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Sample records for supramolecular assembly based

  1. 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.

  2. 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)

  3. 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

  4. 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.

  5. 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.

  6. 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

  7. 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).

  8. 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...

  9. 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

  10. 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.

  11. Building new discrete supramolecular assemblies through the interaction of iso-tellurazole N-oxides with Lewis acids and bases.

    Science.gov (United States)

    Ho, Peter C; Jenkins, Hilary A; Britten, James F; Vargas-Baca, Ignacio

    2017-10-13

    The supramolecular macrocycles spontaneously assembled by iso-tellurazole N-oxides are stable towards Lewis bases as strong as N-heterocyclic carbenes (NHC) but readily react with Lewis acids such as BR 3 (R = Ph, F). The electron acceptor ability of the tellurium atom is greatly enhanced in the resulting O-bonded adducts, which consequently enables binding to a variety of Lewis bases that includes acetonitrile, 4-dimethylaminopyridine, 4,4'-bipyridine, triphenyl phosphine, a N-heterocyclic carbene and a second molecule of iso-tellurazole N-oxide.

  12. A Novel Reconfigurable Logic Unit Based on the DNA-Templated Potassium-Concentration-Dependent Supramolecular Assembly.

    Science.gov (United States)

    Yang, Chunrong; Zou, Dan; Chen, Jianchi; Zhang, Linyan; Miao, Jiarong; Huang, Dan; Du, Yuanyuan; Yang, Shu; Yang, Qianfan; Tang, Yalin

    2018-03-15

    Plenty of molecular circuits with specific functions have been developed; however, logic units with reconfigurability, which could simplify the circuits and speed up the information process, are rarely reported. In this work, we designed a novel reconfigurable logic unit based on a DNA-templated, potassium-concentration-dependent, supramolecular assembly, which could respond to the input stimuli of H + and K + . By inputting different concentrations of K + , the logic unit could implement three significant functions, including a half adder, a half subtractor, and a 2-to-4 decoder. Considering its reconfigurable ability and good performance, the novel prototypes developed here may serve as a promising proof of principle in molecular computers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. 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

  14. 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

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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

  20. Construction of Supramolecular Architectures via Self-assembly

    Institute of Scientific and Technical Information of China (English)

    Takeharu; Haino

    2007-01-01

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

  1. Construction of diverse supramolecular assemblies of dimetal ...

    Indian Academy of Sciences (India)

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

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

    Science.gov (United States)

    Iyoda, Masahiko; Hasegawa, Masashi

    2015-01-01

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

  3. 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.

  4. 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

  5. Nano-self-assemblies based on synthetic analogues of mycobacterial monomycoloyl glycerol and DDA: Supramolecular structure and adjuvant efficacy

    DEFF Research Database (Denmark)

    Martin-Bertelsen, Birte; Korsholm, Karen Smith; Christensen, Dennis

    2016-01-01

    responses. In the present study, we investigated the supramolecular structure and in vivo adjuvant activity of dispersions based on binary mixtures of DDA and an array of synthetic MMG-1 analogues (MMG- 2/3/5/6) displaying longer (MMG-2) or shorter (MMG-3) alkyl chain lengths, or polar headgroup (MMG-5...... for DDA:MMG-3, depending on the DDA:MMG molar ratio. The studies also showed that ULVs were formed, regardless of the structural characteristics of the neat MMG analogues in excess buffer [lamellar (MMG-1/2/5) or inverse hexagonal (MMG-3/6) phases]. Immunization of mice with a chlamydia antigen surface......-adsorbed to DDA:MMG-1/3/6 dispersions revealed that all tested adjuvants were immunoactive and induced strong Th1 and Th17 responses with a potential for a central effector memory profile. The MMG-1 and MMG-6 analogues were equally immunoactive in vivo upon incorporation into DDA liposomes, despite the reported...

  6. 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.

  7. Supramolecular ribbons from amphiphilic trisamides self-assembly.

    Science.gov (United States)

    García, Fátima; Buendía, Julia; Sánchez, Luis

    2011-08-05

    Two amphiphilic C(3)-symmetric OPE-based trisamides have been synthesized and their self-assembling features investigated in solution and on surface. Variable-temperature UV-vis experiments demonstrate the cooperative supramolecular polymerization of these trisamides that self-assemble by the operation of triple C═O···H-N H-bonding arrays between the amide functional groups and π-π stacking between the aromatic units. The helical organization of the aggregates has been demonstrated by circular dichroism at a concentration as low as 1 × 10(-4) M in acetonitrile. In the reported trisamides, the large hydrophobic aromatic core acts as a solvophobic module impeding the interaction between the polar TEG chains and the amide H-bonds. This strategy makes unnecessary the separation of the amide functional groups to the polar tri(ethylene glycol) chains by paraffinic fragments. Achiral trisamide 1 self-assembles into flat ribbon-like structures that experience an amplification of chirality by the addition of a small amount of chiral 2 that generates twisted stripes.

  8. Influence of Odd and Even Alkyl Chains on Supramolecular Nanoarchitecture via Self-Assembly of Tetraphenylethylene-Based AIEgens

    Directory of Open Access Journals (Sweden)

    Mina Salimimarand

    2017-10-01

    Full Text Available The Tetraphenylethylene (TPE based dumbbell shaped molecules TPE-Pi, TPE-Su, TPE-Az, and TPE-Se were synthesised bearing odd-even alkyl chains containing 7, 8, 9 and 10 carbons respectively. These molecules reveal typical Aggregation Induced Emission (AIE behaviour. The influence of the odd or even alkyl chain length was shown by studying the morphology of self-assembled nanostructures formed in a range of tetrahydrofuran (THF/water solvent systems. For example, with a water fraction of 80%, TPE derivatives with odd alkyl chains (TPE-Pi and TPE-Az self-assembled into nanosphere structures, while TPE-Su with 8 alkyl chains formed microbelts and TPE-Se with 10 alkyl chains aggregated into flower-like superstructures. These TPE derivatives also revealed interesting mechanochromic properties upon grinding, fuming and heating, which reveal the importance of molecular stacking in the crystal structure to the luminescent properties of the aggregates .The mechanochromic properties of TPE-Pi, TPE-Su, and TPE-Az were also demonstrated by the process of grounding, fuming, and heating.

  9. 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.

  10. 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.

  11. Small molecule-guided thermoresponsive supramolecular assemblies

    KAUST Repository

    Rancatore, Benjamin J.; Mauldin, Clayton E.; Frechet, Jean; Xu, Ting

    2012-01-01

    Small organic molecules with strong intermolecular interactions have a wide range of desirable optical and electronic properties and rich phase behaviors. Incorporating them into block copolymer (BCP)-based supramolecules opens new routes to generate functional responsive materials. Using oligothiophene- containing supramolecules, we present systematic studies of critical thermodynamic parameters and kinetic pathway that govern the coassemblies of BCP and strongly interacting small molecules. A number of potentially useful morphologies for optoelectronic materials, including a nanoscopic network of oligothiophene and nanoscopic crystalline lamellae, were obtained by varying the assembly pathway. Hierarchical coassemblies of oligothiophene and BCP, rather than macrophase separation, can be obtained. Crystallization of the oligothiophene not only induces chain stretching of the BCP block the oligothiophene is hydrogen bonded to but also changes the conformation of the other BCP coil block. This leads to an over 70% change in the BCP periodicity (e.g., from 31 to 53 nm) as the oligothiophene changes from a melt to a crystalline state, which provides access to a large BCP periodicity using fairly low molecular weight BCP. The present studies have demonstrated the experimental feasibility of generating thermoresponsive materials that convert heat into mechanical energy. Incorporating strongly interacting small molecules into BCP supramolecules effectively increases the BCP periodicity and may also open new opportunities to tailor their optical properties without the need for high molecular weight BCP. © 2012 American Chemical Society.

  12. Small molecule-guided thermoresponsive supramolecular assemblies

    KAUST Repository

    Rancatore, Benjamin J.

    2012-10-23

    Small organic molecules with strong intermolecular interactions have a wide range of desirable optical and electronic properties and rich phase behaviors. Incorporating them into block copolymer (BCP)-based supramolecules opens new routes to generate functional responsive materials. Using oligothiophene- containing supramolecules, we present systematic studies of critical thermodynamic parameters and kinetic pathway that govern the coassemblies of BCP and strongly interacting small molecules. A number of potentially useful morphologies for optoelectronic materials, including a nanoscopic network of oligothiophene and nanoscopic crystalline lamellae, were obtained by varying the assembly pathway. Hierarchical coassemblies of oligothiophene and BCP, rather than macrophase separation, can be obtained. Crystallization of the oligothiophene not only induces chain stretching of the BCP block the oligothiophene is hydrogen bonded to but also changes the conformation of the other BCP coil block. This leads to an over 70% change in the BCP periodicity (e.g., from 31 to 53 nm) as the oligothiophene changes from a melt to a crystalline state, which provides access to a large BCP periodicity using fairly low molecular weight BCP. The present studies have demonstrated the experimental feasibility of generating thermoresponsive materials that convert heat into mechanical energy. Incorporating strongly interacting small molecules into BCP supramolecules effectively increases the BCP periodicity and may also open new opportunities to tailor their optical properties without the need for high molecular weight BCP. © 2012 American Chemical Society.

  13. 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.

