB)

Xu, Ting; Kao, Joseph

2016-11-08

Functional nanocomposites containing nanoparticles of different chemical compositions may exhibit new properties to meet demands for advanced technology. It is imperative to simultaneously achieve hierarchical structural control and to develop rapid, scalable fabrication to minimize degradation of nanoparticle properties and for compatibility with nanomanufacturing. The assembly kinetics of supramolecular nanocomposite in thin films is governed by the energetic cost arising from defects, the chain mobility, and the activation energy for inter-domain diffusion. By optimizing only one parameter, the solvent fraction in the film, the assembly kinetics can be precisely tailored to produce hierarchically structured thin films of supramolecular nanocomposites in approximately one minute. Moreover, the strong wavelength dependent optical anisotropy in the nanocomposite highlights their potential applications for light manipulation and information transmission. The present invention opens a new avenue in designing manufacture-friendly continuous processing for the fabrication of functional nanocomposite thin films.

Geometric Computing for Freeform Architecture

KAUST Repository

Wallner, J.; Pottmann, Helmut

2011-01-01

Geometric computing has recently found a new field of applications, namely the various geometric problems which lie at the heart of rationalization and construction-aware design processes of freeform architecture. We report on our work in this area

A novel Rapid Additive Manufacturing concept for architectural composite shell construction inspired by the shell formation in land snails.

Science.gov (United States)

Felbrich, Benjamin; Wulle, Frederik; Allgaier, Christoph; Menges, Achim; Verl, Alexander; Wurst, Karl-Heinz; Nebelsick, James

2018-01-04

State of the art rapid additive manufacturing (RAM), specifically Fused Filament Fabrication (FFF) has gained popularity among architects, engineers and designers for quick prototyping of technical devices, rapid production of small series and even construction scale fabrication of architectural elements. The spectrum of producible shapes and the resolution of detail, however, are determined and constrained by the layer-based nature of the fabrication process. These aspects significantly limit FFF-based approaches for the prefabrication and in-situ fabrication of freeform shells at the architectural scale. Snails exhibit a shell building process that suggests ways to overcome these limits. They produce a soft, pliable proteinaceous film - the periostracum - which later hardens and serves, among other functions, as a form-giving surface for an inner calcium carbonate layer. Snail shell formation behavior is interpreted from a technical point of view to extract potentially useful aspects for a biomimetic transfer. A RAM concept for continuous extrusion of thin free form composite shells inspired by the snail shell formation is presented. © 2018 IOP Publishing Ltd.

From metal-organic squares to porous zeolite-like supramolecular assemblies

KAUST Repository

Wang, Shuang

2010-12-29

We report the synthesis, structure, and characterization of two novel porous zeolite-like supramolecular assemblies, ZSA-1 and ZSA-2, having zeolite gis and rho topologies, respectively. The two compounds were assembled from functional metal-organic squares (MOSs) via directional hydrogen-bonding interactions and exhibited permanent microporosity and thermal stability up to 300 °C. © 2010 American Chemical Society.

Proteins evolve on the edge of supramolecular self-assembly

Science.gov (United States)

Garcia-Seisdedos, Hector; Empereur-Mot, Charly; Elad, Nadav; Levy, Emmanuel D.

2017-08-01

The self-association of proteins into symmetric complexes is ubiquitous in all kingdoms of life. Symmetric complexes possess unique geometric and functional properties, but their internal symmetry can pose a risk. In sickle-cell disease, the symmetry of haemoglobin exacerbates the effect of a mutation, triggering assembly into harmful fibrils. Here we examine the universality of this mechanism and its relation to protein structure geometry. We introduced point mutations solely designed to increase surface hydrophobicity among 12 distinct symmetric complexes from Escherichia coli. Notably, all responded by forming supramolecular assemblies in vitro, as well as in vivo upon heterologous expression in Saccharomyces cerevisiae. Remarkably, in four cases, micrometre-long fibrils formed in vivo in response to a single point mutation. Biophysical measurements and electron microscopy revealed that mutants self-assembled in their folded states and so were not amyloid-like. Structural examination of 73 mutants identified supramolecular assembly hot spots predictable by geometry. A subsequent structural analysis of 7,471 symmetric complexes showed that geometric hot spots were buffered chemically by hydrophilic residues, suggesting a mechanism preventing mis-assembly of these regions. Thus, point mutations can frequently trigger folded proteins to self-assemble into higher-order structures. This potential is counterbalanced by negative selection and can be exploited to design nanomaterials in living cells.

Self assembly of amphiphilic C60 fullerene derivatives into nanoscale supramolecular structures

Directory of Open Access Journals (Sweden)

Casscells S Ward

2007-08-01

Full Text Available Abstract Background The amphiphilic fullerene monomer (AF-1 consists of a "buckyball" cage to which a Newkome-like dendrimer unit and five lipophilic C12 chains positioned octahedrally to the dendrimer unit are attached. In this study, we report a novel fullerene-based liposome termed 'buckysome' that is water soluble and forms stable spherical nanometer sized vesicles. Cryogenic electron microscopy (Cryo-EM, transmission electron microscopy (TEM, and dynamic light scattering (DLS studies were used to characterize the different supra-molecular structures readily formed from the fullerene monomers under varying pH, aqueous solvents, and preparative conditions. Results Electron microscopy results indicate the formation of bilayer membranes with a width of ~6.5 nm, consistent with previously reported molecular dynamics simulations. Cryo-EM indicates the formation of large (400 nm diameter multilamellar, liposome-like vesicles and unilamellar vesicles in the size range of 50–150 nm diameter. In addition, complex networks of cylindrical, tube-like aggregates with varying lengths and packing densities were observed. Under controlled experimental conditions, high concentrations of spherical vesicles could be formed. In vitro results suggest that these supra-molecular structures impose little to no toxicity. Cytotoxicity of 10–200 μM buckysomes were assessed in various cell lines. Ongoing studies are aimed at understanding cellular internalization of these nanoparticle aggregates. Conclusion In this current study, we have designed a core platform based on a novel amphiphilic fullerene nanostructure, which readily assembles into supra-molecular structures. This delivery vector might provide promising features such as ease of preparation, long-term stability and controlled release.

Hydrodynamic and Thermophoretic Effects on the Supramolecular Chirality of Pyrene-Derived Nanosheets.

Science.gov (United States)

Micali, Norberto; Vybornyi, Mykhailo; Mineo, Placido; Khorev, Oleg; Häner, Robert; Villari, Valentina

2015-06-22

Chiroptical properties of two-dimensional (2D) supramolecular assemblies (nanosheets) of achiral, charged pyrene trimers (Py3 ) are rendered chiral by asymmetric physical perturbations. Chiral stimuli in a cuvette can originate either from controlled temperature gradients or by very gentle stirring. The chiroptical activity strongly depends on the degree of supramolecular order of the nanosheets, which is easily controlled by the method of preparation. The high degree of structural order ensures strong cooperative effects within the aggregates, rendering them more susceptible to external stimuli. The samples prepared by using slow thermal annealing protocols are both CD and LD active (in stagnant and stirred solutions), whereas for isothermally aged samples chiroptical activity was in all cases undetectable. In the case of temperature gradients, the optical activity of 2D assemblies could be recorded for a stagnant solution due to migration of the aggregates from the hottest to the coldest regions of the system. However, a considerably stronger exciton coupling, coinciding with the J-band of the interacting pyrenes, is developed upon subtle vortexing (0.5 Hz, 30 rpm) of the aqueous solution of the nanosheets. The sign of the exciton coupling is inverted upon switching between clockwise and counter-clockwise rotation. The supramolecular chirality is evidenced by the appearance of CD activity. To exclude artefacts from proper CD spectra, the contribution from LD to the observed CD was determined. The data suggest that the aggregates experience asymmetrical deformation and alignment effects because of the presence of chiral flows. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Architecture of Brazil 1900-1990

CERN Document Server

Segawa, Hugo

2013-01-01

Architecture of Brazil: 1900-1990 examines the processes that underpin modern Brazilian architecture under various influences and characterizes different understandings of modernity, evident in the chapter topics of this book. Accordingly, the author does not give overall preference to particular architects nor works, with the exception of a few specific works and architects, including Warchavchik, Niemeyer, Lucio Costa, and Vilanova Artigas. In summary, this book: Meticulously examines the controversies, achievements, and failures in constructing spaces, buildings, and cities in a dynamic country Gives a broad view of Brazilian architecture in the twentieth century Proposes a reinterpretation of the varied approaches of the modern movement up to the Second World War Analyzes ideological impacts of important Brazilian architects including Oscar Niemeyer, Lucio Costa and Vilanova Artigas Discusses work of expatriate architects in Brazil Features over 140 illustrations In Architecture of Brazil: 1900-1990, S...

Prion-like nanofibrils of small molecules (PriSM): A new frontier at the intersection of supramolecular chemistry and cell biology.

Science.gov (United States)

Zhou, Jie; Du, Xuewen; Xu, Bing

2015-01-01

Formed by non-covalent interactions and not defined at genetic level, the assemblies of small molecules in biology are complicated and less explored. A common morphology of the supramolecular assemblies of small molecules is nanofibrils, which coincidentally resembles the nanofibrils formed by proteins such as prions. So these supramolecular assemblies are termed as prion-like nanofibrils of small molecules (PriSM). Emerging evidence from several unrelated fields over the past decade implies the significance of PriSM in biology and medicine. This perspective aims to highlight some recent advances of the research on PriSM. This paper starts with description of the intriguing similarities between PriSM and prions, discusses the paradoxical features of PriSM, introduces the methods for elucidating the biological functions of PriSM, illustrates several examples of beneficial aspects of PriSM, and finishes with the promises and current challenges in the research of PriSM. We anticipate that the research of PriSM will contribute to the fundamental understanding at the intersection of supramolecular chemistry and cell biology and ultimately lead to a new paradigm of molecular (or supramolecular) therapeutics for biomedicine.

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

NARCIS (Netherlands)

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

A striking feature of living systems is their ability to produce motility by amplification of collective molecular motion from the nanoscale up to macroscopic dimensions. Some of nature's protein motors, such as myosin in muscle tissue, consist of a hierarchical supramolecular assembly of very large

Drastic symmetry breaking in supramolecular organization of enantiomerically unbalanced monolayers at surfaces

NARCIS (Netherlands)

Haq, S.; Liu, N.; Humblot, V.; Jansen, A.P.J.; Raval, R.

2009-01-01

There is considerable interest in skewing the transmission of chirality, or 'handedness', from the molecular to the supramolecular level so that single-handed superstructures are created from mixed enantiomer systems. One approach is to flip the chirality of all the molecular building blocks to the

Architectural Geometry and Fabrication-Aware Design

KAUST Repository

Pottmann, Helmut

2013-04-27

Freeform shapes and structures with a high geometric complexity play an increasingly important role in contemporary architecture. While digital models are easily created, the actual fabrication and construction remains a challenge. This is the source of numerous research problems many of which fall into the area of Geometric Computing and form part of a recently emerging research area, called "Architectural Geometry". The present paper provides a short survey of research in Architectural Geometry and shows how this field moves towards a new direction in Geometric Modeling which aims at combining shape design with important aspects of function and fabrication. © 2013 Kim Williams Books, Turin.