  14. Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Surbella, Robert G. [Department; Ducati, Lucas C. [Department; Pellegrini, Kristi L. [Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; McNamara, Bruce K. [Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Autschbach, Jochen [Department; Schwantes, Jon M. [Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Cahill, Christopher L. [Department

    2017-07-26

    A family of twelve supramolecular [AnO2Cl4]2- (An = U, Np, Pu) containing compounds assembled via hydrogen and halogen bonds donated by substituted 4-X-pyridinium cations (X = H, Cl, Br, I) is reported. These materials were prepared from a room-temperature synthesis wherein crystallization of unhydrolyzed and valence pure [An(VI)O2Cl4]2- (An = U, Np, Pu) tectons are the norm. We present a hierarchy of assembly criteria based on crystallographic observations, and subsequently quantify the strengths of the non-covalent interactions using Kohn-Sham density functional calculations. We provide, for the first time, a detailed description of the electrostatic potentials (ESPs) of the actinyl tetrahalide dianions and reconcile crystallographically observed structural motifs and non-covalent interaction (NCI) acceptor-donor pairings. Our findings indicate that the average electrostatic potential across the halogen ligands (the acceptors) changes by only ~2 kJ mol-1 across the AnO22+ series, indicating the magnitude of the potential is independent of the metal center. The role of the cation is therefore critical in directing structural motifs and dictating the resulting hydrogen and halogen bond strengths, the former being stronger due to the positive charge centralized on the pyridyl nitrogen N-H+. Subsequent analyses using the Quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) approaches support this conclusion and highlight the structure directing role of the cations. Whereas one can infer that the 2 Columbic attraction is the driver for assembly, the contribution of the non-covalent interaction is to direct the molecular-level arrangement (or disposition) of the tectons.

  15. 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

  16. 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.

  17. Artificial Nacre from Supramolecular Assembly of Graphene Oxide.

    Science.gov (United States)

    Wang, Yang; Li, Ting; Ma, Piming; Zhang, Shengwen; Zhang, Hongji; Du, Mingliang; Xie, Yi; Chen, Mingqing; Dong, Weifu; Ming, Weihua

    2018-06-14

    Inspired by the "brick-and-mortar" structure and remarkable mechanical performance of nacre, many efforts have been devoted to fabricating nacre-mimicking materials. Herein, a class of graphene oxide (GO) based artificial nacre material with quadruple hydrogen-bonding interactions was fabricated by functionalization of polydopamine-capped graphene oxide (PDG) with 2-ureido-4[1 H]-pyrimidinone (UPy) self-complementary quadruple hydrogen-bonding units followed by supramolecular assembly process. The artificial nacre displays a strict "brick-and-mortar" structure, with PDG nanosheets as the brick and UPy units as the mortar. The resultant nanocomposite shows an excellent balance of strength and toughness. Because of the strong strengthening via quadruple hydrogen bonding, the tensile strength and toughness can reach 325.6 ± 17.8 MPa and 11.1 ± 1.3 MJ m -3 , respectively, thus exceeding natural nacre, and reaching 3.6 and 10 times that of a pure GO artificial nacre. Furthermore, after further H 2 O treatment, the resulting H 2 O-treated PDG-UPy actuator displays significant bending actuations when driven by heat. This work provides a pathway for the development of artificial nacre for their potential applications in energy conversion, temperature sensor, and thermo-driven actuator.

  18. Energy Landscapes for the Self-Assembly of Supramolecular Polyhedra

    Science.gov (United States)

    Russell, Emily R.; Menon, Govind

    2016-06-01

    We develop a mathematical model for the energy landscape of polyhedral supramolecular cages recently synthesized by self-assembly (Sun et al. in Science 328:1144-1147, 2010). Our model includes two essential features of the experiment: (1) geometry of the organic ligands and metallic ions; and (2) combinatorics. The molecular geometry is used to introduce an energy that favors square-planar vertices (modeling {Pd}^{2+} ions) and bent edges with one of two preferred opening angles (modeling boomerang-shaped ligands of two types). The combinatorics of the model involve two-colorings of edges of polyhedra with four-valent vertices. The set of such two-colorings, quotiented by the octahedral symmetry group, has a natural graph structure and is called the combinatorial configuration space. The energy landscape of our model is the energy of each state in the combinatorial configuration space. The challenge in the computation of the energy landscape is a combinatorial explosion in the number of two-colorings of edges. We describe sampling methods based on the symmetries of the configurations and connectivity of the configuration graph. When the two preferred opening angles encompass the geometrically ideal angle, the energy landscape exhibits a very low-energy minimum for the most symmetric configuration at equal mixing of the two angles, even when the average opening angle does not match the ideal angle.

  19. 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

  20. Macromolecularly crowded in vitro microenvironments accelerate the production of extracellular matrix-rich supramolecular assemblies.

    Science.gov (United States)

    Kumar, Pramod; Satyam, Abhigyan; Fan, Xingliang; Collin, Estelle; Rochev, Yury; Rodriguez, Brian J; Gorelov, Alexander; Dillon, Simon; Joshi, Lokesh; Raghunath, Michael; Pandit, Abhay; Zeugolis, Dimitrios I

    2015-03-04

    Therapeutic strategies based on the principles of tissue engineering by self-assembly put forward the notion that functional regeneration can be achieved by utilising the inherent capacity of cells to create highly sophisticated supramolecular assemblies. However, in dilute ex vivo microenvironments, prolonged culture time is required to develop an extracellular matrix-rich implantable device. Herein, we assessed the influence of macromolecular crowding, a biophysical phenomenon that regulates intra- and extra-cellular activities in multicellular organisms, in human corneal fibroblast culture. In the presence of macromolecules, abundant extracellular matrix deposition was evidenced as fast as 48 h in culture, even at low serum concentration. Temperature responsive copolymers allowed the detachment of dense and cohesive supramolecularly assembled living substitutes within 6 days in culture. Morphological, histological, gene and protein analysis assays demonstrated maintenance of tissue-specific function. Macromolecular crowding opens new avenues for a more rational design in engineering of clinically relevant tissue modules in vitro.

  1. 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.

  2. Self-Assembled Supramolecular Architectures Lyotropic Liquid Crystals

    CERN Document Server

    Garti, Nissim

    2012-01-01

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

  3. 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

  4. 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

  5. Narrowing the diversification of supramolecular assemblies by preorganization.

    Science.gov (United States)

    Wang, Zhongyan; Liang, Chunhui; Shang, Yuna; He, Shuangshuang; Wang, Ling; Yang, Zhimou

    2018-03-13

    We designed and synthesized three phosphorylated peptides as precursors of the same peptide Nap-YYY. We found that different precursors led to different materials with almost identical chemical compositions at the final stages. Only Nap-YpYY could form very uniform nanofibers in a stable supramolecular hydrogel by enzyme-instructed self-assembly (EISA) at the physiological temperature (37 °C). In contrast, de-phosphorylation of the other two precursors (Nap-pYYY and Nap-YYpY) resulted in diverse nanostructures in metastable hydrogels with precipitates. The formation of uniform nanomaterials in the stable hydrogels was due to the preorganization property of the precursor Nap-YpYY, which facilitated rapid folding and accelerated the kinetics of hydrogelation of the resulting peptide Nap-YYY generated by the EISA process. Our study demonstrated the importance of the precursor for the self-assembly of nanomaterials and provided a useful strategy to manipulate them.

  6. 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.

  7. From micelle supramolecular assemblies in selective solvents to isoporous membranes

    KAUST Repository

    Nunes, Suzana Pereira

    2011-08-16

    The supramolecular assembly of PS-b-P4VP copolymer micelles induced by selective solvent mixtures was used to manufacture isoporous membranes. Micelle order in solution was confirmed by cryo-scanning electron microscopy in casting solutions, leading to ordered pore morphology. When dioxane, a solvent that interacts poorly with the micelle corona, was added to the solution, polymer-polymer segment contact was preferential, increasing the intermicelle contact. Immersion in water gave rise to asymmetric porous membranes with exceptional pore uniformity and high porosity. The introduction of a small number of carbon nanotubes to the casting solution improved the membrane stability and the reversibility of the gate response in the presence of different pH values. © 2011 American Chemical Society.

  8. From micelle supramolecular assemblies in selective solvents to isoporous membranes

    KAUST Repository

    Nunes, Suzana Pereira; Karunakaran, Madhavan; Neelakanda, Pradeep; Behzad, Ali Reza; Hooghan, Bobby; Sougrat, Rachid; He, Haoze; Peinemann, Klaus-Viktor

    2011-01-01

    The supramolecular assembly of PS-b-P4VP copolymer micelles induced by selective solvent mixtures was used to manufacture isoporous membranes. Micelle order in solution was confirmed by cryo-scanning electron microscopy in casting solutions, leading to ordered pore morphology. When dioxane, a solvent that interacts poorly with the micelle corona, was added to the solution, polymer-polymer segment contact was preferential, increasing the intermicelle contact. Immersion in water gave rise to asymmetric porous membranes with exceptional pore uniformity and high porosity. The introduction of a small number of carbon nanotubes to the casting solution improved the membrane stability and the reversibility of the gate response in the presence of different pH values. © 2011 American Chemical Society.

  9. A redox-assisted supramolecular assembly of manganese oxide nanotube

    International Nuclear Information System (INIS)

    Tao Li; Sun Chenggao; Fan Meilian; Huang Caijuan; Wu Hailong; Chao Zisheng; Zhai Hesheng

    2006-01-01

    In this paper, we report the hydrothermal synthesis of manganese oxide nanotube from an aqueous medium of pH 7, using KMnO 4 and MnCl 2 as inorganic precursors, polyoxyethylene (10) nonyl phenyl ether (TX-10) a surfactant and acetaldehyde an additive. The characterization of X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and N 2 adsorption at 77 K (BET) reveals that the synthesized manganese oxide nanotube has a mesopore size of ca. 3.65 nm and a wall thickness of ca. 12 nm, with the wall being composed of microporous crystals of monoclinic manganite. The X-ray photoelectron spectroscopy (XPS) result demonstrates a decrease of the binding energy of the Mn 3+ in the manganese oxide nanotube, which may be related to both the nanotubular morphology and the crystalline pore wall. A mechanism of a redox-assisted supramolecular assembly, regulated by acetaldehyde, is postulated

  10. 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.

  11. Supramolecular domains in mixed peptide self-assembled monolayers on gold nanoparticles.

    Science.gov (United States)

    Duchesne, Laurence; Wells, Geoff; Fernig, David G; Harris, Sarah A; Lévy, Raphaël

    2008-09-01

    Self-organization in mixed self-assembled monolayers of small molecules provides a route towards nanoparticles with complex molecular structures. Inspired by structural biology, a strategy based on chemical cross-linking is introduced to probe proximity between functional peptides embedded in a mixed self-assembled monolayer at the surface of a nanoparticle. The physical basis of the proximity measurement is a transition from intramolecular to intermolecular cross-linking as the functional peptides get closer. Experimental investigations of a binary peptide self-assembled monolayer show that this transition happens at an extremely low molar ratio of the functional versus matrix peptide. Molecular dynamics simulations of the peptide self-assembled monolayer are used to calculate the volume explored by the reactive groups. Comparison of the experimental results with a probabilistic model demonstrates that the peptides are not randomly distributed at the surface of the nanoparticle, but rather self-organize into supramolecular domains.

  12. 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.

  13. 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.

  14. 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.

  15. Structural Consequences of Anionic Host-Cationic Guest Interactions in a Supramolecular Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael D.; Johnson, Darren W.; Szigethy, Geza; Davis, Anna V.; Teat, Simon J.; Oliver, Allen G.; Bergman, Robert G.; Raymond, Kenneth N.

    2008-07-09

    The molecular structure of the self-assembled supramolecular assembly [M{sub 4}L{sub 6}]{sup 12-} has been explored with different metals (M = Ga{sup III}, Fe{sup III}, Ti{sup IV}) and different encapsulated guests (NEt{sub 4}{sup +}, BnNMe{sub 3}{sup +}, Cp{sub 2}Co{sup +}, Cp*{sub 2}Co{sup +}) by X-ray crystallography. While the identity of the metal ions at the vertices of the M{sub 4}L{sub 6} structure is found to have little effect on the assembly structure, encapsulated guests significantly distort the size and shape of the interior cavity of the assembly. Cations on the exterior of the assembly are found to interact with the assembly through either {pi}-{pi}, cation-{pi}, or CH-{pi} interactions. In some cases, the exterior guests interact with only one assembly, but cations with the ability to form multiple {pi}-{pi} interactions are able to interact with adjacent assemblies in the crystal lattice. The solvent accessible cavity of the assembly is modeled using the rolling probe method and found to range from 253-434 {angstrom}{sup 3}, depending on the encapsulated guest. Based on the volume of the guest and the volume of the cavity, the packing coefficient for each host-guest complex is found to range from 0.47-0.67.

  16. 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.

  17. 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

  18. 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

  19. A novel self-assembly with zinc porphyrin coordination polymer for enhanced photocurrent conversion in supramolecular solar cells

    International Nuclear Information System (INIS)

    Cao, Jing; Liu, Jia-Cheng; Deng, Wen-Ting; Li, Ren-Zhi; Jin, Neng-Zhi

    2013-01-01

    Graphical abstract: An innovative type of self-assembly based on acetohydrazide zinc porphyrin coordination polymer has been prepared in supramolecular solar cells. - Highlights: • A novel assembly with acetohydrazide porphyrin coordination polymer. • The assembly based on porphyrin is prepared as parallel sample. • Coordination polymer-based assembly shows enhanced photoelectronic behavior. • A series of different organic acid ligands as anchoring groups are prepared. - Abstract: In this work, a novel acetohydrazide zinc porphyrin-based coordination polymer (CP)-isonicotinic acid self-assembly by metal-ligand axial coordination to modify the nano-structured TiO 2 electrode surface has been investigated in photoelectrochemical device. Compared to the assembly based on corresponding zinc porphyrin combined with isonicotinic acid by metal-ligand axial coordination, CP-isonicotinic acid assembly exhibits a significantly enhanced photoelectronic behavior. In addition, a series of different organic acid ligands were prepared to probe the impact of their structures on the photoelectronic performances of their corresponding assemblies-sensitized cells. This study affords a novel type of self-assembly to functionalize the nanostructured TiO 2 electrode surface in supramolecular solar cells

  20. Self-Assembly, Interfacial Nanostructure, and Supramolecular Chirality of the Langmuir-Blodgett Films of Some Schiff Base Derivatives without Alkyl Chain

    Directory of Open Access Journals (Sweden)

    Tifeng Jiao

    2013-01-01

    Full Text Available A special naphthyl-containing Schiff base derivative, N,N′-bis(2-hydroxy-1-naphthylidene-1,2-phenylenediamine, was synthesized, and its coordination with various metal ions in situ at the air/water interface has been investigated. Although the ligand contains no alkyl chain, it can be spread on water surface. When metal ions existed in the subphase, an interfacial coordination between the ligand and different metal ions occurred in the spreading film, while different Nanostructures were fabricated in the monolayers. Interestingly to note that among various metal ions, only the in situ coordination-induced Cu(II-complex film showed supramolecular chirality, although the multilayer films from the ligand or preformed complex are achiral. The chirality of the in situ Cu(II-coordinated Langmuir film was developed due to the special distorted coordination reaction and the spatial limitation at the air/water interface. A possible organization mechanism at the air/water interface was suggested.

  1. 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.

  2. 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

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. Graphene–cyclodextrin–cytochrome c layered assembly with improved electron transfer rate and high supramolecular recognition capability

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Cheng-Bin; Guo, Cong-Cong; Jiang, Dan; Tang, Qian, E-mail: qiantang@swu.edu.cn; Liu, Chang-Hua; Ma, Xue-Bing

    2014-06-01

    This study aimed to develop a new graphene-based layered assembly, named graphene–cyclodextrin–cytochrome c with improved electron transfer rate. This assembly has combined high conductivity of graphene nanosheets (GNs), selectively binding properties and electronegativity of cyclodextrins (CDs), as well as electropositivity of cytochrome c (Cyt c). This assembly can also mimic the confined environments of the intermembrane space of mitochondria. A β-cyclodextrin (β-CD) functionalized GN (GN–CD) assembly was initially prepared by a simple wet-chemical strategy, i.e., in situ thermal reduction of graphene oxide with hydrazine hydrate in the presence of β-CD. Cyt c was then intercalated to the GN–CD assembly to form a layered self-assembled structure, GN–CD–Cyt c, through electrostatic interaction. Compared with GNs and GN–CD, GN–CD–Cyt c assembly displayed improved electron transfer rate and high supramolecular recognition capability toward six probe molecules. - Highlights: • A new tertiary layered assembly named GN–CD–Cyt c was prepared. • Compared with GNs and GN–CD, GN–CD–Cyt c shows improved electron transfer rate. • GN–CD–Cyt c displays high supramolecular recognition capability.

  10. Graphene–cyclodextrin–cytochrome c layered assembly with improved electron transfer rate and high supramolecular recognition capability

    International Nuclear Information System (INIS)

    Gong, Cheng-Bin; Guo, Cong-Cong; Jiang, Dan; Tang, Qian; Liu, Chang-Hua; Ma, Xue-Bing

    2014-01-01

    This study aimed to develop a new graphene-based layered assembly, named graphene–cyclodextrin–cytochrome c with improved electron transfer rate. This assembly has combined high conductivity of graphene nanosheets (GNs), selectively binding properties and electronegativity of cyclodextrins (CDs), as well as electropositivity of cytochrome c (Cyt c). This assembly can also mimic the confined environments of the intermembrane space of mitochondria. A β-cyclodextrin (β-CD) functionalized GN (GN–CD) assembly was initially prepared by a simple wet-chemical strategy, i.e., in situ thermal reduction of graphene oxide with hydrazine hydrate in the presence of β-CD. Cyt c was then intercalated to the GN–CD assembly to form a layered self-assembled structure, GN–CD–Cyt c, through electrostatic interaction. Compared with GNs and GN–CD, GN–CD–Cyt c assembly displayed improved electron transfer rate and high supramolecular recognition capability toward six probe molecules. - Highlights: • A new tertiary layered assembly named GN–CD–Cyt c was prepared. • Compared with GNs and GN–CD, GN–CD–Cyt c shows improved electron transfer rate. • GN–CD–Cyt c displays high supramolecular recognition capability

  11. 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.

  12. 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.

  13. 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.

  14. 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.

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

    Science.gov (United States)

    Tantakitti, Faifan

    Supramolecular chemistry is a powerful tool to create a material of a defined structure with tunable properties. This strategy has led to catalytically active, bioactive, and environment-responsive materials, among others, that are valuable in applications ranging from sensor technology to energy and medicine. Supramolecular polymers formed by peptide amphiphiles (PAs) have been especially relevant in tissue regeneration due to their ability to form biocompatible structures and mimic many important signaling molecules in biology. These supramolecular polymers can form nanofibers that create networks which mimic natural extracellular matrices. PA materials have been shown to induce growth of blood vessels, bone, cartilage, and nervous tissue, among others. The work described in this thesis not only studied the relationship between molecular structure and functions of PA assemblies, but also uncovered a powerful link between the energy landscape of their supramolecular self-assembly and the ability of PA materials to interact with cells. In chapter 2, it is argued that fabricating fibrous nanostructures with defined mechanical properties and decoration with bioactive molecules is not sufficient to create a material that can effectively communicate with cells. By systemically placing the fibronectin-derived RGDS epitope at increasing distances from the surface of PA nanofibers through a linker of one to five glycine residues, integrin-mediated RGDS signaling was enhanced. The results suggested that the spatial presentation of an epitope on PA nanofibers strongly influences the bioactivity of the PA substrates. In further improving functionality of a PA-based scaffold to effectively direct cell growth and differentiation, chapter 3 explored the use of a cell microcarrier to compartmentalize and simultaneously tune insoluble and soluble signals in a single matrix. PA nanofibers were incorporated at the surface of the microcarrier in order to promote cell adhesion, while

  16. 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

  17. 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

  18. 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.

  19. 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.