Supramolecular Ferric Porphyrins as Cyanide Receptors in Aqueous Solution

Science.gov (United States)

2011-01-01

All fundamental data about binding of the cyanide to a supramolecular complex composed of a per-O-methylated β-cyclodextrin dimer having an imidazole linker (Im3CD) and an anionic ferric porphyrin (Fe(III)TPPS) indicate that the Fe(III)TPPS/Im3CD complex is much better as an cyanide receptor in vivo than hydroxocobalamin, whose cyanide binding ability is lowered by its strong binding to serum proteins in the blood. PMID:24900285

Temporality and Memory in Architecture: Hagia Sophia

Directory of Open Access Journals (Sweden)

Yüksel Burçin Nur

2017-12-01

Full Text Available Istanbul, having hosted many civilizations and cultures, has a long and important past. Due to its geopolitical locations, the city has been the capital of two civilizations—Ottoman and Byzantine Empires—which left its traces in the history of the world. Architectural and symbolic monuments built by these civilizations made an impression in all communities making the city a center of attraction. After each and every damage caused by wars, civil strifes, and natural disasters, maximum effort has been made to restore these symbolic buildings. Attitude of a society to a piece of art or an architectural construction defined as historical artifact is shown in interventions, architectural supplementations and restorations to buildings to keep them alive. As a result of this attitude, it is accepted that buildings are perceived as a place of memory and symbolized with the city. The most important symbolic monument of the city, Ayasofya (Hagia Sophia, was found as the Church of the Byzantine Emperor in the year 360, then converted into the Mosque of the Ottoman Sultan, and now serves as one of the best-known museums of Turkey. With architectural additions requested by Byzantine emperors and Ottoman sultans, restorations and other functional changes; Hagia Sophia had become a monument witnessing its own changes as well as its surroundings while collecting memories. Accordingly, Hagia Sophia can be described as an immortal building.  Immortality is out of time notion, however it is a reflection of time effects as well. Immortality is about resisting to time. A construction from the past which appreciates as time passes will also exist in the future preserving its value. The building has been strengthened with the memory phenomenon formed during construction, incidents that the building witnessed in its location, restorations, architectural supplementations and the perception of the world heritage. The main purpose of this presentation is to show how

Metal-driven and covalent synthesis of supramolecular grids from racks: a convergent approach to heterometallic and heteroleptic nanostructures.

Science.gov (United States)

Schmittel, Michael; Kalsani, Venkateshwarlu; Bats, Jan W

2005-06-13

Supramolecular nanogrids were prepared from dynamic supramolecular racks through the coupling of terminal alkynes using either a covalent (with CuCl/O(2)) or a coordinative (with [trans-(PEt(3))(2)PtCl(2)]) approach. Because of the rapid equilibration of the racks (as tested by exchange reactions), oligomeric adducts potentially formed in the coupling process will selectively furnish the nanogrids through an entropically driven self-repair mechanism. To ascertain the structural assignment, the nanogrids were also synthesized by an independent strategy.

Public buildings architecture built between 1868 until 1900: Part one

Directory of Open Access Journals (Sweden)

Roter-Blagojević Mirjana Z.

2003-01-01

Full Text Available The main transformation courses in Serbia and its capital have been portrayed covering the period of the 19th century's last three decades, i.e. the aftermath of the partial national liberation from the centuries lasting Turkish occupation. Political and economic changes in the princedom and later the kingdom of Serbia prompted the capital's swift transformation and the construction of numerous edifices, especially those accommodating government or public institutions. The construction of the Royal Theatre several Ministries, schools, hotels and other public edifices brought to the capital the new building spirit clearly influenced by the European historic style architecture. Through a chronological overview of the major stateowned and public edifices construction and their architectural form analyses, some key characteristics of this period's architecture in Serbia have been elucidated, with reference to some authors` importance and their relationship with the European building art. The emphasis is put on the reflection of certain phases, which the architectural form had undergone at the end of the 19th century. The changes became manifest through the permanent enrichment of the architectural expression and the construction advancement, thereby achieving the European centers standing. The creation of closer links with the adjacent neighborhoods, namely Zemun and Pancevo and subsequently with the broader European surroundings, particularly Budapest and Vienna, where most of the authors came from, introduced the European academic architecture spirit into Serbian architecture. However, in the first period, analysed in part one of this study, by the end of the 60s and during the 70s of the 19th century, because of adverse political and economic times, only a fairly small number of public edifices were built. Distinguished are the Theatre at the Stambol Gate, the new hotel at the Serbian Crown, and the hotel Russia, in whose formal expression the

Supramolecular nanoparticles generated by the self-assembly of polyrotaxanes for antitumor drug delivery

Directory of Open Access Journals (Sweden)

Liu R

2012-10-01

Full Text Available Rong Liu,1,2,* Yusi Lai,1,* Bin He,1 Yuan Li,1 Gang Wang,1 Shuang Chang,1 Zhongwei Gu1 1National Engineering Research Center for Biomaterials, Sichuan University, Chengdu, China; 2Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China*These authors contributed equally to this paperAbstract: A new approach of fabricating supramolecular nanoparticles generated by self-assembly polyrotaxanes for antitumor drug delivery has been reported. Cinnamic-acid-modified poly(ethylene glycol chains were threaded in a-cyclodextrins to form polyrotaxanes. The polyrotaxanes self-assembled supramolecular nanoparticles. The morphology of the nanoparticles was changed from nanovesicle to micelle after the antitumor drug, doxorubicin, was loaded. The release profile of the drug-loaded nanoparticles was investigated, and it was found that the sustaining release time could last for 32 hours. The drug-loaded nanoparticles were co-cultured with mouse 4T1 breast cancer cells with a drug concentration of 10 µg/mL; the cell survival rate was 3.3% after a 72-hour incubation. In an in vivo study of breast cancer in a mouse model, the drug-loaded nanoparticles were injected in the tail veins of mice with a dose of 5 mg/kg body weight. The tumor inhibition rate of drug-loaded nanoparticles was 53%, which was better than that of doxorubicin hydrochloride. The cardiac toxicity of doxorubicin was decreased greatly after the encapsulation into supramolecular polyrotaxane nanoparticles.Keywords: polyrotaxane, self-assembly, nanoparticle, doxorubicin, supermolecular

Future city architecture for optimal living

CERN Document Server

Pardalos, Panos

2015-01-01

  This book offers a wealth of interdisciplinary approaches to urbanization strategies in architecture centered on growing concerns about the future of cities and their impacts on essential elements of architectural optimization, livability, energy consumption and sustainability. It portrays the urban condition in architectural terms, as well as the living condition in human terms, both of which can be optimized by mathematical modeling as well as mathematical calculation and assessment.   Special features include:   ·        new research on the construction of future cities and smart cities   ·        discussions of sustainability and new technologies designed to advance ideas to future city developments   Graduate students and researchers in architecture, engineering, mathematical modeling, and building physics will be engaged by the contributions written by eminent international experts from a variety of disciplines including architecture, engineering, modeling, optimization, and relat...

Growth anomalies in supramolecular networks: 4,4'-biphenyldicarboxylic acid on Cu(001)

NARCIS (Netherlands)

Schwarz, Daniel; van Gastel, Raoul; Zandvliet, Henricus J.W.; Poelsema, Bene

2013-01-01

We have used low energy electron microscopy to demonstrate how the interaction of 4,4 ′ -biphenyldicarboxylic acid (BDA) molecules with (steps on) the Cu(001) surface determines the structure of supramolecular BDA networks on a mesoscopic length scale. Our in situ real time observations reveal that

Supramolecular Chirality: Solvent Chirality Transfer in Molecular Chemistry and Polymer Chemistry

Directory of Open Access Journals (Sweden)

Michiya Fujiki

2014-08-01

Full Text Available Controlled mirror symmetry breaking arising from chemical and physical origin is currently one of the hottest issues in the field of supramolecular chirality. The dynamic twisting abilities of solvent molecules are often ignored and unknown, although the targeted molecules and polymers in a fluid solution are surrounded by solvent molecules. We should pay more attention to the facts that mostly all of the chemical and physical properties of these molecules and polymers in the ground and photoexcited states are significantly influenced by the surrounding solvent molecules with much conformational freedom through non-covalent supramolecular interactions between these substances and solvent molecules. This review highlights a series of studies that include: (i historical background, covering chiral NaClO3 crystallization in the presence of d-sugars in the late 19th century; (ii early solvent chirality effects for optically inactive chromophores/fluorophores in the 1960s–1980s; and (iii the recent development of mirror symmetry breaking from the corresponding achiral or optically inactive molecules and polymers with the help of molecular chirality as the solvent use quantity.

Enhancing SERS by Means of Supramolecular Charge Transfer

Science.gov (United States)

Wong, Eric; Flood, Amar; Morales, Alfredo

2009-01-01

In a proposed method of sensing small quantities of molecules of interest, surface enhanced Raman scattering (SERS) spectroscopy would be further enhanced by means of intermolecular or supramolecular charge transfer. There is a very large potential market for sensors based on this method for rapid detection of chemical and biological hazards. In SERS, the Raman signals (vibrational spectra) of target molecules become enhanced by factors of the order of 108 when those molecules are in the vicinities of nanostructured substrate surfaces that have been engineered to have plasmon resonances that enhance local electric fields. SERS, as reported in several prior NASA Tech Briefs articles and elsewhere, has remained a research tool and has not yet been developed into a practical technique for sensing of target molecules: this is because the short range (5 to 20 nm) of the field enhancement necessitates engineering of receptor molecules to attract target molecules to the nanostructured substrate surfaces and to enable reliable identification of the target molecules in the presence of interferants. Intermolecular charge-transfer complexes have been used in fluorescence-, photoluminescence-, and electrochemistry-based techniques for sensing target molecules, but, until now, have not been considered for use in SERS-based sensing. The basic idea of the proposed method is to engineer receptor molecules that would be attached to nanostructured SERS substrates and that would interact with the target molecules to form receptor-target supramolecular charge-transfer complexes wherein the charge transfer could be photoexcited.

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

Science.gov (United States)

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

2018-02-01

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

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

Science.gov (United States)

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

2018-02-01

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

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

Science.gov (United States)

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

2017-12-01

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

Layered Architecture for Quantum Computing

Directory of Open Access Journals (Sweden)

N. Cody Jones

2012-07-01

Full Text Available We develop a layered quantum-computer architecture, which is a systematic framework for tackling the individual challenges of developing a quantum computer while constructing a cohesive device design. We discuss many of the prominent techniques for implementing circuit-model quantum computing and introduce several new methods, with an emphasis on employing surface-code quantum error correction. In doing so, we propose a new quantum-computer architecture based on optical control of quantum dots. The time scales of physical-hardware operations and logical, error-corrected quantum gates differ by several orders of magnitude. By dividing functionality into layers, we can design and analyze subsystems independently, demonstrating the value of our layered architectural approach. Using this concrete hardware platform, we provide resource analysis for executing fault-tolerant quantum algorithms for integer factoring and quantum simulation, finding that the quantum-dot architecture we study could solve such problems on the time scale of days.

Design of low-power coarse-grained reconfigurable architectures

CERN Document Server

Kim, Yoonjin

2010-01-01

Coarse-grained reconfigurable architecture (CGRA) has emerged as a solution for flexible, application-specific optimization of embedded systems. Helping you understand the issues involved in designing and constructing embedded systems, Design of Low-Power Coarse-Grained Reconfigurable Architectures offers new frameworks for optimizing the architecture of components in embedded systems in order to decrease area and save power. Real application benchmarks and gate-level simulations substantiate these frameworks.The first half of the book explains how to reduce power in the configuration cache. T

Ligand Bridging-Angle-Driven Assembly of Molecular Architectures Based on Quadruply Bonded Mo-Mo Dimers

Energy Technology Data Exchange (ETDEWEB)

Li, Jian-Rong; Yakovenko, Andrey A; Lu, Weigang; Timmons, Daren J; Zhuang, Wenjuan; Yuan, Daqiang; Zhou, Hong-Cai

2010-12-15

A systematic exploration of the assembly of Mo₂(O₂C-)₄-based metal–organic molecular architectures structurally controlled by the bridging angles of rigid organic linkers has been performed. Twelve bridging dicarboxylate ligands were designed to be of different sizes with bridging angles of 0, 60, 90, and 120° while incorporating a variety of nonbridging functional groups, and these ligands were used as linkers. These dicarboxylate linkers assemble with quadruply bonded Mo–Mo clusters acting as nodes to give 13 molecular architectures, termed metal–organic polygons/polyhedra with metal cluster node arrangements of a linear shape, triangle, octahedron, and cuboctahedron/anti-cuboctahedron. The syntheses of these complexes have been optimized and their structures determined by single-crystal X-ray diffraction. The results have shown that the shape and size of the resulting molecular architecture can be controlled by tuning the bridging angle and size of the linker, respectively. Functionalization of the linker can adjust the solubility of the ensuing molecular assembly but has little or no effect on the geometry of the product. Preliminary gas adsorption, spectroscopic, and electrochemical properties of selected members were also studied. The present work is trying to enrich metal-containing supramolecular chemistry through the inclusion of well-characterized quadruply bonded Mo–Mo units into the structures, which can widen the prospect of additional electronic functionality, thereby leading to novel properties.