  20. Self-assembly of poly(ionic liquid) (PIL)-based amphiphilic homopolymers into vesicles and supramolecular structures with dyes and silver nanoparticles

    KAUST Repository

    Manojkumar, Kasina

    2017-04-27

    The incorporation of both hydrophilic and hydrophobic segments in homopolymers leads to their self-assembly into nanostructures in selective solvents, owing to their amphiphilic character. Here we report the RAFT polymerization of N-imidazole-3-propylmethacrylamide and the further quaternization of the resulting polymer with different alkyl bromides of a varying chain length, which afforded well-defined polymeric ionic liquids (PILs) 1-4. These PILs are characterized by the presence of both hydrophobic alkyl chains and hydrophilic ionic moieties, allowing their spontaneous self-assembly in water, forming distinct polymeric vesicles (= polymersomes) the size of which can be varied as a function of alkyl chain length. As demonstrated by the dye-encapsulation study, a particular organic-soluble PIL, 3, consisting of a dodecyl side-chain enabled the transfer of the water-soluble Rose Bengal dye, from an aqueous solution to the organic phase. In addition, polymersomes obtained from a PIL (2) featuring butyl side chains were used as templates and polymeric stabilizers of silver nanoparticles (NPs), i.e. leading to AgNP@PIL hybrids, as observed by transmission electron microscopy (TEM). It was found that the extent of functionalization of polymersomes by the Ag-based NPs varied greatly before and after the end-group removal of the PIL. Altogether, this report emphasizes the facile synthesis of amphiphilic homoPILs and their manipulation in water for dye encapsulation and for stabilization of silver NPs.

  1. Self-assembly of poly(ionic liquid) (PIL)-based amphiphilic homopolymers into vesicles and supramolecular structures with dyes and silver nanoparticles

    KAUST Repository

    Manojkumar, Kasina; Mecerreyes, David; Taton, Daniel; Gnanou, Yves; Vijayakrishna, Kari

    2017-01-01

    The incorporation of both hydrophilic and hydrophobic segments in homopolymers leads to their self-assembly into nanostructures in selective solvents, owing to their amphiphilic character. Here we report the RAFT polymerization of N-imidazole-3-propylmethacrylamide and the further quaternization of the resulting polymer with different alkyl bromides of a varying chain length, which afforded well-defined polymeric ionic liquids (PILs) 1-4. These PILs are characterized by the presence of both hydrophobic alkyl chains and hydrophilic ionic moieties, allowing their spontaneous self-assembly in water, forming distinct polymeric vesicles (= polymersomes) the size of which can be varied as a function of alkyl chain length. As demonstrated by the dye-encapsulation study, a particular organic-soluble PIL, 3, consisting of a dodecyl side-chain enabled the transfer of the water-soluble Rose Bengal dye, from an aqueous solution to the organic phase. In addition, polymersomes obtained from a PIL (2) featuring butyl side chains were used as templates and polymeric stabilizers of silver nanoparticles (NPs), i.e. leading to AgNP@PIL hybrids, as observed by transmission electron microscopy (TEM). It was found that the extent of functionalization of polymersomes by the Ag-based NPs varied greatly before and after the end-group removal of the PIL. Altogether, this report emphasizes the facile synthesis of amphiphilic homoPILs and their manipulation in water for dye encapsulation and for stabilization of silver NPs.

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

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael; Bergman, Robert; Raymond, Kenneth

    2009-04-10

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

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

    International Nuclear Information System (INIS)

    Pluth, Michael; Bergman, Robert; Raymond, Kenneth

    2009-01-01

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

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. Supramolecular Langmuir monolayers and multilayered vesicles of self-assembling DNA–lipid surface structures and their further implications in polyelectrolyte-based cell transfections

    Energy Technology Data Exchange (ETDEWEB)

    Demirsoy, Fatma Funda Kaya [Ankara University, The Central Laboratory of The Institute of Biotechnology (Turkey); Eruygur, Nuraniye [Gazi University, Department of Pharmacognosy, Faculty of Pharmacy (Turkey); Süleymanoğlu, Erhan, E-mail: erhans@mail.ru [Gazi University, Department of Pharmaceutical Chemistry, Faculty of Pharmacy (Turkey)

    2015-01-15

    The basic interfacial characteristics of DNA–lipid recognitions have been studied. The complex structures of individual unbound DNA molecules and their binary and ternary complexes with zwitterionic lipids and divalent cations were followed by employing lipid monolayers at the air–liquid interfaces, as well as by performing various microscopic, spectroscopic, and thermodynamic measurements with multilayered vesicles. The pressure-area isotherms depicted that Mg{sup 2+}-ions increase the surface pressure of lipid films and thus give rise to electrostatic and hydrophobic lipid–DNA interactions in terms of DNA adsorption, adhesion, and compaction. These features were further approached by using multilamellar vesicles with a mean diameter of 850 nm, where a metal ion-directed nucleic acid compaction and condensation effects were shown. The data obtained show the effectiveness of Langmuir monolayers and lipid multilayers in studying nucleic acid–lipid recognitions. The data provide with further details and support previous reports on mainly structural features of these recognitions. Biomolecular surface recognition events were presented in direct link with spectral and thermodynamic features of lipid vesicle–polynucleotide complex formations. The results serve to build a theoretical model considering the use of neutral lipids in lipoplex designs as a polyelectrolyte alternatives to the currently employed cytotoxic cationic liposomes. The supramolecular structures formed and their possible roles in interfacial electrostatic and hydrophobic mechanisms of endosomal escape in relevant cell transfection assays are particularly emphasized.

  9. Supramolecular Langmuir monolayers and multilayered vesicles of self-assembling DNA–lipid surface structures and their further implications in polyelectrolyte-based cell transfections

    International Nuclear Information System (INIS)

    Demirsoy, Fatma Funda Kaya; Eruygur, Nuraniye; Süleymanoğlu, Erhan

    2015-01-01

    The basic interfacial characteristics of DNA–lipid recognitions have been studied. The complex structures of individual unbound DNA molecules and their binary and ternary complexes with zwitterionic lipids and divalent cations were followed by employing lipid monolayers at the air–liquid interfaces, as well as by performing various microscopic, spectroscopic, and thermodynamic measurements with multilayered vesicles. The pressure-area isotherms depicted that Mg 2+ -ions increase the surface pressure of lipid films and thus give rise to electrostatic and hydrophobic lipid–DNA interactions in terms of DNA adsorption, adhesion, and compaction. These features were further approached by using multilamellar vesicles with a mean diameter of 850 nm, where a metal ion-directed nucleic acid compaction and condensation effects were shown. The data obtained show the effectiveness of Langmuir monolayers and lipid multilayers in studying nucleic acid–lipid recognitions. The data provide with further details and support previous reports on mainly structural features of these recognitions. Biomolecular surface recognition events were presented in direct link with spectral and thermodynamic features of lipid vesicle–polynucleotide complex formations. The results serve to build a theoretical model considering the use of neutral lipids in lipoplex designs as a polyelectrolyte alternatives to the currently employed cytotoxic cationic liposomes. The supramolecular structures formed and their possible roles in interfacial electrostatic and hydrophobic mechanisms of endosomal escape in relevant cell transfection assays are particularly emphasized

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-09-27

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

  11. 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

  12. Regulated assembly of a supramolecular centrosome scaffold in vitro

    DEFF Research Database (Denmark)

    Woodruff, J. B.; Wueseke, O.; Viscardi, V.

    2015-01-01

    are not well understood. In Caenorhabditis elegans, PCM assembly requires the coiled-coil protein SPD-5. We found that recombinant SPD-5 could polymerize to form micrometer-sized porous networks in vitro. Network assembly was accelerated by two conserved regulators that control PCM assembly in vivo, Polo...

  13. 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

  14. Helical self-organization and hierarchical self-assembly of an oligoheterocyclic pyridine-pyridazine strand into extended supramolecular fibers.

    Science.gov (United States)

    Cuccia, Louis A; Ruiz, Eliseo; Lehn, Jean-Marie; Homo, Jean-Claude; Schmutz, Marc

    2002-08-02

    The synthesis and characterization of an alternating pyridine-pyridazine strand comprising thirteen heterocycles are described. Spontaneous folding into a helical secondary structure is based on a general molecular self-organization process enforced by the conformational information encoded within the primary structure of the molecular strand itself. Conformational control based on heterocyclic "helicity codons" illustrates a strategy for designing folding properties into synthetic oligomers (foldamers). Strong intermolecular interactions of the highly ordered lock-washer subunits of compound 3 results in hierarchical supramolecular self-assembly into protofibrils and fibrils. Compound 3 also forms mechanically stable two-dimensional Langmuir-Blodgett and cast thin films.

  15. Conjugated material self-assembly : towards supramolecular electronics

    NARCIS (Netherlands)

    Leclère, P.E.L.G.; Surin, M.; Cavallini, 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

    Properties of organic electronic materials in solid-state are determined as individual molecules and molecular assembly. It is essential to optimize conjugated materials to control performance of molecular assembly that constitute electronic devices such as light-emitting diodes and solar cells, and

  16. 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.

  17. 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

  18. From fundamental supramolecular chemistry to self-assembled nanomaterials and medicines and back again - how Sam inspired SAMul.

    Science.gov (United States)

    Smith, David K

    2018-05-08

    This feature article provides a personal insight into the research from my group over the past 10 years. In particular, the article explains how, inspired in 2005 by meeting my now-husband, Sam, who had cystic fibrosis, and who in 2011 went on to have a double lung transplant, I took an active decision to follow a more applied approach to some of our research, attempting to use fundamental supramolecular chemistry to address problems of medical interest. In particular, our strategy uses self-assembly to fabricate biologically-active nanosystems from simple low-molecular-weight building blocks. These systems can bind biological polyanions in highly competitive conditions, allowing us to approach applications in gene delivery and coagulation control. In the process, however, we have also developed new fundamental principles such as self-assembled multivalency (SAMul), temporary 'on-off' multivalency, and adaptive/shape-persistent multivalent binding. By targeting materials with applications in drug formulation and tissue engineering, we have discovered novel self-assembling low-molecular-weight hydrogelators based on the industrially-relevant dibenzylidenesorbitol framework and developed innovative approaches to spatially-resolved gels and functional multicomponent hybrid hydrogels. In this way, taking an application-led approach to research has also delivered significant academic value and conceptual advances. Furthermore, beginning to translate fundamental supramolecular chemistry into real-world applications, starts to demonstrate the power of this approach, and its potential to transform the world around us for the better.

  19. Hierarchical assembly of branched supramolecular polymers from (cyclic Peptide)-polymer conjugates.

    Science.gov (United States)

    Koh, Ming Liang; Jolliffe, Katrina A; Perrier, Sébastien

    2014-11-10

    We report the synthesis and assembly of (N-methylated cyclic peptide)-polymer conjugates for which the cyclic peptide is attached to either the α- or both α- and ω- end groups of a polymer. A combination of chromatographic, spectroscopic, and scattering techniques reveals that the assembly of the conjugates follows a two-level hierarchy, initially driven by H-bond formation between two N-methylated cyclic peptides, followed by unspecific, noncovalent aggregation of this peptide into small domains that behave as branching points and lead to the formation of branched supramolecular polymers.

  20. 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.

  1. 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

    -overrich" hexamers and octamers, leads to surface-independent self-assembly of microfibers-helical or rodlike depending on the groups attached to the same identical inner core-that are crystalline, fluorescent, and conductive and display chirality despite the lack of chiral carbon atoms on the building blocks. Supramolecular polymorphic microfibers are also formed, and they are characterized by very different functional properties. The second, based on a rigid oligothiophene-S,S-dioxide, leads to coassembled protein-oligothiophene microfibers that are physiologically formed inside live cells. The oligothiophene-S,S-dioxide can indeed spontaneously cross the membrane of live cells and be directed toward the perinuclear region, where it is recognized and incorporated by specific peptides during the formation of fibrillar proteins without being harmful to the cells. Coassembled oligothiophene-protein microfibers are progressively formed through a cell-mediated physiological process. Thanks to the oligothiophene blocks, the microfibers possess fluorescence and charge-conduction properties. By means of fluorescence imaging, we demonstrated that various types of live cells seeded on these microfibers were able to internalize and degrade them, experiencing in turn different effects on their morphology and viability, suggesting a possible use of the microfibers as multiscale biomaterials to direct cell behavior. On the whole, our results show the great versatility of oligothiophene building blocks and allow us to foresee that their capabilities of spontaneous assembly in the most different environments could be exploited in much more exciting research fields than those explored to date.

  2. Controlling Photoconductivity in PBI Films by Supramolecular Assembly.

    Science.gov (United States)

    Draper, Emily R; Archibald, Lewis J; Nolan, Michael C; Schweins, Ralf; Zwijnenburg, Martijn A; Sproules, Stephen; Adams, Dave J

    2018-03-15

    Perylene bisimides (PBIs) self-assemble in solution. The solubility of the PBIs is commonly changed through the choice of substituents at the imide positions. It is generally assumed this substitution does not affect the electronic properties of the PBI, and that the properties of the self-assembled aggregate are essentially that of the isolated molecule. However, substituents do affect the self-assembly, resulting in potentially different packing in the formed aggregates. Here, we show that the photoconductivity of films formed from a library of substituted PBIs varies strongly with the substituent and demonstrate that this is due to the different ways in which they pack. Our results open the possibility for tuning the optoelectronic properties of self-assembled PBIs by controlling the aggregate structure through careful choice of substituent, as demonstrated by us here optimising the photoconductivity of PBI films in this way. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  3. 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 ...

  4. 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....

  5. Graphene-cyclodextrin-cytochrome c layered assembly with improved electron transfer rate and high supramolecular recognition capability.

    Science.gov (United States)

    Gong, Cheng-Bin; Guo, Cong-Cong; Jiang, Dan; Tang, Qian; Liu, Chang-Hua; Ma, Xue-Bing

    2014-06-01

    This study aimed to develop a new graphene-based layered assembly, named graphene-cyclodextrin-cytochrome c with improved electron transfer rate. This assembly has combined high conductivity of graphene nanosheets (GNs), selectively binding properties and electronegativity of cyclodextrins (CDs), as well as electropositivity of cytochrome c (Cyt c). This assembly can also mimic the confined environments of the intermembrane space of mitochondria. A β-cyclodextrin (β-CD) functionalized GN (GN-CD) assembly was initially prepared by a simple wet-chemical strategy, i.e., in situ thermal reduction of graphene oxide with hydrazine hydrate in the presence of β-CD. Cyt c was then intercalated to the GN-CD assembly to form a layered self-assembled structure, GN-CD-Cyt c, through electrostatic interaction. Compared with GNs and GN-CD, GN-CD-Cyt c assembly displayed improved electron transfer rate and high supramolecular recognition capability toward six probe molecules. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Generation of Supramolecular Chirality around Twofold Rotational or Helical Axes in Crystalline Assemblies of Achiral Components

    Directory of Open Access Journals (Sweden)

    Mikiji Miyata

    2015-10-01

    Full Text Available A multi-point approximation method clarifies supramolecular chirality of twofold rotational or helical assemblies as well as bundles of the one-dimensional (1D assemblies. While one-point approximation of materials claims no chirality generation of such assemblies, multi-point approximations do claim possible generation in the 1D assemblies of bars and plates. Such chirality derives from deformations toward three-axial directions around the helical axes. The chiral columns are bundled in chiral ways through symmetry operations. The preferable right- or left-handed columns are bundled together to yield chiral crystals with right- or left-handedness, respectively, indicating that twofold helix symmetry operations cause chiral crystals composed of achiral components via a three-stepwise and three-directional process.

  7. 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

  8. 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

  9. Complexation-induced supramolecular assembly drives metal-ion extraction.

    Science.gov (United States)

    Ellis, Ross J; Meridiano, Yannick; Muller, Julie; Berthon, Laurence; Guilbaud, Philippe; Zorz, Nicole; Antonio, Mark R; Demars, Thomas; Zemb, Thomas

    2014-09-26

    Combining experiment with theory reveals the role of self-assembly and complexation in metal-ion transfer through the water-oil interface. The coordinating metal salt Eu(NO3)3 was extracted from water into oil by a lipophilic neutral amphiphile. Molecular dynamics simulations were coupled to experimental spectroscopic and X-ray scattering techniques to investigate how local coordination interactions between the metal ion and ligands in the organic phase combine with long-range interactions to produce spontaneous changes in the solvent microstructure. Extraction of the Eu(3+)-3(NO3(-)) ion pairs involves incorporation of the "hard" metal complex into the core of "soft" aggregates. This seeds the formation of reverse micelles that draw the water and "free" amphiphile into nanoscale hydrophilic domains. The reverse micelles interact through attractive van der Waals interactions and coalesce into rod-shaped polynuclear Eu(III) -containing aggregates with metal centers bridged by nitrate. These preorganized hydrophilic domains, containing high densities of O-donor ligands and anions, provide improved Eu(III) solvation environments that help drive interfacial transfer, as is reflected by the increasing Eu(III) partitioning ratios (oil/aqueous) despite the organic phase approaching saturation. For the first time, this multiscale approach links metal-ion coordination with nanoscale structure to reveal the free-energy balance that drives the phase transfer of neutral metal salts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Two-photon absorption of a supramolecular pseudoisocyanine J-aggregate assembly

    International Nuclear Information System (INIS)

    Belfield, Kevin D.; Bondar, Mykhailo V.; Hernandez, Florencio E.; Przhonska, Olga V.; Yao, Sheng

    2006-01-01

    Linear spectral properties, including excitation anisotropy, of pseudoisocyanine or 1,1'-diethyl-2,2'-cyanine iodide (PIC) J-aggregates in aqueous solutions with J-band position at 573 nm were investigated. Two-photon absorption of PIC J-aggregates and monomer molecules was studied using an open aperture Z-scan technique. A strong enhancement of the two-photon absorption cross-section of PIC in the supramolecular J-aggregate assembly was observed in aqueous solution. This enhancement is attributed to a strong coupling of the molecular transition dipoles. No two-photon absorption at the peak of the J-band was detected

  11. Protein-based polymers that bond to DNA : design of virus-like particles and supramolecular nanostructures

    NARCIS (Netherlands)

    Hernandez Garcia, A.

    2014-01-01

    In this thesis it is demonstrated that it is possible to use Protein-based Polymers (PbPs) as synthetic binders of DNA (or any other negatively charged polyelectrolyte). The PbPs co-assemble with their DNA templates to form highly organized virus-like particles and supramolecular structures. A

  12. A versatile strategy towards non-covalent functionalization of graphene by surface-confined supramolecular self-assembly of Janus tectons

    Directory of Open Access Journals (Sweden)

    Ping Du

    2015-03-01

    Full Text Available Two-dimensional (2D, supramolecular self-assembly at surfaces is now well-mastered with several existing examples. However, one remaining challenge to enable future applications in nanoscience is to provide potential functionalities to the physisorbed adlayer. This work reviews a recently developed strategy that addresses this key issue by taking advantage of a new concept, Janus tecton materials. This is a versatile, molecular platform based on the design of three-dimensional (3D building blocks consisting of two faces linked by a cyclophane-type pillar. One face is designed to steer 2D self-assembly onto C(sp2-carbon-based flat surfaces, the other allowing for the desired functionality above the substrate with a well-controlled lateral order. In this way, it is possible to simultaneously obtain a regular, non-covalent paving as well as supramolecular functionalization of graphene, thus opening interesting perspectives for nanoscience applications.

  13. 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.

  14. 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.

  15. 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.