Ligand bridging-angle-driven assembly of molecular architectures based on quadruply bonded Mo-Mo dimers.

Science.gov (United States)

Li, Jian-Rong; Yakovenko, Andrey A; Lu, Weigang; Timmons, Daren J; Zhuang, Wenjuan; Yuan, Daqiang; Zhou, Hong-Cai

2010-12-15

A systematic exploration of the assembly of Mo2(O2C-)4-based metal-organic molecular architectures structurally controlled by the bridging angles of rigid organic linkers has been performed. Twelve bridging dicarboxylate ligands were designed to be of different sizes with bridging angles of 0, 60, 90, and 120° while incorporating a variety of nonbridging functional groups, and these ligands were used as linkers. These dicarboxylate linkers assemble with quadruply bonded Mo-Mo clusters acting as nodes to give 13 molecular architectures, termed metal-organic polygons/polyhedra with metal cluster node arrangements of a linear shape, triangle, octahedron, and cuboctahedron/anti-cuboctahedron. The syntheses of these complexes have been optimized and their structures determined by single-crystal X-ray diffraction. The results have shown that the shape and size of the resulting molecular architecture can be controlled by tuning the bridging angle and size of the linker, respectively. Functionalization of the linker can adjust the solubility of the ensuing molecular assembly but has little or no effect on the geometry of the product. Preliminary gas adsorption, spectroscopic, and electrochemical properties of selected members were also studied. The present work is trying to enrich metal-containing supramolecular chemistry through the inclusion of well-characterized quadruply bonded Mo-Mo units into the structures, which can widen the prospect of additional electronic functionality, thereby leading to novel properties.

A chiroptical switch based on supramolecular chirality transfer through alkyl chain entanglement and dynamic covalent bonding.

Science.gov (United States)

Lv, Kai; Qin, Long; Wang, Xiufeng; Zhang, Li; Liu, Minghua

2013-12-14

Chirality transfer is an interesting phenomenon in Nature, which represents an important step to understand the evolution of chiral bias and the amplification of the chirality. In this paper, we report the chirality transfer via the entanglement of the alkyl chains between chiral gelator molecules and achiral amphiphilic Schiff base. We have found that although an achiral Schiff base amphiphile could not form organogels in any kind of organic solvents, it formed co-organogels when mixed with a chiral gelator molecule. Interestingly, the chirality of the gelator molecules was transferred to the Schiff base chromophore in the mixed co-gels and there was a maximum mixing ratio for the chirality transfer. Furthermore, the supramolecular chirality was also produced based on a dynamic covalent chemistry of an imine formed by the reaction between an aldehyde and an amine. Such a covalent bond of imine was formed reversibly depending on the pH variation. When the covalent bond was formed the chirality transfer occurred, when it was destroyed, the transfer stopped. Thus, a supramolecular chiroptical switch is obtained based on supramolecular chirality transfer and dynamic covalent chemistry.

Supramolecular binding and release of sulfide and hydrosulfide anions in water.

Science.gov (United States)

Vázquez, J; Sindelar, V

2018-06-05

Hydrogen sulfide (H2S) has become an important target for research due to its physiological properties as well as its potential applications in medicine. In this work, supramolecular binding of sulfide (S2-) and hydrosulfide (HS-) anions in water is presented for the first time. Bambusurils were used to slow down the release of these anions in water.

41 CFR 102-76.60 - To which facilities does the Architectural Barriers Act apply?

Science.gov (United States)

2010-07-01

... PROPERTY 76-DESIGN AND CONSTRUCTION Architectural Barriers Act § 102-76.60 To which facilities does the Architectural Barriers Act apply? (a) The Architectural Barriers Act applies to any facility that is intended... the Architectural Barriers Act apply? 102-76.60 Section 102-76.60 Public Contracts and Property...

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

NARCIS (Netherlands)

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

2015-01-01

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

Islamic Architecture and Arch

Directory of Open Access Journals (Sweden)

Mohammed Mahbubur Rahman

2015-01-01

Full Text Available The arch, an essential architectural element since the early civilizations, permitted the construction of lighter walls and vaults, often covering a large span. Visually it was an important decorative feature that was trans-mitted from architectural decoration to other forms of art worldwide. In early Islamic period, Muslims were receiving from many civilizations, which they improved and re-introduced to bring about the Renaissance. Arches appeared in Mesopotamia, Indus, Egyptian, Babylonian, Greek and Assyrian civilizations; but the Romans applied the technique to a wide range of structures. The Muslims mastered the use and design of the arch, employed for structural and functional purposes, progressively meeting decorative and symbolic pur-poses. Islamic architecture is characterized by arches employed in all types of buildings; most common uses being in arcades. This paper discusses the process of assimilation and charts how they contributed to other civilizations.

Geometric Rationalization for Freeform Architecture

KAUST Repository

Jiang, Caigui

2016-06-20

The emergence of freeform architecture provides interesting geometric challenges with regards to the design and manufacturing of large-scale structures. To design these architectural structures, we have to consider two types of constraints. First, aesthetic constraints are important because the buildings have to be visually impressive. Sec- ond, functional constraints are important for the performance of a building and its e cient construction. This thesis contributes to the area of architectural geometry. Specifically, we are interested in the geometric rationalization of freeform architec- ture with the goal of combining aesthetic and functional constraints and construction requirements. Aesthetic requirements typically come from designers and architects. To obtain visually pleasing structures, they favor smoothness of the building shape, but also smoothness of the visible patterns on the surface. Functional requirements typically come from the engineers involved in the construction process. For exam- ple, covering freeform structures using planar panels is much cheaper than using non-planar ones. Further, constructed buildings have to be stable and should not collapse. In this thesis, we explore the geometric rationalization of freeform archi- tecture using four specific example problems inspired by real life applications. We achieve our results by developing optimization algorithms and a theoretical study of the underlying geometrical structure of the problems. The four example problems are the following: (1) The design of shading and lighting systems which are torsion-free structures with planar beams based on quad meshes. They satisfy the functionality requirements of preventing light from going inside a building as shad- ing systems or reflecting light into a building as lighting systems. (2) The Design of freeform honeycomb structures that are constructed based on hex-dominant meshes with a planar beam mounted along each edge. The beams intersect without

Modern Church Construction in Urals. Problems and Prospects

Science.gov (United States)

Surin, D. N.; Tereshina, O. B.

2017-11-01

The article analyzes the problems of the modern Orthodox church architecture in Russia, special attention is paid to the problems of the Ural region. It justifies the importance of addressing to this issue connected with the Orthodox traditions revival in Russia over the last decades and the need to compensate for tens of thousands of the churches destroyed in the Soviet period. The works on the theory and history of the Russian architecture and art, studies of the architectural heritage and the art of building of the Ural craftsmen are used as a scientific and methodological base for the church architecture development. The article discloses the historically formed architectural features of the Russian Orthodox churches the artistic image of which is designed to create a certain religious and aesthetic experience. It is stated that the restoration of the Russian church construction tradition is possible on the background of architectural heritage. It sets the tendencies and vital tasks in church construction and outlines a complex of measures to solve these tasks at the public and regional levels.

Marc-Antoine Laugier’s aesthetic postulates of architectural theory

Directory of Open Access Journals (Sweden)

Kuletin-Ćulafić Irena

2010-01-01

Full Text Available Views on architecture that hold a significant position in architectural theory are the ones by Marc-Antoine Laugier, a French theoretician from the 18th century. The research on his architectural theory that have been carried out so far are quite stereotypical and concern Laugier’s concept of primitive hut as his only significant contribution to architectural theory. It is well-known that the concept of primitive hut plays an important role in Laugier’s theory and it is what actually maintained his reputation up to now. However, by singling out this concept as an independent one, one actually neglects all the other aspects of Laugier’s theory. The aim of this paper is to present multidimensionality of Laugier’s architectural aesthetics by crossing the borders of architecture and viewing Laugier’s ideas in cultural, philosophical, religious and historical context, as well as applying the integrative process and considering the spiritual paths of the enlightenment movement in the mid-18th century. A special attention is paid to considering the aesthetic aspect which represents the gist and an inevitable part of Laugier’s architectural theory. His aesthetic theory is important in forming the classicist style, and despite its radical character, it influenced many architects in France and the rest of Europe. We may see Laugier as one of the first modernists considering his structuralist logic of the constructive circuit of architecture and aesthetic modesty of decoration. Laugier’s functionalist attitude that the constructive circuit should at the same time represent a decorative element of architecture confirms the thesis that modernist approach has its roots in the 18th century.

A Review of Enterprise Architecture Use in Defence

Science.gov (United States)

2014-09-01

dictionary of terms; • architecture description language; • architectural information (pertaining both to specific projects and higher level...UNCLASSIFIED 59 Z39.19 2005 Monolingual Controlled Vocabularies, National Information Standards Organisation, Bethesda: NISO Press, 2005. BABOK 2009...togaf/ Z39.19 2005 ANSI/NISO Z39.19 – Guidelines for the Construction, Format, and Management of Monolingual Controlled Vocabularies, Bethesda: NISO

Electrochemical supramolecular recognition of hemin-carbon composites

Science.gov (United States)

Le, Hien Thi Ngoc; Jeong, Hae Kyung

2018-04-01

Hemin-graphite oxide-carbon nanotube (hemin-GO-CNT) and hemin-thermally reduced graphite oxide-carbon nanotube (hemin-TRGO-CNT) composites are synthesized and investigated for the electrochemical supramolecular recognition by electron transfer between biomolecules (dopamine and hydrogen peroxide) and the composite electrodes. Redox reaction mechanisms of two composites with dopamine and hydrogen peroxide are explained in detail by using cyclic voltammetry and differential pulse voltammetry. Hemin-TRGO-CNT displays higher electrochemical detection for dopamine and hydrogen peroxide than that of hemin-GO-CNT, exhibiting enhancement of the electron transfer due to the effective immobilization of redox couple of hemin (Fe2+/Fe3+) on the TRGO-CNT surface.

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

Science.gov (United States)

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

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

NARCIS (Netherlands)

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

2012-01-01

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

Supramolecular Control of Oligothienylenevinylene-Fullerene Interactions: Evidence for a Ground-State EDA Complex

NARCIS (Netherlands)

McClenaghan, N.D.; Grote, Z.; Darriet, K.; Zimine, M.Y.; Williams, R.M.; De Cola, L.; Bassani, D.M.

2005-01-01

Complementary hydrogen-bonding interactions between a barbituric acid-substituted fullerene derivative (1) and corresponding receptor (2) bearing thienylenevinylene units are used to assemble a 1:1 supramolecular complex ( K ) 5500 M-1). Due to the close proximity of the redox-active moieties within

Polymetallic lanthanide (III) complexes for the design of new luminescent materials

International Nuclear Information System (INIS)

Marchal, C.

2008-09-01

The incorporation of f elements in highly organized polymetallic complexes is of great interest in supramolecular chemistry and allows the combination of their nano-scopic size with the magnetic or optical properties of the metal ions. However due to the difficulty in controlling the coordination environment of these ions, the assembly of lanthanide-based polynuclear architectures has lagged behind that of other systems. These factors make the rational design for the construction of supramolecular lanthanide complexes quite challenging. In order to better understand the factors determining the assembly of lanthanide-based polymetallic arrays, we designed two different types of organic ligands, which favor, in one case, formation of infinite polymetallic complexes (coordination polymers), and in the case the assembly of discrete polymetallic architectures. Thus, we show that the use of flexible and multi-dentate picolinate-derivative ligands enables the formation of infinite and luminescent infinite frameworks which display very interesting luminescent properties. Geometry of the ligand has a great influence on the final network architecture. Particularly, implementation of four picolinate units within a tetrapodal ligand results in the controlled assembly of 1-D coordination polymers. Conversely to favor the controlled assembly of discrete polymetallic arrays we use dissymmetric ligands which displays low denticity. Complexation studies of a tridentate 8- hydroxyquinoline-derivative ligand as well as a tetradentate ligand possessing an oxazoline ring are presented. (author)

The analysis of cultural architectural trends in Crisan locality

Directory of Open Access Journals (Sweden)

SELA Florentina

2010-09-01

Full Text Available The paper presents data about the identification and analyse of the traditional architectural elements in Crisan locality knowing that the tourism activity is in a continuous development. The field research (during November 2007 enabled us to develop a qualitative and quantitative analysis in terms of identification of traditional architecture elements, their conservation status, and frequency of traditional building materials use, decorative elements and specificcolors used in construction architecture. Further, based on collected data, was realized the chart - Distribution for TraditionalArchitecture Index (TAI on the distance from the center of Crisan locality, showing that in Crisan locality the houses were and are built without taking into account any rule, destroying thus traditional architecture.

Trend analysis of modern high-rise construction

Science.gov (United States)

Radushinsky, Dmitry; Gubankov, Andrey; Mottaeva, Asiiat

2018-03-01

The article reviews the main trends of modern high-rise construction considered a number of architectural, engineering and technological, economic and image factors that have influenced the intensification of construction of high-rise buildings in the 21st century. The key factors of modern high-rise construction are identified, which are associated with an attractive image component for businessmen and politicians, with the ability to translate current views on architecture and innovations in construction technologies and the lobbying of relevant structures, as well as the opportunity to serve as an effective driver in the development of a complex of national economy sectors with the achievement of a multiplicative effect. The estimation of the priority nature of participation of foreign architectural bureaus in the design of super-high buildings in Russia at the present stage is given. The issue of economic expediency of construction of high-rise buildings, including those with only a residential function, has been investigated. The connection between the construction of skyscrapers as an important component of the image of cities in the marketing of places and territories, the connection of the availability of a high-rise center, the City, with the possibilities of attracting a "creative class" and the features of creating a large working space for specialists on the basis of territorial proximity and density of high-rise buildings.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

stacking and hydrogen bonding. Introduction of an electron push-pull system induces molecule IV to be planar and a C = O… supramolecular interaction is observed as well. Strong electron withdrawing and donating groups also ensure formation of a higher order two and three dimensional supramolecular architecture ...

Synthesis and characterization of metallo-supramolecular polymers from thiophene-based unimers bearing pybox ligands

Czech Academy of Sciences Publication Activity Database

Hladysh, S.; Václavková, D.; Vrbata, D.; Bondarev, D.; Havlíček, D.; Svoboda, Jan; Zedník, J.; Vohlídal, J.

2017-01-01

Roč. 7, č. 18 (2017), s. 10718-10728 ISSN 2046-2069 Institutional support: RVO:61389013 Keywords : metallo-supramolecular polymers * XPS Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 3.108, year: 2016

Comparison of Human Exploration Architecture and Campaign Approaches

Science.gov (United States)

Goodliff, Kandyce; Cirillo, William; Mattfeld, Bryan; Stromgren, Chel; Shyface, Hilary

2015-01-01

As part of an overall focus on space exploration, National Aeronautics and Space Administration (NASA) continues to evaluate potential approaches for sending humans beyond low Earth orbit (LEO). In addition, various external organizations are studying options for beyond LEO exploration. Recent studies include NASA's Evolvable Mars Campaign and Design Reference Architecture (DRA) 5.0, JPL's Minimal Mars Architecture; the Inspiration Mars mission; the Mars One campaign; and the Global Exploration Roadmap (GER). Each of these potential exploration constructs applies unique methods, architectures, and philosophies for human exploration. It is beneficial to compare potential approaches in order to better understand the range of options available for exploration. Since most of these studies were conducted independently, the approaches, ground rules, and assumptions used to conduct the analysis differ. In addition, the outputs and metrics presented for each construct differ substantially. This paper will describe the results of an effort to compare and contrast the results of these different studies under a common set of metrics. The paper will first present a summary of each of the proposed constructs, including a description of the overall approach and philosophy for exploration. Utilizing a common set of metrics for comparison, the paper will present the results of an evaluation of the potential benefits, critical challenges, and uncertainties associated with each construct. The analysis framework will include a detailed evaluation of key characteristics of each construct. These will include but are not limited to: a description of the technology and capability developments required to enable the construct and the uncertainties associated with these developments; an analysis of significant operational and programmatic risks associated with that construct; and an evaluation of the extent to which exploration is enabled by the construct, including the destinations

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

Czech Academy of Sciences Publication Activity Database

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

2015-01-01

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

Construction Management for Conventional Facilities of Proton Accelerator

International Nuclear Information System (INIS)

Kim, Jun Yeon; Cho, Jin Sam; Lee, Jae Sang

2008-05-01

Proton Engineering Frontier Project, puts its aim to building 100MeV 20mA linear proton accelerator which is national facility for NT, BT, IT, and future technologies, expected to boost up the national industry competitiveness. This R and D, Construction Management is in charge of the supportive works as site selection, architecture and engineering of conventional facilities, and overall construction management. The major goals of this work are as follows: At first, architecture and engineering of conventional facilities. Second, construction management, audit and inspection on construction of conventional facilities. Lastly, cooperation with the project host organization for adjusting technical issues of overall construction. In this research, We reviewed the basic design and made a detail design of conventional facilities. Preparation for construction license, site improvement and access road construction is fulfilled. Also, we made the technical support for project host as follows : selection of project host organization and host site selection, construction technical work for project host organization and procedure management

Eight supramolecular assemblies constructed from bis(benzimidazole) and organic acids through strong classical hydrogen bonding and weak noncovalent interactions

Science.gov (United States)

Jin, Shouwen; Wang, Daqi

2014-05-01

Eight crystalline organic acid-base adducts derived from alkane bridged bis(N-benzimidazole) and organic acids (2,4,6-trinitrophenol, p-nitrobenzoic acid, m-nitrobenzoic acid, 3,5-dinitrobenzoic acid, 5-sulfosalicylic acid and oxalic acid) were prepared and characterized by X-ray diffraction analysis, IR, mp, and elemental analysis. Of the eight compounds five are organic salts (1, 4, 6, 7 and 8) and the other three (2, 3, and 5) are cocrystals. In all of the adducts except 1 and 8, the ratio of the acid and the base is 2:1. All eight supramolecular assemblies involve extensive intermolecular classical hydrogen bonds as well as other noncovalent interactions. The role of weak and strong noncovalent interactions in the crystal packing is ascertained. These weak interactions combined, all the complexes displayed 3D framework structure. The results presented herein indicate that the strength and directionality of the classical N+-H⋯O-, O-H⋯O, and O-H⋯N hydrogen bonds (ionic or neutral) and other nonbonding associations between acids and ditopic benzimidazoles are sufficient to bring about the formation of cocrystals or organic salts.

Photoresponsive Molecular Recognition and Adhesion of Vesicles in a Competitive Ternary Supramolecular System

NARCIS (Netherlands)

Nalluri, Siva Krishna Mohan; Bultema, Jelle B.; Boekema, Egbert J.; Ravoo, Bart Jan

A competitive photoresponsive supramolecular system is formed in a dilute aqueous solution of three components: vesicles of amphiphilic alpha-cyclodextrin host 1a, divalent p-methylphenyl guest 2 or divalent p-methylbenzamide guest 3, and photoresponsive azobenzene monovalent guest 5. Guests 2 and 3

Understanding the molecular mechanisms involved in the interfacial self-healing of supramolecular rubbers

NARCIS (Netherlands)

Bose, R.K.; Garcia Espallargas, S.J.; Van der Zwaag, S.

2013-01-01

Supramolecular rubbers based on 2-aminoethylimidazolidone and fatty acids with epoxy crosslinks have been shown to self-heal via multiple hydrogen bonding sites. In this work, several tools are used to investigate the molecular mechanisms taking place at the interface to understand cohesive healing

Supramolecular Coordination Assemblies Constructed From Multifunctional Azole-Containing Carboxylic Acids

Directory of Open Access Journals (Sweden)

Yuheng Deng

2010-05-01

Full Text Available This paper provides a brief review of recent progress in the field of metal coordination polymers assembled from azole-containing carboxylic acids and gives a diagrammatic summary of the diversity of topological structures in the resulting infinite metal-organic coordination networks (MOCNs. Azole-containing carboxylic acids are a favorable kind of multifunctional ligand to construct various metal complexes with isolated complexes and one, two and three dimensional structures, whose isolated complexes are not the focus of this review. An insight into the topology patterns of the infinite coordination polymers is provided. Analyzed topologies are compared with documented topologies and catalogued by the nature of nodes and connectivity pattern. New topologies which are not available from current topology databases are described and demonstrated graphically.

Enzyme-Like Catalysis of the Nazarov Cyclization by Supramolecular Encapsulation

Energy Technology Data Exchange (ETDEWEB)

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

2010-03-29

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

D-amino acid-containing supramolecular nanofibers for potential cancer therapeutics.

Science.gov (United States)

Wang, Huaimin; Feng, Zhaoqianqi; Xu, Bing

2017-02-01

Nanostructures formed by peptides that self-assemble in water through non-covalent interactions have attracted considerable attention because peptides possess several unique advantages, such as modular design and easiness of synthesis, convenient modification with known functional motifs, good biocompatibility, low immunogenicity and toxicity, inherent biodegradability, and fast responses to a wide range of external stimuli. After about two decades of development, peptide-based supramolecular nanostructures have already shown great potentials in the fields of biomedicine. Among a range of biomedical applications, using such nanostructures for cancer therapy has attracted increased interests since cancer remains the major threat for human health. Comparing with L-peptides, nanostructures containing peptides made of D-amino acid (i.e., D-peptides) bear a unique advantage, biostability (i.e., resistance towards most of endogenous enzymes). The exploration of nanostructures containing D-amino acids, especially their biomedical applications, is still in its infancy. Herein we review the recent progress of D-amino acid-containing supramolecular nanofibers as an emerging class of biomaterials that exhibit unique features for the development of cancer therapeutics. In addition, we give a brief perspective about the challenges and promises in this research direction. Copyright © 2016 Elsevier B.V. All rights reserved.