  16. Force and time-dependent self-assembly, disruption and recovery of supramolecular peptide amphiphile nanofibers.

    Science.gov (United States)

    Dikecoglu, F Begum; Topal, Ahmet E; Ozkan, Alper D; Tekin, E Deniz; Tekinay, Ayse B; Guler, Mustafa O; Dana, Aykutlu

    2018-07-13

    Biological feedback mechanisms exert precise control over the initiation and termination of molecular self-assembly in response to environmental stimuli, while minimizing the formation and propagation of defects through self-repair processes. Peptide amphiphile (PA) molecules can self-assemble at physiological conditions to form supramolecular nanostructures that structurally and functionally resemble the nanofibrous proteins of the extracellular matrix, and their ability to reconfigure themselves in response to external stimuli is crucial for the design of intelligent biomaterials systems. Here, we investigated real-time self-assembly, deformation, and recovery of PA nanofibers in aqueous solution by using a force-stabilizing double-pass scanning atomic force microscopy imaging method to disrupt the self-assembled peptide nanofibers in a force-dependent manner. We demonstrate that nanofiber damage occurs at tip-sample interaction forces exceeding 1 nN, and the damaged fibers subsequently recover when the tip pressure is reduced. Nanofiber ends occasionally fail to reconnect following breakage and continue to grow as two individual nanofibers. Energy minimization calculations of nanofibers with increasing cross-sectional ellipticity (corresponding to varying levels of tip-induced fiber deformation) support our observations, with high-ellipticity nanofibers exhibiting lower stability compared to their non-deformed counterparts. Consequently, tip-mediated mechanical forces can provide an effective means of altering nanofiber integrity and visualizing the self-recovery of PA assemblies.

  17. Asymmetric noncovalent synthesis of self-assembled one-dimensional stacks by a chiral supramolecular auxiliary approach

    NARCIS (Netherlands)

    George, S.J.; Tomovic, Z.; Averbeke, Van B.; Beljonne, D.; Lazzaroni, R.; Schenning, A.P.H.J.; Meijer, E.W.

    2012-01-01

    Stereoselective noncovalent synthesis of one-dimensional helical self-assembled stacks of achiral oligo(p-phenylenevinylene) ureidotriazine (AOPV3) monomers is obtained by a chiral supramolecular auxiliary approach. The racemic mixture of helical stacks of achiral AOPV3 molecules is converted into

  18. 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.

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

    Science.gov (United States)

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

    2017-07-01

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

  20. Competitive Self-Assembly Manifests Supramolecular Darwinism in Soft-Oxometalates

    Science.gov (United States)

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

    2015-09-01

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

  1. Self-assembly of a supramolecular square between [Ni(dppe(TOF2] and 4,4'-Bipyridine

    Directory of Open Access Journals (Sweden)

    Paulo Torres

    2013-08-01

    Full Text Available The main interest of this research is to contribute to the development and understanding of supramolecular chemistry and molecular architectures, which are constructed by the self-assembly of supramolecular entities. Therefore, the synthesis and characterization (IR, UV, 1H NMR, 31P, 19F, 1H-1H COSY of a nickel (II supramolecular square [7] was performed through the synthesis between nickel chloride [1] and diphenylphosphinoethane (dppe [2] to form the precursor complex [Ni(dppeCl2] [3]. This was followed by the synthesis of the complex of interest, [Ni(dppe(TOF2] [5], using the precursor and silver trifluoromethanesulfonate (Ag-TOF. Finally, the self-assembly was performed between the complex [1,2-bis(diphenylphosphinoethanebistriflatonickel(II] [Ni(dppe(OSO2CF32] [5] and the organic ligand 4,4'-bipyridine [6], which act as vertex and edge, respectively.According to various analyses, it was found that the self-assembly generated only one supramolecular species; a square is the most probable thermodynamic structure.

  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.

  3. Sensitization effects of supramolecular assemblies on the luminescence of terbium-ion prulifloxacin complexes

    Energy Technology Data Exchange (ETDEWEB)

    Wang Hong; Yi Chongyue; Li Xue; Fang Fang [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Yang Yajiang, E-mail: yjyang@mail.hust.edu.c [School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2011-04-15

    Luminescence enhancement of terbium-ion prulifloxacin complexes (Tb(III)-PUFX) in supramolecular hydrogels formed by assembly of 1,3:2,4-di-O-benzylidene-D-sorbitol (DBS) was investigated by steady-state fluorescence, varying temperature fluorescence and time-resolved fluorescence. The luminescence images show that Tb(III)-PUFX were dispersed in the DBS gels. The luminescence intensity of Tb(III)-PUFX in the DBS gels was significantly increased in comparison with that in corresponding aqueous solutions. The varying temperature fluorescent spectra show that the luminescence intensity of Tb(III)-PUFX decreased with an increase in the temperature. This implies that the luminescence enhancement of Tb(III)-PUFX is related to the dissociation and the formation of the DBS assemblies. Time-resolved fluorescence measurements show slower rotational motion in DBS gels in comparison with that in the corresponding aqueous solutions. This may be ascribed to a unique microstructure of three-dimensional network formed by DBC aggregates, resulting in deactivation of the nonradiative relaxation. The images of field emission scanning electron microscopy and polarized optical microscopy indicate that the morphology of the DBS assemblies was not influenced upon addition of Tb(III)-PUFX to the DBS gels.

  4. 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

  5. Supramolecular Self-Assembly of Histidine-Capped-Dialkoxy-Anthracene: A Visible Light Triggered Platform for facile siRNA Delivery

    KAUST Repository

    Patil, Sachin; Moosa, Basem; Alsaiari, Shahad; Alamoudi, Kholod; Alshamsan, Aws; Almailk, Abdulaziz; Adil, Karim; Eddaoudi, Mohamed; Khashab, Niveen M.

    2016-01-01

    Supramolecular self-assembly of histidine-capped-dialkoxy-anthracene (HDA) results in the formation of light responsive nanostructures.Single-crystal X-ray diffraction analysis of HDA shows two types of hydrogen bonding. The first hydrogen bond

  6. Luminescent lanthanide complexes with 4-acetamidobenzoate: Synthesis, supramolecular assembly via hydrogen bonds, crystal structures and photoluminescence

    International Nuclear Information System (INIS)

    Yin Xia; Fan Jun; Wang Zhihong; Zheng Shengrun; Tan Jingbo; Zhang Weiguang

    2011-01-01

    Four new luminescent complexes, namely, [Eu(aba) 2 (NO 3 )(C 2 H 5 OH) 2 ] (1), [Eu(aba) 3 (H 2 O) 2 ].0.5 (4, 4'-bpy).2H 2 O (2), [Eu 2 (aba) 4 (2, 2'-bpy) 2 (NO 3 ) 2 ].4H 2 O (3) and [Tb 2 (aba) 4 (phen) 2 (NO 3 ) 2 ].2C 2 H 5 OH (4) were obtained by treating Ln(NO 3 ) 3 .6H 2 O and 4-acetamidobenzoic acid (Haba) with different coligands (4, 4'-bpy=4, 4'-bipyridine, 2, 2'-bpy=2, 2'-bipyridine, and phen=1, 10-phenanthroline). They exhibit 1D chains (1-2) and dimeric structures (3-4), respectively. This structural variation is mainly attributed to the change of coligands and various coordination modes of aba molecules. Moreover, the coordination units are further connected via hydrogen bonds to form 2D even 3D supramolecular networks. These complexes show characteristic emissions in the visible region at room temperature. In addition, thermal behaviors of four complexes have been investigated under air atmosphere. The relationship between the structures and physical properties has been discussed. - Graphical abstract: Structure variation of four complexes is attributed to the change of coligands and various coordination modes of aba molecules. Moreover, they show characteristic emissions in the visible region. Highlights: → Auxiliary ligands have played the crucial roles on the structures of the resulting complexes. → Isolated structure units are further assembled via H-bonds to form supramolecular networks. → These solid-state complexes exhibit strong, characteristic emissions in the visible region.

  7. 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.

  8. Water-Insoluble Photosensitizer Nanocolloids Stabilized by Supramolecular Interfacial Assembly towards Photodynamic Therapy

    Science.gov (United States)

    Liu, Yamei; Ma, Kai; Jiao, Tifeng; Xing, Ruirui; Shen, Guizhi; Yan, Xuehai

    2017-02-01

    Nanoengineering of hydrophobic photosensitizers (PSs) is a promising approach for improved tumor delivery and enhanced photodynamic therapy (PDT) efficiency. A variety of delivery carriers have been developed for tumor delivery of PSs through the enhanced permeation and retention (EPR) effect. However, a high-performance PS delivery system with minimum use of carrier materials with excellent biocompatibility is highly appreciated. In this work, we utilized the spatiotemporal interfacial adhesion and assembly of supramolecular coordination to achieve the nanoengineering of water-insoluble photosensitizer Chlorin e6 (Ce6). The hydrophobic Ce6 nanoparticles are well stabilized in a aqueous medium by the interfacially-assembled film due to the coordination polymerization of tannic acid (TA) and ferric iron (Fe(III)). The resulting Ce6@TA-Fe(III) complex nanoparticles (referenced as Ce6@TA-Fe(III) NPs) significantly improves the drug loading content (~65%) and have an average size of 60 nm. The Ce6@TA-Fe(III) NPs are almost non-emissive as the aggregated states, but they can light up after intracellular internalization, which thus realizes low dark toxicity and excellent phototoxicity under laser irradiation. The Ce6@TA-Fe(III) NPs prolong blood circulation, promote tumor-selective accumulation of PSs, and enhanced antitumor efficacy in comparison to the free-carrier Ce6 in vivo evaluation.

  9. Carbohydrates in Supramolecular Chemistry.

    Science.gov (United States)

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

    2016-02-24

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

  10. Template Syntheses, Crystal Structures and Supramolecular Assembly of Hexaaza Macrocyclic Copper(II) Complexes

    International Nuclear Information System (INIS)

    Kim, Taehyung; Kim, Ju Chang; Lough, Alan J.