Urban Sustainability through Public Architecture

Directory of Open Access Journals (Sweden)

Soomi Kim

2018-04-01

Full Text Available As the sustainability of contemporary cities has gained emphasis, interest in architecture has increased, due to its social and public responsibility. Since sustainability is linked to public values, research on sustainable public spaces is an important way to secure sustainability in cities. Based on this, we analyzed the sustainability of European cities by examining the design methods of public architecture according to the region. The aim of the study is to derive architectural methodology corresponding to local characteristics, and to suggest issues to consider in public architecture design to promote urban sustainability based on this. First, regarding the environmental aspect, it can be observed that there is an effort to secure sustainability. Second, in terms of social sustainability, historical value remains as a trace of architectural place, so that it continues in people’s memory. In addition, public architecture provides public places where citizens can gather and enjoy programs, while the architectural methods showed differences influenced by cultural conditions. Third, in economic sustainability, it was shown that energy saving was achieved through cost reduction through recycling of materials, facilities, or environmental factors. In conclusion, the issues to be considered in public architectural design are the voiding of urban space through architectural devices in the construction method. In other words, the intention is to form “ground” that attempts to be part of the city, and thereby create better places. Since skin and material have a deep relationship with the environment, they should have the durability and an outer skin that are suitable for the regional environment. Finally, sustainability is to be utilized through the influx of programs that meet local and environmental characteristics. Design research into public architecture that is oriented towards urban sustainability will be a task to be carried out by the

Supramolecular polyaniline hydrogel as a support for urease

International Nuclear Information System (INIS)

Słoniewska, Anna; Pałys, Barbara

2014-01-01

Supramolecular hydrogels of conducting polymers are successfully used in bioelectrochemistry because of their mechanical and swelling properties of gels added to the specific electron transport properties of conducting polymers. We have studied polyaniline-poly(styrene sulfonate) (PANI–PSS) hydrogel as a substrate for the urease. The hydrogels were synthesized at pH = 0 and pH = 5. PANI–PSS hydrogel is a supramolecular self-assembly material consisting of positively-charged PANI chains and negatively-charged PSS chains. The hydrogel was studied by cyclic voltammetry, infrared and Raman spectroscopy and Scanning Electron Microscopy (SEM). Raman spectra revealed presence of phenazine rings in the hydrogel structure. Phenazine rings form covalent cross-linkers contributing to the hydrogel mechanical stability. The covalent cross-linkers influence the cyclic voltammetry responses of the hydrogel in acidic media. We tested the activity of urease immobilized in the PANI–PSS hydrogel by the physical adsorption or by the covalent bonding with the carbodiimide reaction. The enzyme immobilized in hydrogels prepared at higher pH value reveals significantly higher sensitivity. The method of the enzyme immobilization has smaller impact on the sensitivity. All hydrogel sensors reveal largely higher sensitivity to urea comparing to urease immobilized in the typical electrochemically deposited PANI films. The sensitivity of urease covalently bond to the hydrogel obtained at pH = 5 was as high as 1693 μA/(mol dm 3 ). The sensor response was linear in the urea concentration range from 10 −4 to 7 × 10 −2 mol/dm 3

Supramolecular structure of a perylene derivative in thin films deposited by physical vapor deposition

International Nuclear Information System (INIS)

Fernandes, Jose D.; Aoki, Pedro H.B.; Constantino, Carlos J.J.; Junior, Wagner D.M.; Teixeira, Silvio R.

2014-01-01

Full text: Thin films of a perylene derivative, the bis butylimido perylene (BuPTCD), were produced using thermal evaporation (PVD, physical vapor deposition). The main objective is to investigate the supramolecular structure of the BuPTCD in these PVD films, which implies to control the thickness and to determine the molecular organization, morphology at micro and nanometer scales and crystallinity. This supramolecular structure is a key factor in the optical and electrical properties of the film. The ultraviolet-visible absorption revealed an uniform growth of the PVD films. The optical and atomic force microscopy images showed a homogeneous surface of the film at micro and nanometer scales. A preferential orientation of the molecules in the PVD films was determined via infrared absorption. The X-ray diffraction showed that both powder and PVD film are in the crystalline form. (author)

Supramolecular structure of jackfruit seed starch and its relationship with digestibility and physicochemical properties.

Science.gov (United States)

Chen, Jin; Liang, Yi; Li, Xiaoxi; Chen, Ling; Xie, Fengwei

2016-10-05

The influence of supramolecular structure on the physicochemical properties and digestibility of jackfruit seed starch (JSS) were investigated. Compared with maize and cassava starches (MS and CS), JSS had smaller granules and higher amylose content (JSS: 24.90%; CS: 16.68%; and MS: 22.42%), which contributed to higher gelatinization temperature (To: 81.11°C) and setback viscosity (548.9mPas). From scanning electron microscopy, the digestion of JSS was observed mainly at the granule surface. Due to its higher crystallinity (JSS: 30.6%; CS: 30.3%; and MS: 27.4%) and more ordered semi-crystalline lamellae, JSS had a high RS content (74.26%) and melting enthalpy (19.61J/g). In other words, the supramolecular structure of JSS extensively determined its digestibility and resistance to heat and mechanical shear treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

dimensional architectures via hydrogen bonds

Indian Academy of Sciences (India)

Administrator

organization and has potential applications in the field of magnetism ... The concepts of crystal engineering ... 4. However, the utilization of hydrogen bond supramolecular syn- ... sembling the coordination networks by designing the ligands ...

Co-assembly of Peptide Amphiphiles and Lipids into Supramolecular Nanostructures Driven by Anion-π Interactions

Energy Technology Data Exchange (ETDEWEB)

Yu, Zhilin; Erbas, Aykut; Tantakitti, Faifan; Palmer, Liam C.; Jackman, Joshua A.; Olvera de la Cruz, Monica; Cho, Nam-Joon; Stupp, Samuel I. (Nanyang); (NWU)

2017-06-01

Co-assembly of binary systems driven by specific non-covalent interactions can greatly expand the structural and functional space of supramolecular nanostructures. We report here on the self-assembly of peptide amphiphiles and fatty acids driven primarily by anion-π interactions. The peptide sequences investigated were functionalized with a perfluorinated phenylalanine residue to promote anion-π interactions with carboxylate headgroups in fatty acids. These interactions were verified here by NMR and circular dichroism experiments as well as investigated using atomistic simulations. Positioning the aromatic units close to the N-terminus of the peptide backbone near the hydrophobic core of cylindrical nanofibers leads to strong anion-π interactions between both components. With a low content of dodecanoic acid in this position, the cylindrical morphology is preserved. However, as the aromatic units are moved along the peptide backbone away from the hydrophobic core, the interactions with dodecanoic acid transform the cylindrical supramolecular morphology into ribbon-like structures. Increasing the ratio of dodecanoic acid to PA leads to either the formation of large vesicles in the binary systems where the anion-π interactions are strong, or a heterogeneous mixture of assemblies when the peptide amphiphiles associate weakly with dodecanoic acid. Our findings reveal how co-assembly involving designed specific interactions can drastically change supramolecular morphology and even cross from nano to micro scales.

Architectural Environment: A Resource Kit.

Science.gov (United States)

J.B. Speed Art Museum, Louisville, KY.

There are many ways to approach the investigation of architecture. One can look at structural form, climate and topography, the aesthetics of style and decoration, building function, historical factors, cultural meanings, or technology and techniques associated with construction. This resource kit touches upon a few of these approaches, ranging…

Organização supramolecular da ftalocianina de cobalto(II e seu efeito na oxidação do aminoácido cisteína Supramolecular organization of cobalt (II phthalocyanine on the pathway of cysteine oxidation

Directory of Open Access Journals (Sweden)

Amanda Costa Santos

2010-01-01

Full Text Available The interest in the chemistry of cobalt (II tetrasulfonated phthalocyanine (PcTsCo comes mainly from its macrocycle-ligand structure combined with their special chemical characteristics, such as high solubility, well-defined redox reactions and remarkable optical absorption in the visible region. In this work, we use layer-by-layer technique in order to assemble CoTsPc and poly(allylaminehydrochloride (PAH in hybrid supramolecular system. The electronic spectroscopy and cyclic voltammetry techniques were utilized to study PAH/CoTsPc multilayers growth and the cysteine catalytic oxidation. PAH/CoTsPc showed high electrochemical stability and worthwhile to mention is the remarkable influence of supramolecular arrangement on the final redox properties of the system.

On the kinetics of body versus end evaporation and addition of supramolecular polymers

NARCIS (Netherlands)

Tiwari, Nitin S.; van der Schoot, Paul

2017-01-01

Abstract.: The kinetics of the self-assembly of supramolecular polymers is dictated by how monomers, dimers, trimers etc., attach to and detach from each other. It is for this reasons that researchers have proposed a plethora of pathways to explain the kinetics of various self-assembling

On the kinetics of body versus end evaporation and addition of supramolecular polymers

NARCIS (Netherlands)

Tiwari, N.; van der Schoot, P.P.A.M.

2017-01-01

The kinetics of the self-assembly of supramolecular polymers is dictated by how monomers, dimers, trimers etc., attach to and detach from each other. It is for this reasons that researchers have proposed a plethora of pathways to explain the kinetics of various self-assembling supramolecules,

Understanding Periodic Dislocations in 2D Supramolecular Crystals: The PFP/Ag(111) Interface

DEFF Research Database (Denmark)

Goiri, E.; García Lastra, Juan Maria; Corso, M.

2012-01-01

In-plane dislocation networks arise in both inorganic and organic films as a way of relieving the elastic strain that builds up at the substrate interface. In molecule/surface systems, supramolecular interactions are weak and more complex (compared to the atomic bonds in inorganic films), and the...

An intelligent anticorrosion coating based on pH-responsive supramolecular nanocontainers

International Nuclear Information System (INIS)

Chen Tao; Fu Jiajun

2012-01-01

The hollow mesoporous silica nanoparticles (HMSNs), which have been used as the nanocontainers for the corrosion inhibitor, benzotriazole, were fabricated using the hard-template method. Alkaline-responsive HMSNs based on cucurbit[6]uril (CB[6])/bisammonium supramolecular complex and acid-responsive HMSNs based on α-cyclodextrin (α-CD)/aniline supramolecular complex, which operate in water, have been achieved and characterized by solid-state NMR, thermogravimetry analysis, scanning electron microscopy, transmission electron microscopy and N 2 adsorption-desorption analysis. The two elaborately designed nanocontainers show the pH-controlled encapsulation/release behaviors for benzotriazole molecules. Equal amounts of the alkaline- and acid-responsive nanocontainers were uniformly distributed in the hybrid zirconia-silica sol–gel coating and thus formed the intelligent anticorrosion coating. The self-healing property of AA2024 alloy coated with the intelligent anticorrosion coating is evaluated by electrochemical impedance spectroscopy (EIS). The sol–gel coating doped with the pH-responsive nanocontainers clearly demonstrates long-term corrosion protection performances when compared to the undoped sol–gel coating, which is attributed to the release of corrosion inhibitor from the nanocontainers after feeling the changes of environmental pH values near the corroded areas. (paper)

Construction of pegylated multilayer architectures via (strept)avidin/biotin interactions

International Nuclear Information System (INIS)

Dai Zhifei; Wilson, John T.; Chaikof, Elliot L.

2007-01-01

Pegylated multilayer architectures were fabricated as films on planar substrates, as shells on colloidal particles, or as free-standing hollow capsules using layer-by-layer (LbL) self-assembly of biotinylated poly-L-lysine (PLL) and (strept)avidin. Poly(ethylene glycol) (PEG) was incorporated into the multilayer architectures by assembly with biotin-derivatized poly(L-lysine)-g-poly(ethylene glycol)(PPB). Stepwise growth of multilayers was followed by UV-vis spectroscopy and the formation of core-shells and hollow capsules characterized by means of confocal laser scanning microscopy (CLSM) and transmission electron microscopy (TEM). Both absorbance and TEM data suggest that approximately two layers of FITC-avidin were adsorbed with each surface deposition. In contrast, use of unmodified PLL did not lead to formation of multilayer coatings, confirming that (strept)avidin-biotin interactions were responsible for film growth even in the presence of electrostatic repulsive forces between PLL and avidin and the steric hindrance of associated PEG chains. This technique provides new opportunities for the generation of robust films with tailored interfacial binding and transport properties

Two new hydrogen bond-supported supramolecular compounds assembly from polyoxovanadate and organoamines

International Nuclear Information System (INIS)

Duan Weijie; Cui Xiaobing; Xu Yan; Xu Jiqing; Yu Haihui; Yi Zhihui; Cui Jiwen; Wang Tiegang

2007-01-01

Two novel organic-inorganic hybrid compounds based on organoamines and polyoxovanadates formulated as (H 2 dien) 4 [H 10 V 18 O 42 (PO 4 )](PO 4 ).2H 2 O (1) (dien=diethylenetriamine) and (Him) 8 [HV 18 O 42 (PO 4 )] (2) (im=imidazole) have been prepared under hydrothermal conditions by using different starting materials, and characterized by elemental analyses, IR, ESR, XPS, TGA and single-crystal X-ray diffraction analyses. Crystal data for compound 1: C 16 H 74 N 12 O 52 V 18 P 2 , Monoclinic, space group C2/c, a=23.9593(4) A, b=13.0098(2) A, c=20.1703(4) A, β=105.566(3) o , V=6056.6(19) A 3 , Z=4; for compound 2, C 24 H 41 N 16 O 46 V 18 P, Tetragonal, space group I4/mmm, a=13.5154(8) A, b=13.5154(8) A, c=19.1136 A, β=90 o , V=3491.4(3) A 3 , Z=2. Compound 1 consists of protonated diens together with polyoxovanadates [H 10 V 18 O 42 (PO 4 )] 5- . Compound 2 is composed of protonated ims and polyoxovanadates [HV 18 O 42 (PO 4 )] 8- . There are hydrogen-bonding interactions between polyoxovanadates and different organoamines in 1 and 2. Polyoxovanadates are linked through H 2 dien into a three-dimensional network via hydrogen bonds in 1, while polyoxovanadates are linked by Him into a two-dimensional layer network via hydrogen bonds in 2. The crystal packing patterns of the two compounds reveal various supramolecular frameworks. - Graphical abstract: Two new organic-inorganic hybrid compounds based on [V 18 O 42 (PO 4 )] building blocks have been hydrothermally synthesized. 1 is the first 3-D supramolecular network structure consisting of [V 18 O 42 (PO 4 )] unit, while 2 possesses 2-D layered supramolecular structure

A New Supramolecular Route for Using Rod-Coil Block Copolymers in Photovoltaic Applications

Science.gov (United States)

Mezzenga, Raffaele; Sary, Nicolas; Richard, Fanny; Brochon, Cyril; Leclerc, Nicolas; Leveque, Patrick; Audinot, Jean Nicolas; Heiser, Thomas; Hadziioannou, Georges; Berson, Solenn

2010-03-01

We propose a new supramolecular strategy to blend together rod-coil poly(3-hexylthiophene)-poly(4-vinylpyridine) (P3HTP4VP) block copolymers and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). The P4VP and PCBM are mixed together by weak supramolecular interactions, and the resulting materials exhibit microphase separated morphologies of electron-donor and electron-acceptor rich domains. The microphase segregated P3HT-rod domains act as electron-donating species and the homogeneous P4VP block:PCBM blend acts as the electron-acceptor domain. We describe the photovoltaic performance of standard and inverted devices whose active layer is composed thereof and show the effect of finely engineering the interfacial properties of the active layer to obtain competitive photovoltaic performance with superior thermal stability. (1) N. Sary, F. Richard, C. Brochon, N. Leclerc, P. Leveque, JN Audinot, S. Berson, T. Heiser, G. Hadziioannou, R. Mezzenga, Adv. Mater. in Press (2010)

Self-assembly of heterogeneous supramolecular structures with uniaxial anisotropy.

Science.gov (United States)

Ruiz-Osés, M; Gonzalez-Lakunza, N; Silanes, I; Gourdon, A; Arnau, A; Ortega, J E

2006-12-28

Uniaxial anisotropy in two-dimensional self-assembled supramolecular structures is achieved by the coadsorption of two different linear molecules with complementary amine and imide functionalization. The two-dimensional monolayer is defined by a one-dimensional stack of binary chains, which can be forced to line up along steps in vicinal surfaces. The competing driving forces in the self-organization process are discussed in light of the structures observed during single molecule adsorption and coadsorption on flat and vicinal surfaces and the corresponding theoretical calculations.

Automatic Assignment of Methyl-NMR Spectra of Supramolecular Machines Using Graph Theory.

Science.gov (United States)

Pritišanac, Iva; Degiacomi, Matteo T; Alderson, T Reid; Carneiro, Marta G; Ab, Eiso; Siegal, Gregg; Baldwin, Andrew J

2017-07-19

Methyl groups are powerful probes for the analysis of structure, dynamics and function of supramolecular assemblies, using both solution- and solid-state NMR. Widespread application of the methodology has been limited due to the challenges associated with assigning spectral resonances to specific locations within a biomolecule. Here, we present Methyl Assignment by Graph Matching (MAGMA), for the automatic assignment of methyl resonances. A graph matching protocol examines all possibilities for each resonance in order to determine an exact assignment that includes a complete description of any ambiguity. MAGMA gives 100% accuracy in confident assignments when tested against both synthetic data, and 9 cross-validated examples using both solution- and solid-state NMR data. We show that this remarkable accuracy enables a user to distinguish between alternative protein structures. In a drug discovery application on HSP90, we show the method can rapidly and efficiently distinguish between possible ligand binding modes. By providing an exact and robust solution to methyl resonance assignment, MAGMA can facilitate significantly accelerated studies of supramolecular machines using methyl-based NMR spectroscopy.

Utilizing redox-chemistry to elucidate the nature of exciton transitions in supramolecular dye nanotubes

NARCIS (Netherlands)

Eisele, D. M.; Cone, C. W.; Bloemsma, E. A.; Vlaming, S. M.; van der Kwaak, C. G. F.; Silbey, R. J.; Bawendi, M. G.; Knoester, J.; Rabe, J. P.; Vanden Bout, D. A.

Supramolecular assemblies that interact with light have recently garnered much interest as well-defined nanoscale materials for electronic excitation energy collection and transport. However, to control such complex systems it is essential to understand how their various parts interact and whether

Rationalization with ruled surfaces in architecture

DEFF Research Database (Denmark)

Steenstrup, Kasper Hornbak

This thesis addresses the problems of rationalizing and segmenting large scale 3D models, and how to handle difficult production constraints in this area. The design choices when constructing large scale architecture are influenced by the budget. Therefore I strive to minimize the amount of time...... and material needed for production. This makes advanced free form architecture viable for low cost projects, allowing the architects to realize their designs. By pre-cutting building blocks using hot wire robots, the amount of milling necessary can be reduced drastically. I do this by rationalizing...

Service commitments and capabilities across ArchiMate architectural layers

NARCIS (Netherlands)

Nardi, Julio Cesar; A. Almeida, João Paulo; Pereira, Maiara Candido; de Almeida Falbo, Ricardo; Iacob, Maria Eugenia; van Sinderen, Marten J.; Ferreira Pires, Luis

ArchiMate is a widely adopted enterprise architecture modeling language that includes the “service‿ construct as a key structuring element across its enterprise layers. A previous analysis of the use of this construct within ArchiMate’s business layer concluded that it fails to represent some

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

OpenAIRE

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

2014-01-01

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

Solar energy in building construction practice. Solar architecture and solar engineering - fundamentals and uses. Sonnenenergie in der Baupraxis. Solar-Architektur und Solar-Technik - Grundlagen und Anwendungen

Energy Technology Data Exchange (ETDEWEB)

Weik, H.; Hahn, G.; Marschall, F.; Meister, H.; Peters, W.; Ranft, F.

1991-01-01

This anthology presents a number of overall suggestions for modern, trend-setting building construction. Details are given about active in addition to passive solar energy utilization, i.e. combinations of solar architecture and solar engineering. In an intelligible way accessible to non-physicist readers, part one discusses the related physicotechnical and town-planning fundamentals. Parts two and three are dedicated to building construction practice. They discuss the various problems of solar energy utilization from the point of view of architects, and refer to economic aspects and thermal insulation. Numerous pictures, diagrams and tables complete the book. (BWI) With 59 figs.

Statics of Historic Masonry Constructions

CERN Document Server

Como, Mario

2013-01-01

Masonry constructions are the great majority of the buildings in Europe’s historic centres and the most important monuments in its architectural heritage. Given the age of much of these constructions, the demand for safety assessments and restoration projects is pressing and constant. This book aims to help fill this demand presenting a comprehensive new statics of masonry constructions. The book, result of thirty years of research and professional experience, gives the fundamentals of statics of the masonry solid, then applied to the study of statics of arches, piers and vaults. Further, combining engineering and architecture and through an interdisciplinary approach, the book investigates the statical behaviour of many historic monuments, as the Pantheon, the Colosseum,  the domes of S. Maria del Fiore in Florence and of St. Peter in Rome, the Tower of Pisa, the Gothic Cathedrals and the Masonry Buildings under seismic actions.

Integration of molecular machines into supramolecular materials: actuation between equilibrium polymers and crystal-like gels.

Science.gov (United States)

Mariani, Giacomo; Goujon, Antoine; Moulin, Emilie; Rawiso, Michel; Giuseppone, Nicolas; Buhler, Eric

2017-11-30

In this article, the dynamic structure of complex supramolecular polymers composed of bistable [c2]daisy chain rotaxanes as molecular machines that are linked by ureidopyrimidinones (Upy) as recognition moieties was studied. pH actuation of the integrated mechanically active rotaxanes controls the contraction/extension of the polymer chains as well as their physical reticulation. Small-angle neutron and X-ray scattering were used to study in-depth the nanostructure of the contracted and extended polymer aggregates in toluene solution. The supramolecular polymers comprising contracted nanomachines were found to be equilibrium polymers with a mass that is concentration dependent in dilute and semidilute regimes. Surprisingly, the extended polymers form a gel network with a crystal-like internal structure that is independent of concentration and reminiscent of a pearl-necklace network.

Geometric Computing for Freeform Architecture

KAUST Repository

Wallner, J.

2011-06-03

Geometric computing has recently found a new field of applications, namely the various geometric problems which lie at the heart of rationalization and construction-aware design processes of freeform architecture. We report on our work in this area, dealing with meshes with planar faces and meshes which allow multilayer constructions (which is related to discrete surfaces and their curvatures), triangles meshes with circle-packing properties (which is related to conformal uniformization), and with the paneling problem. We emphasize the combination of numerical optimization and geometric knowledge.

Light Responsive Two-Component Supramolecular Hydrogel: A Sensitive Platform for Humidity Sensors

KAUST Repository

Samai, Suman

2016-02-15

The supramolecular assembly of anionic azobenzene dicarboxylate and cationic cetyltrimethylammonium bromide (CTAB) formed a stimuli responsive hydrogel with a critical gelation concentration (CGC) of 0.33 wt%. This self-sustainable two-component system was able to repair damage upon light irradiation. Moreover, it was successfully employed in the fabrication of highly sensitive humidity sensors for the first time.

Light Responsive Two-Component Supramolecular Hydrogel: A Sensitive Platform for Humidity Sensors

KAUST Repository

Samai, Suman; Sapsanis, Christos; Patil, Sachin; Ezzeddine, Alaa; Moosa, Basem; Omran, Hesham; Emwas, Abdul-Hamid M.; Salama, Khaled N.; Khashab, Niveen M.

2016-01-01

The supramolecular assembly of anionic azobenzene dicarboxylate and cationic cetyltrimethylammonium bromide (CTAB) formed a stimuli responsive hydrogel with a critical gelation concentration (CGC) of 0.33 wt%. This self-sustainable two-component system was able to repair damage upon light irradiation. Moreover, it was successfully employed in the fabrication of highly sensitive humidity sensors for the first time.

A shared synapse architecture for efficient FPGA implementation of autoencoders.

Science.gov (United States)

Suzuki, Akihiro; Morie, Takashi; Tamukoh, Hakaru

2018-01-01

This paper proposes a shared synapse architecture for autoencoders (AEs), and implements an AE with the proposed architecture as a digital circuit on a field-programmable gate array (FPGA). In the proposed architecture, the values of the synapse weights are shared between the synapses of an input and a hidden layer, and between the synapses of a hidden and an output layer. This architecture utilizes less of the limited resources of an FPGA than an architecture which does not share the synapse weights, and reduces the amount of synapse modules used by half. For the proposed circuit to be implemented into various types of AEs, it utilizes three kinds of parameters; one to change the number of layers' units, one to change the bit width of an internal value, and a learning rate. By altering a network configuration using these parameters, the proposed architecture can be used to construct a stacked AE. The proposed circuits are logically synthesized, and the number of their resources is determined. Our experimental results show that single and stacked AE circuits utilizing the proposed shared synapse architecture operate as regular AEs and as regular stacked AEs. The scalability of the proposed circuit and the relationship between the bit widths and the learning results are also determined. The clock cycles of the proposed circuits are formulated, and this formula is used to estimate the theoretical performance of the circuit when the circuit is used to construct arbitrary networks.