    2013-01-01

    Two new hexaaza macrocyclic copper(II) complexes were prepared by a template method and structurally characterized. In the solid state, they were self-assembled by intermolecular interactions to form the corresponding supramolecules 1 and 2, respectively. In the structure of 1, the copper(II) macrocycles are bridged by a tp ligand to form a macrocyclic copper(II) dimer. The dimer extends its structure by intermolecular forces such as hydrogen bonds and C-H···π interactions, resulting in the formation of a double stranded 1D supramolecule. In 2, the basic structure is a monomeric copper(II) macrocycle with deprotonated imidazole pendants. An undulated 1D hydrogen bonded array is achieved through hydrogen bonds between imidazole pendants and secondary amines, where the imidazole pendants act as a hydrogen bond acceptor. The 1D hydrogen bonded supramolecular chain is supported by C-H···π interactions between the methyl groups of acetonitrile ligands and imidazole pendants of the copper(II) macrocycles. In both complexes, the introduction of imidazoles to the macrocycle as a pendant plays an important role for the formation of supramolecules, where they act as intermolecular hydrogen bond donors and/or acceptors, C-H···π and π-π interactions

  11. Assembly of one-dimensional supramolecular objects: From monomers to networks

    Science.gov (United States)

    Sayar, Mehmet; Stupp, Samuel I.

    2005-07-01

    One-dimensional supramolecular aggregates can form networks at exceedingly low concentrations. Recent experiments in several laboratories, including our own, have demonstrated the formation of gels by these systems at concentrations well under 1% by weight. The systems of interest in our laboratory form either cylindrical nanofibers or ribbons as a result of strong noncovalent interactions among monomers. The stiffness and interaction energies among these thread-like objects can vary significantly depending on the chemical structure of the monomers used. We have used Monte Carlo simulations to study the structure of the threads and their ability to form networks through bundle formation. The persistence length of the threads was found to be strongly affected not only by stiffness, but also by the strength of attractive two-body interactions among thread segments. The relative values of stiffness and attractive two-body interaction strength determine if threads collapse or create bundles. Only in the presence of sufficiently long threads and bundle formation can these systems assemble into networks of high connectivity.

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

    Directory of Open Access Journals (Sweden)

    Yao Wang

    2014-05-01

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

  13. Supramolecular assembly of group 11 phosphorescent metal complexes for chemosensors of alcohol derivatives

    Science.gov (United States)

    Lintang, H. O.; Ghazalli, N. F.; Yuliati, L.

    2018-04-01

    We report on systematic study on vapochromic sensing of ethanol by using phosphorescent trinuclear metal pyrazolate complexes with supramolecular assembly of weak intermolecular metal-metal interactions using 4-(3,5-dimethoxybenzyl)-3,5-dimethyl pyrazole ligand (1) and group 11 metal ions (Cu(I), Ag(I), Au(I)). Upon excitation at 284, the resulting complexes showed emission bands with a peak centered at 616, 473 and 612 nm for 2(Cu), 2(Ag) and 2(Au), respectively. Chemosensor 2(Cu) showed positive response to ethanol vapors in 5 mins by blue-shifting its emission band from 616 to 555 nm and emitting bright orange to green. Otherwise 2(Au) gave shifting from its emission band centered at 612 to 587 nm with Δλ of 25 nm (41%) and color changes from red-orange to light green-orange while 2(Ag) showed quenching in its original emission intensity at 473 nm in 40% with color changes from dark green to less emissive. These results demonstrate that sensing capability of chemosensor 2(Cu) with suitable molecular design of ligand and metal ion in the complex is due to the formation of a weak intermolecular hydrogen bonding interaction of O atom at the methoxy of the benzyl ring with the OH of the vapors at the outside of the molecules.

  14. Supramolecular assembly of a series of chiral dendrimers in interfacial films

    International Nuclear Information System (INIS)

    Yuan Jing; Deng Guojun; Fan Qinghua; Liu Minghua

    2004-01-01

    Supramolecular assembly and interfacial properties of a series of novel binaphthyl containing dendrimers from generation 1 through generation 4 have been investigated at the air/water interface and in solid substrates. Due to the lack of either long alkyl chains or strong hydrophilic groups, the dendrimer molecules tend to aggregate together to form stable two-dimensional ultrathin films, as verified by π-A and A-t measurements. Atomic force microscope (AFM) measurements of the transferred one-layer ultrathin films indicate that all the dendrimers show disk-like morphologies, which could be varied in particle size upon changing the surface pressure. The height profiles reveal that the height of the disks is between that of a monolayer and a bilayer, indicating that they are formed due to the aggregation of dendrimers with a distortion and/or partial overlapping. Circular dichroism (CD) spectra of the transferred multilayer films show Cotton effects due to the exciton couplet of the aromatic moieties adjacent to the bis(diphenylphosphino)-binaphthyl moiety, which is an active catalytic site for the dendrimer. With the increment of the generation, the intensity of the Cotton effects increased, suggesting that the optical active site of the dendrimer can be controlled by the outside wedge

  15. 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.

  16. Functionalized Nanostructures: Redox-Active Porphyrin Anchors for Supramolecular DNA Assemblies

    KAUST Repository

    Börjesson, Karl

    2010-09-28

    We have synthesized and studied a supramolecular system comprising a 39-mer DNA with porphyrin-modified thymidine nucleosides anchored to the surface of large unilamellar vesicles (liposomes). Liposome porphyrin binding characteristics, such as orientation, strength, homogeneity, and binding site size, was determined, suggesting that the porphyrin is well suited as a photophysical and redox-active lipid anchor, in comparison to the inert cholesterol anchor commonly used today. Furthermore, the binding characteristics and hybridization capabilities were studied as a function of anchor size and number of anchoring points, properties that are of importance for our future plans to use the addressability of these redox-active nodes in larger DNA-based nanoconstructs. Electron transfer from photoexcited porphyrin to a lipophilic benzoquinone residing in the lipid membrane was characterized by steady-state and time-resolved fluorescence and verified by femtosecond transient absorption. © 2010 American Chemical Society.

  17. 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.

  18. Self-assembled materials and supramolecular chemistry within microfluidic environments: from common thermodynamic states to non-equilibrium structures.

    Science.gov (United States)

    Sevim, S; Sorrenti, A; Franco, C; Furukawa, S; Pané, S; deMello, A J; Puigmartí-Luis, J

    2018-05-01

    Self-assembly is a crucial component in the bottom-up fabrication of hierarchical supramolecular structures and advanced functional materials. Control has traditionally relied on the use of encoded building blocks bearing suitable moieties for recognition and interaction, with targeting of the thermodynamic equilibrium state. On the other hand, nature leverages the control of reaction-diffusion processes to create hierarchically organized materials with surprisingly complex biological functions. Indeed, under non-equilibrium conditions (kinetic control), the spatio-temporal command of chemical gradients and reactant mixing during self-assembly (the creation of non-uniform chemical environments for example) can strongly affect the outcome of the self-assembly process. This directly enables a precise control over material properties and functions. In this tutorial review, we show how the unique physical conditions offered by microfluidic technologies can be advantageously used to control the self-assembly of materials and of supramolecular aggregates in solution, making possible the isolation of intermediate states and unprecedented non-equilibrium structures, as well as the emergence of novel functions. Selected examples from the literature will be used to confirm that microfluidic devices are an invaluable toolbox technology for unveiling, understanding and steering self-assembly pathways to desired structures, properties and functions, as well as advanced processing tools for device fabrication and integration.

  19. Supramolecular Assembly of Comb-like Macromolecules Induced by Chemical Reactions that Modulate the Macromolecular Interactions In Situ.

    Science.gov (United States)

    Xia, Hongwei; Fu, Hailin; Zhang, Yanfeng; Shih, Kuo-Chih; Ren, Yuan; Anuganti, Murali; Nieh, Mu-Ping; Cheng, Jianjun; Lin, Yao

    2017-08-16

    Supramolecular polymerization or assembly of proteins or large macromolecular units by a homogeneous nucleation mechanism can be quite slow and require specific solution conditions. In nature, protein assembly is often regulated by molecules that modulate the electrostatic interactions of the protein subunits for various association strengths. The key to this regulation is the coupling of the assembly process with a reversible or irreversible chemical reaction that occurs within the constituent subunits. However, realizing this complex process by the rational design of synthetic molecules or macromolecules remains a challenge. Herein, we use a synthetic polypeptide-grafted comb macromolecule to demonstrate how the in situ modulation of interactions between the charged macromolecules affects their resulting supramolecular structures. The kinetics of structural formation was studied and can be described by a generalized model of nucleated polymerization containing secondary pathways. Basic thermodynamic analysis indicated the delicate role of the electrostatic interactions between the charged subunits in the reaction-induced assembly process. This approach may be applicable for assembling a variety of ionic soft matters that are amenable to chemical reactions in situ.

  20. 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.

  1. 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.

  2. 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)

    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.

  3. Supramolecular assembly of biological molecules purified from bovine nerve cells: from microtubule bundles and necklaces to neurofilament networks

    International Nuclear Information System (INIS)

    Needleman, Daniel J; Jones, Jayna B; Raviv, Uri; Ojeda-Lopez, Miguel A; Miller, H P; Li, Y; Wilson, L; Safinya, C R

    2005-01-01

    With the completion of the human genome project, the biosciences community is beginning the daunting task of understanding the structures and functions of a large number of interacting biological macromolecules. Examples include the interacting molecules involved in the process of DNA condensation during the cell cycle, and in the formation of bundles and networks of filamentous actin proteins in cell attachment, motility and cytokinesis. In this proceedings paper we present examples of supramolecular assembly based on proteins derived from the vertebrate nerve cell cytoskeleton. The axonal cytoskeleton in vertebrate neurons provides a rich example of bundles and networks of neurofilaments, microtubules (MTs) and filamentous actin, where the nature of the interactions, structures, and structure-function correlations remains poorly understood. We describe synchrotron x-ray diffraction, electron microscopy, and optical imaging data, in reconstituted protein systems purified from bovine central nervous system, which reveal unexpected structures not predicted by current electrostatic theories of polyelectrolyte bundling, including three-dimensional MT bundles and two-dimensional MT necklaces

  4. 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

  5. Effects of subtle differences in ligand constitution and conformation in metallo-supramolecular self-assembled polygons.