Insights in Architecture. Resources in Education.

Science.gov (United States)

Skena, K. George

1996-01-01

Focuses on new technological advances in the design process and especially the use of new materials to construct architectural marvels. Discusses the innovations of Le Corbusier, Mies van de Rohe, and Frank Lloyd Wright. Includes a student quiz and possible student outcomes. (JOW)

Review of The Architecture of Mud and Qudad DVDs

Directory of Open Access Journals (Sweden)

Dr. Enrico Fodde

2007-03-01

Full Text Available This superb documentary by Caterina Borelli is a study of the craftsmanship involved in the construction of the mud brick architecture of the Hadramaut and Do'an valleys of the Yemen, and the cultural aspects of a traditional architecture which incorporates an understanding of buildings which dates back centuries. Expanding the existing knowledge of these earthen heritage properties, examining their behaviour in the local climate and the preservation of traditional craftsmanship as part of a sustainable conservation future are the other prominent concerns of this work. The traditional heritage of the Hadramaut and Do'an regions in the south east of the Yemen are entirely constructed from loam. Throughout the centuries, the population has developed very sophisticated building techniques, and created a unique architectural environment. Spectacular structures such as ten-story mud brick tower houses rise up from green valleys that are surrounded by arid mountains. As in other parts of the world, with the advent of modern materials such as cement, indigenous construction and conservation practices carried out by craftsmen are rendered intellectually invisible by a process similar to the drawing of a veil. The elimination of these practices equals the erosion of centuries of building and conservation culture. As this heritage is rapidly disappearing, as shown by these obsolete construction techniques, this documentary is an excellent archive for future generations.

Contingent self-definition and amorphous regions: a dynamic approach to place brand architecture

OpenAIRE

Dinnie, Keith

2017-01-01

This article explores the concept of contingent self-definition, whereby place brands employ flexible self-definitional approaches in constructing their place brand architecture. Adopting a view of regions as social constructs, the article builds on and extends previous work on place brand architecture by identifying the underlying factors that drive contingent self-definition decisions. Based on an empirical study of professionals tasked with managing region brands in the Netherlands, eleven...

Hijazi Architectural Object Library (haol)

Science.gov (United States)

Baik, A.; Boehm, J.

2017-02-01

As with many historical buildings around the world, building façades are of special interest; moreover, the details of such windows, stonework, and ornaments give each historic building its individual character. Each object of these buildings must be classified in an architectural object library. Recently, a number of researches have been focusing on this topic in Europe and Canada. From this standpoint, the Hijazi Architectural Objects Library (HAOL) has reproduced Hijazi elements as 3D computer models, which are modelled using a Revit Family (RFA). The HAOL will be dependent on the image survey and point cloud data. The Hijazi Object such as Roshan and Mashrabiyah, become as vocabulary of many Islamic cities in the Hijazi region such as Jeddah in Saudi Arabia, and even for a number of Islamic historic cities such as Istanbul and Cairo. These architectural vocabularies are the main cause of the beauty of these heritage. However, there is a big gap in both the Islamic architectural library and the Hijazi architectural library to provide these unique elements. Besides, both Islamic and Hijazi architecture contains a huge amount of information which has not yet been digitally classified according to period and styles. Due to this issue, this paper will be focusing on developing of Heritage BIM (HBIM) standards and the HAOL library to reduce the cost and the delivering time for heritage and new projects that involve in Hijazi architectural styles. Through this paper, the fundamentals of Hijazi architecture informatics will be provided via developing framework for HBIM models and standards. This framework will provide schema and critical information, for example, classifying the different shapes, models, and forms of structure, construction, and ornamentation of Hijazi architecture in order to digitalize parametric building identity.

Construction of hybrid photosynthetic units using peripheral and core antennae from two different species of photosynthetic bacteria: detection of the energy transfer from bacteriochlorophyll a in LH2 to bacteriochlorophyll b in LH1.

Science.gov (United States)

Fujii, Ritsuko; Shimonaka, Shozo; Uchida, Naoko; Gardiner, Alastair T; Cogdell, Richard J; Sugisaki, Mitsuru; Hashimoto, Hideki

2008-01-01

Typical purple bacterial photosynthetic units consist of supra-molecular arrays of peripheral (LH2) and core (LH1-RC) antenna complexes. Recent atomic force microscopy pictures of photosynthetic units in intact membranes have revealed that the architecture of these units is variable (Scheuring et al. (2005) Biochim Bhiophys Acta 1712:109-127). In this study, we describe methods for the construction of heterologous photosynthetic units in lipid-bilayers from mixtures of purified LH2 (from Rhodopseudomonas acidophila) and LH1-RC (from Rhodopseudomonas viridis) core complexes. The architecture of these reconstituted photosynthetic units can be varied by controlling ratio of added LH2 to core complexes. The arrangement of the complexes was visualized by electron-microscopy in combination with Fourier analysis. The regular trigonal array of the core complexes seen in the native photosynthetic membrane could be regenerated in the reconstituted membranes by temperature cycling. In the presence of added LH2 complexes, this trigonal symmetry was replaced with orthorhombic symmetry. The small lattice lengths for the latter suggest that the constituent unit of the orthorhombic lattice is the LH2. Fluorescence and fluorescence-excitation spectroscopy was applied to the set of the reconstituted membranes prepared with various proportions of LH2 to core complexes. Remarkably, even though the LH2 complexes contain bacteriochlorophyll a, and the core complexes contain bacteriochlorophyll b, it was possible to demonstrate energy transfer from LH2 to the core complexes. These experiments provide a first step along the path toward investigating how changing the architecture of purple bacterial photosynthetic units affects the overall efficiency of light-harvesting.

Supramolecular Layer-by-Layer Assembly of 3D Multicomponent Nanostructures via Multivalent Molecular Recognition

NARCIS (Netherlands)

Ling, X.Y.; Phang, In Yee; Reinhoudt, David; Vancso, Gyula J.; Huskens, Jurriaan

2008-01-01

The supramolecular layer-by-layer assembly of 3D multicomponent nanostructures of nanoparticles is demonstrated. Nanoimprint lithography (NIL) was used as the patterning tool for making patterned β-cyclodextrin (CD) self-assembled monolayers (SAMs) and for the confinement of nanoparticles on the

Spatiotemporal Features of the Three-Dimensional Architectural Landscape in Qingdao, China.

Science.gov (United States)

Zhang, Peifeng

2015-01-01

The evolution and development of the three-dimensional (3D) architectural landscape is the basis of proper urban planning, eco-environment construction and the improvement of environmental quality. This paper presents the spatiotemporal characteristics of the 3D architectural landscape of the Shinan and Shibei districts in Qingdao, China, based on buildings' 3D information extracted from Quickbird images from 2003 to 2012, supported by Barista, landscape metrics and GIS. The results demonstrated that: (1) Shinan and Shibei districts expanded vertically and urban land use intensity increased noticeably from year to year. (2) Significant differences in the 3D architectural landscape existed among the western, central and eastern regions, and among the 26 sub-districts over the study period. The differentiation was consistent with the diverse development history, function and planning of the two districts. Finally, we found that population correlates positively with the variation in the 3D architectural landscape. This research provides an important reference for related studies, urban planning and eco-city construction.

Building Process and Architectural Planning Characteristics of Daehan Hospital Main Building

Directory of Open Access Journals (Sweden)

Geauchul LEE

2016-04-01

Full Text Available This paper explores the introduction process of Daehan Hospital from Japan as the modern medical facility in Korea, and the architectural planning characteristics as a medical facility through the detailed building process of Daehan Hospital main building. The most noticeable characteristic of Daehan Hospital is that it was designed and constructed not by Korean engineers but by Japanese engineers. Therefore, Daehan Hospital was influenced by Japanese early modern medical facility, and Japanese engineers modeled Daehan Hospital main building on Tokyo Medical School main building which was constructed in 1876 as the first national medical school and hospital. The architectural type of Tokyo Medical School main building was a typical school architecture in early Japanese modern period which had a middle corridor and a pseudo Western-style tower, but Tokyo Medical School main building became the model of a medical facility as the symbol of the medical department in Tokyo Imperial University. This was the introduction and transplantation process of Japanese modern ‘model’ like as other modern systems and technologies during the Korean modern transition period. However, unlike Tokyo Medical School main building, Daehan Hospital main building was constructed not as a wooden building but as a masonry building. Comparing with the function of Daehan Hospital main building, its architectural form and construction costs was excessive scale, which was because Japanese Resident-General of Korea had the intention of ostentation that Japanese modernity was superior to Korean Empire.

[Building Process and Architectural Planning Characteristics of Daehan Hospital Main Building].

Science.gov (United States)

Lee, Geauchul

2016-04-01

This paper explores the introduction process of Daehan Hospital from Japan as the modern medical facility in Korea, and the architectural planning characteristics as a medical facility through the detailed building process of Daehan Hospital main building. The most noticeable characteristic of Daehan Hospital is that it was designed and constructed not by Korean engineers but by Japanese engineers. Therefore, Daehan Hospital was influenced by Japanese early modern medical facility, and Japanese engineers modeled Daehan Hospital main building on Tokyo Medical School main building which was constructed in 1876 as the first national medical school and hospital. The architectural type of Tokyo Medical School main building was a typical school architecture in early Japanese modern period which had a middle corridor and a pseudo Western-style tower, but Tokyo Medical School main building became the model of a medical facility as the symbol of the medical department in Tokyo Imperial University. This was the introduction and transplantation process of Japanese modern 'model' like as other modern systems and technologies during the Korean modern transition period. However, unlike Tokyo Medical School main building, Daehan Hospital main building was constructed not as a wooden building but as a masonry building. Comparing with the function of Daehan Hospital main building, its architectural form and construction costs was excessive scale, which was because Japanese Resident-General of Korea had the intention of ostentation that Japanese modernity was superior to Korean Empire.

Cu(II) coordination polymers constructed by tetrafluoroterephthalic acid and varied imidazole-containing ligands: Syntheses, structures and properties

Science.gov (United States)

Liu, Kang; Sun, Yayong; Deng, Liming; Cao, Fan; Han, Jishu; Wang, Lei

2018-02-01

Six new copper(II) coordination polymers combining 2,3,5,6-tetrafluoroterephthalatic acid (H2tfBDC) and diverse imidazole-containing ligands, {[Cu(tfBDC)(1,2-bix)2]·2(H2O)}n (1), {Cu(tfBDC)(Im)2}n (2), {[Cu(1,4-bmimb)2(H2O)]·(tfBDC)·2(H2O)}n (3), {Cu(1,4-bimb)2(H2O)2·(tfBDC)}n (4), {[Cu(1,3-bix)2(H2O)2]·(tfBDC)·6(H2O)}n (5) and {[Cu(1,4-bix)2(H2O)2]·(tfBDC)·(1,4-bix)·4(H2O)}n (6) (1,2-bix = 1,2-bis(imidazole-1-ylmethyl)-benzene, Im = imidazole, 1,4-bmimb = 1,4-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene, 1,4-bimb = 1,4-bis(imidazol-1-yl)-butane, 1,3-bix = 1,3-bis(imidazole-1-ylmethyl)-benzene, 1,4-bix = 1,4-bis(imidazole-1-ylmethyl)-benzene), have been obtained and structurally verified by single-crystal X-ray diffraction analyses and further characterized by powder X-ray diffraction (PXRD), elemental analyses and infrared spectroscopy (IR). Single crystal X-ray diffraction analysis revealed that 1 is 2D 4-connected sql topology (point symbol: {44·62}) based on a single metal ion node. Compound 2 is characterized as an infinite 1D chain structure, which is further extended into a 2D layer through N-H···O hydrogen bonds and then a 3D supramolecular architecture via π···π stacking interactions. Note that 2 was prepared through an in situ ligand reaction in which N,N'-carbonyldiimidazole (cdi) broke up into imidazole ligand. Compound 3 possesses a 3D 4-fold interpenetrated architecture with 4-connected dia topology (Schläfli symbol: {66}) in which tfBDC2- is stabilized in the channel by hydrogen bonds. Compounds 4-6 are all linear 1D coordination polymers. In 4, the free tfBDC2- ligand acts as a μ4-bridge to link four coordinated water molecules from the chain to construct a 2D structure via hydrogen bonds. While in 5 and 6, the uncoordinated tfBDC2- ligands and multimeric water clusters is responsible for the conversion of these 1D coordination polymers into 3D supramolecular assemblies through O-H⋯O hydrogen bonding interactions. Moreover

Exploring Socio-material Orderings in Ethnography of Architectural Design

DEFF Research Database (Denmark)

Lotz, Katrine; Stang Våland, Marianne

How can the socio-material assemblages involved in contemporary ‘doings of architecture’ be identified and studied? The paper discusses recent transformations within architectural design practice and the extended network of local actors and technologies mobilized in contemporary building...... construction. Interested in examining how the current requirements in the field are – and can be - handled in architectural production, we aim to contribute to the ongoing development of ethnography of Architectural Design (Yaneva 2008, 2009, 2012). In our research, we focus on recent requirements...... in contemporary architectural design. We attempt to follow the actors in detail through their socio-material involvements and ‘architectural inventions’ such as visualized motives of space, materials, atmospheres, buildingparts and -components, and to explore how relations continuously tie and untie as a means...

Architecture oriented modeling and simulation method for combat mission profile

Directory of Open Access Journals (Sweden)

CHEN Xia

2017-05-01

Full Text Available In order to effectively analyze the system behavior and system performance of combat mission profile, an architecture-oriented modeling and simulation method is proposed. Starting from the architecture modeling,this paper describes the mission profile based on the definition from National Military Standard of China and the US Department of Defense Architecture Framework(DoDAFmodel, and constructs the architecture model of the mission profile. Then the transformation relationship between the architecture model and the agent simulation model is proposed to form the mission profile executable model. At last,taking the air-defense mission profile as an example,the agent simulation model is established based on the architecture model,and the input and output relations of the simulation model are analyzed. It provides method guidance for the combat mission profile design.

Constructing an Archive Yearbook 2015/2016

DEFF Research Database (Denmark)

Skafte Andersen, Mathias; Axelson, Hlyrnur; Benniche, Khedidja

2016-01-01

Constructing an Archive—Yearbook 2015/2016 contains a collection of student works conducted during the Fall semester of 2015 and the Spring semester of 2016 at the Aarhus School of Architecture. The publication has been designed and edited by the students and teachers of the studio Constructing a...

Space-Time and Architecture

Science.gov (United States)

Field, F.; Goodbun, J.; Watson, V.

Architects have a role to play in interplanetary space that has barely yet been explored. The architectural community is largely unaware of this new territory, for which there is still no agreed method of practice. There is moreover a general confusion, in scientific and related fields, over what architects might actually do there today. Current extra-planetary designs generally fail to explore the dynamic and relational nature of space-time, and often reduce human habitation to a purely functional problem. This is compounded by a crisis over the representation (drawing) of space-time. The present work returns to first principles of architecture in order to realign them with current socio-economic and technological trends surrounding the space industry. What emerges is simultaneously the basis for an ecological space architecture, and the representational strategies necessary to draw it. We explore this approach through a work of design-based research that describes the construction of Ocean; a huge body of water formed by the collision of two asteroids at the Translunar Lagrange Point (L2), that would serve as a site for colonisation, and as a resource to fuel future missions. Ocean is an experimental model for extra-planetary space design and its representation, within the autonomous discipline of architecture.

Molecular and supramolecular speciation of monoamide extractant systems

International Nuclear Information System (INIS)

Ferru, G.

2012-01-01

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

Study on Reverse Engineering of Historical Architecture Based on 3D Laser Scanner

International Nuclear Information System (INIS)

Cheng, X J; Jin, W

2006-01-01

Repair and maintenance of historical architecture includes reinforcement of configuration, repair of figure and so on. All these need surveying information such as blueprint etc. 3D laser scanning technology is one of the important technique methods to acquire spatial data. It scans the architecture point by point quickly; registers and joints point cloud to simulate the shape by computer; reconstructs 3D model accurately finally. It also produces construction drawing including ichnography, elevation, and cutaway. In addition, detail structure and vignette can be got by close-range photogrammetry method, which produces the orthoimage and linear drawing. This method is especially fit for surveying historical architecture that lacks construction records

Energy and Architecture: The Solar and Conservation Potential. Worldwatch Paper 40.

Science.gov (United States)

Flavin, Christopher

This monograph explores how architecture is influenced by and is responding to the global energy dilemma. Emphasis is placed on conservation techniques (using heavy insulation) and on passive solar construction (supplying most of a building's heating, cooling, and lighting requirements by sunlight). The basic problem is that architecture, like…

From green architecture to architectural green

DEFF Research Database (Denmark)

Earon, Ofri

2011-01-01

that describes the architectural exclusivity of this particular architecture genre. The adjective green expresses architectural qualities differentiating green architecture from none-green architecture. Currently, adding trees and vegetation to the building’s facade is the main architectural characteristics...... they have overshadowed the architectural potential of green architecture. The paper questions how a green space should perform, look like and function. Two examples are chosen to demonstrate thorough integrations between green and space. The examples are public buildings categorized as pavilions. One......The paper investigates the topic of green architecture from an architectural point of view and not an energy point of view. The purpose of the paper is to establish a debate about the architectural language and spatial characteristics of green architecture. In this light, green becomes an adjective...

Principles of sustainable development of the territory and priorities of architectural and urban construction activity

Science.gov (United States)

Dontsov, Dmitry; Yushkova, Natalia

2017-01-01

The paper is aimed at detecting conceptual conflicts within the architectural and urban construction activity (AUCA), defining their reasons and substantiating ways to decrease adverse effects they caused. Methods of causes and effects analyses are used, as well as evolutional and comparative analyses. They allow defining the laws to form activity model in modern environment, whose elements are ranked. Relevance of the paper is based on defining scientific and theoretical grounds of necessity to improve methodology of AUCA via its adaption to the imperatives of state management. System analyses enabled to prove practicability of considering factors of institution environment for reorganization of the model of AUCA, which provide the fullest implementation of sustainable development principles. It was proved that territorial planning is not only the leading type of AUCA, but also integrator for functioning structures of state management within planning of social and economic development. As main result of the paper consist in detection of the perspective ways for evolution of modern methodology due to increasing interdisciplinary aspect leading to the qualitative renewal of territorial management principles.

Molecular printboards as a general platform for protein immobilization: A supramolecular solution to nonspecific adsorption

NARCIS (Netherlands)

Ludden, M.J.W.; Mulder, A.; Tampe, Robert; Reinhoudt, David; Huskens, Jurriaan

2007-01-01

Be specific: A supramolecular adsorbate consisting of an adamantyl group (red) and an oligo(ethylene glycol) chain has been designed to prevent nonspecific protein adsorption at cyclodextrin molecular printboards. The adamantyl group allows specific and reversible interactions. Specific

Is the materialization of architecture necessarily material?

Directory of Open Access Journals (Sweden)

Čarapić Ana

2008-01-01

Full Text Available Architectural dematerialization process has started in the first half of the previous century, and has intensively developed at the beginning of this one. Architectural form decomposition on homo­geneous envelope and dependent internal structure, affect on façade materials to liberate from the ballast of supported role, and to gain the privilege to be the main holder of symbolic and sensual dimension. Therefore, on semantic level, they became primary driving force of dematerialization of form, and architecture in the whole. With new technological development, continuity in 'relieving' of matter has been brought to the extreme. Striving for complete liberty of conventional firmness and stability (in functional and phenomenal mode architecture take over the efemer 'week' substances from nature: water, air light, sound, and turn them in it's proper frame. Therefore, the general thesis of this paper is the absurd of architectural materialization with it's on demateriality. Being brought to the turning point, this absurd transforms both architecture (as artificial matter as well as nature itself. The goal of this paper is to predicate principles of material, formal and architectural genesis, in relation to the theoretical sources, as well as by examples of two developed constructions (pavilion 'Blur building' by Diller & Skofidio, and 'Tower of sound' by Toyo Ito.

Unraveling the Solution-State Supramolecular Structures of Donor-Acceptor Polymers and their Influence on Solid-State Morphology and Charge-Transport Properties.

Science.gov (United States)

Zheng, Yu-Qing; Yao, Ze-Fan; Lei, Ting; Dou, Jin-Hu; Yang, Chi-Yuan; Zou, Lin; Meng, Xiangyi; Ma, Wei; Wang, Jie-Yu; Pei, Jian

2017-11-01

Polymer self-assembly in solution prior to film fabrication makes solution-state structures critical for their solid-state packing and optoelectronic properties. However, unraveling the solution-state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution-state structure and the charge-transport properties in field-effect transistors. Here, for the first time, it is revealed that the thin-film morphology of a conjugated polymer inherits the features of its solution-state supramolecular structures. A "solution-state supramolecular structure control" strategy is proposed to increase the electron mobility of a benzodifurandione-based oligo(p-phenylene vinylene) (BDOPV)-based polymer. It is shown that the solution-state structures of the BDOPV-based conjugated polymer can be tuned such that it forms a 1D rod-like structure in good solvent and a 2D lamellar structure in poor solvent. By tuning the solution-state structure, films with high crystallinity and good interdomain connectivity are obtained. The electron mobility significantly increases from the original value of 1.8 to 3.2 cm 2 V -1 s -1 . This work demonstrates that "solution-state supramolecular structure" control is critical for understanding and optimization of the thin-film morphology and charge-transport properties of conjugated polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ISLAMIZATION OF CONTEMPORARY ARCHITECTURE: SHIFTING THE PARADIGM OF ISLAMIC ARCHITECTURE

Directory of Open Access Journals (Sweden)

Mustapha Ben- Hamouche

2012-03-01

objectives of the paper consist of counter-criticizing orientalists’ views that overwhelm our libraries and references systems, and that consider the first stage of Islamic civilization, within which architecture is part, as a mere cut-and-paste process and, at best, a synthesis of these pre-Islamic heritages, and overcoming the prevailing historicist approach, and open new scopes for future generations to instate a new era of islamization that permits digesting the contemporary Western thoughts in a conscious, critical, and constructive way.

Towards a Sustainable Architecture

OpenAIRE

Patuel Chust, Pascual

2014-01-01

The growing awareness of the importance of ecology in the last decades has led many architects to rethink their construction proposals to make them more respectful of the environment and sustainability. The present article analyzes the legislation, conferences and international declarations (Earth Summit, Declaration of Interdependence for a Sustainable Future, Introduction to Sustainable Design) that have advocated the practice of a more ecological architecture. Also examined ...

Modular assembly of low-dimensional coordination architectures on metal surfaces

International Nuclear Information System (INIS)

Stepanow, Sebastian; Lin, Nian; Barth, Johannes V

2008-01-01

The engineering of highly organized molecular architectures has attracted strong interest because of its potential for novel materials and functional nanoscopic devices. An important factor in the development, integration, and exploitation of such systems is the capability to prepare them on surfaces or in nanostructured environments. Recent advances in supramolecular design on metal substrates provide atomistic insight into the underlying self-assembly processes, mainly by scanning tunneling microscopy observations. This review summarizes progress in noncovalent synthesis strategies under ultra-high vacuum conditions employing metal ions as coordination centers directing the molecular organization. The realized metallosupramolecular compounds and arrays combine the properties of their constituent metal ions and organic ligands, and present several attractive features: their redox, magnetic and spin-state transitions. The presented exemplary molecular level studies elucidate the arrangement of organic adsorbates on metal surfaces, demonstrating the interplay between intermolecular and molecule-substrate interactions that needs to be controlled for the fabrication of low-dimensional structures. The understanding of metallosupramolecular organization and metal-ligand interactions on solid surfaces is important for the control of structure and concomitant function