    Science.gov (United States)

    Brusilowskij, Boris; Dzyuba, Egor V; Troff, Ralf W; Schalley, Christoph A

    2011-12-07

    3,3'-Bis(pyridin-[n]-ylethynyl)biphenyl (n = 3, 4) and the corresponding 2,2'-bipyridines assemble with (dppp)Pt(II) triflate into metallo-supramolecular polygons. Depending on the position of the terminal pyridine N atoms, the assembly reaction leads to different equilibrium products. With the slow ligand exchange on Pt(II) complexes, the equilibrium is reached on a many-hour time-scale. During the assembly process, larger polygons form under kinetic control. This was confirmed by time-dependent (1)H and (31)P NMR spectroscopy in line with complementary ESI mass spectrometric experiments. The constitutional difference in the pyridine N-atom position is reflected in the tandem mass spectra of the complex ions. In addition, a highly specific fragmentation process of mass-selected M(3)L(3) ions was observed, which proceeds through a ring contraction yielding smaller M(2)L(2) ions.

  6. 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

  7. 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.

  8. Mesoscopic self-organization of a self-assembled supramolecular rectangle on highly oriented pyrolytic graphite and Au(111) surfaces.

    Science.gov (United States)

    Gong, Jian-Ru; Wan, Li-Jun; Yuan, Qun-Hui; Bai, Chun-Li; Jude, Hershel; Stang, Peter J

    2005-01-25

    A self-assembled supramolecular metallacyclic rectangle was investigated with scanning tunneling microscopy on highly oriented pyrolytic graphite and Au(111) surfaces. The rectangles spontaneously adsorb on both surfaces and self-organize into well ordered adlayers. On highly oriented pyrolytic graphite, the long edge of the rectangle stands on the surface, forming a 2D molecular network. In contrast, the face of the rectangle lays flat on the Au(111) surface, forming linear chains. The structures and intramolecular features obtained through high-resolution scanning tunneling microscopy imaging are discussed.

  9. Improved enzyme-mediated synthesis and supramolecular self-assembly of naturally occurring conjugates of beta-sitosterol

    Czech Academy of Sciences Publication Activity Database

    Wimmerová, Martina; Siglerová, Věra; Šaman, David; Šlouf, Miroslav; Kaletová, Eva; Wimmer, Zdeněk

    2017-01-01

    Roč. 117, JAN (2017), s. 38-43 ISSN 0039-128X R&D Projects: GA MŠk LD15012; GA MŠk(CZ) LO1507 Institutional support: RVO:61389030 ; RVO:61388963 ; RVO:61389013 Keywords : glycosides * esterification * resolution * sterols * esters * foods * l. * beta-Sitosterol * Acylated steryl glycoside * Lipase * Ionic liquid * Supramolecular self-assembly * Pharmacological activity Subject RIV: CC - Organic Chemistry; CD - Macromolecular Chemistry (UMCH-V) OBOR OECD: Organic chemistry; Polymer science (UMCH-V); Organic chemistry (UOCHB-X) Impact factor: 2.282, year: 2016

  10. Direct and quantitative characterization of dynamic ligand exchange between coordination-driven self-assembled supramolecular polygons.

    Science.gov (United States)

    Zheng, Yao-Rong; Stang, Peter J

    2009-03-18

    The direct observation of dynamic ligand exchange between Pt-N coordination-driven self-assembled supramolecular polygons (triangles and rectangles) has been achieved using stable (1)H/(2)D isotope labeling of the pyridyl donors and electrospray ionization mass spectrometry combined with NMR spectroscopy. Both the thermodynamic and kinetic aspects of such exchange processes have been established on the basis of quantitative mass spectral results. Further investigation has shown that the exchange is highly dependent on experimental conditions such as temperature, solvent, and the counteranions.

  11. Geometry directed self-selection in the coordination-driven self-assembly of irregular supramolecular polygons.

    Science.gov (United States)

    Zheng, Yao-Rong; Northrop, Brian H; Yang, Hai-Bo; Zhao, Liang; Stang, Peter J

    2009-05-01

    The self-assembly of irregular metallo-supramolecular hexagons and parallelograms has been achieved in a self-selective manner upon mixing 120 degrees unsymmetrical dipyridyl ligands with 60 degrees or 120 degrees organoplatinum acceptors in a 1:1 ratio. The polygons have been characterized using (31)P and (1)H multinuclear NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS) as well as X-ray crystallography. Geometric features of the molecular subunits direct the self-selection process, which is supported by molecular force field computations.

  12. Charge Effect on the Formation of Polyoxometalate-Based Supramolecular Polygons Driven by Metal Coordination.

    Science.gov (United States)

    Piot, Madeleine; Hupin, Sébastien; Lavanant, Hélène; Afonso, Carlos; Bouteiller, Laurent; Proust, Anna; Izzet, Guillaume

    2017-07-17

    The metal-driven self-assembly of a Keggin-based hybrid bearing two remote pyridine units was investigated. The resulting supramolecular species were identified by combination of 2D diffusion NMR spectroscopy (DOSY) and electrospray ionization mass spectrometry (ESI-MS) as a mixture of molecular triangles and squares. This behavior is different from that of the structural analogue Dawson-based hybrid displaying a higher charge, which only led to the formation of molecular triangles. This study highlights the decisive effect of the charge of the POMs in their self-assembly processes that disfavors the formation of large assemblies. An isothermal titration calorimetry (ITC) experiment confirmed the stronger binding in the case of the Keggin hybrids. A correlation between the diffusion coefficient D and the molecular mass M of the POM-based building block and its coordination oligomers was also observed. We show that the diffusion coefficient of these compounds is mainly determined by their occupied volume rather than by their shape.

  13. Organic-inorganic hybrid supramolecular assemblies based on isomers [H{sub x}As{sub 2}Mo{sub 6}O{sub 26}]{sup (6-x)-} clusters

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Zhi-Feng [College of Material Science and Engineering, Heilongjiang University of Science and Technology, Harbin (China); Su, Zhan-Hua; Cong, Bo-Wen; Zhao, Wen-Qi; Ma, Xiu-Juan [School of Chemistry and Chemical Engineering, Harbin Normal University, Harbin (China)

    2017-08-16

    The arsenomolybdates [H{sub 2}As{sub 2}Mo{sub 6}O{sub 26}(H{sub 2}O)].(H{sub 2}biyb){sub 2}.2H{sub 2}O (1) and [H{sub 3}As{sub 2}Mo{sub 6}O{sub 26}].(H{sub 3}pt){sub 2} (2) [biyb = 1,4-bis(imidazol-1-ylmethyl)benzene, pt = 4'-(3{sup ''}-pyridyl)-2,3':6'3{sup ''}-terpyridine] were synthesized via hydrothermal method. The structures of the compounds were characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR spectroscopy, and TG analysis. Compounds 1 and 2 exhibit two isomeric forms of [H{sub x}As{sub 2}Mo{sub 6}O{sub 26}]{sup (6-x)-}. The structure of 1 is constructed from the B-type [H{sub 2}As{sub 2}Mo{sub 6}O{sub 26}(H{sub 2}O)]{sup 4-} polyanions and free biyb ligands via weak interactions to form 3D supramolecular framework with a {3.4.5"3.6}{3.4"3.5"2}{3.5.6}{sup 2}{3.5"2}{sup 2} topology structure. In compound 2, the A-type [H{sub 3}As{sub 2}Mo{sub 6}O{sub 26}]{sup 3-} clusters are surrounded by pt ligands through hydrogen bond interactions forming 3D supramolecular framework with a {4"3.6"3}{sup 2}{4"6.6"6.8"3} topology structure. The electrochemical behaviors, electrocatalytic and photocatalytic activities of 1 and 2 are detected. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Self-assembly of a triangle-shaped, hexaplatinum-incorporated, supramolecular amphiphile in solution and at interfaces.

    Science.gov (United States)

    Maran, Umamageswaran; Britt, David; Fox, Christopher B; Harris, Joel M; Orendt, Anita M; Conley, Hiram; Davis, Robert; Hlady, Vladamir; Stang, Peter J

    2009-08-24

    The self-assembly and characterization of a novel supramolecular amphiphile built from a new 60 degree amphiphilic precursor that incorporates hydrophilic platinum(II) metals and hydrophobic dioctadecyloxy chains is reported. The amphiphilic macrocycle and its precursor compound have been characterized by multinuclear NMR spectroscopy, ESI-MS, and other standard techniques. The coacervate morphology of the amphiphile at the liquid-liquid interface has been studied by using confocal optical microscopy and in situ Raman spectroscopy. The self-assembly of the amphiphilic macrocycle at the air-water interface has been investigated through Langmuir-trough techniques. The study indicates the possible formation of surface micelle-like aggregates. The disparity between the experimental molecular areas and those derived from molecular models support the idea of aggregation. AFM images of the surface aggregates show the formation of a flat topology with arbitrary ridgelike patterns. Reasonable molecular-packing arrangements are proposed to explain the molecular organization within the observed structures.

  15. A multilayered supramolecular self-assembled structure from soybean oil by in situ polymerization and its applications.

    Science.gov (United States)

    Kavitha, Varadharajan; Gnanamani, Arumugam

    2013-05-01

    The present study emphasizes in situ transformation of soybean oil to self-assembled supramolecular multilayered biopolymer material. The said polymer material was characterized and the entrapment efficacy of both hydrophilic and hydrophobic moieties was studied. In brief, soybean oil at varying concentration was mixed with mineral medium and incubated under agitation (200 rpm) at 37 degrees C for 240 h. Physical observations were made till 240 h and the transformed biopolymer was separated and subjected to physical, chemical and functional characterization. The maximum size of the polymer material was measured as 2 cm in diameter and the cross sectional view displayed the multilayered onion rings like structures. SEM analysis illustrated the presence of multilayered honeycomb channeled structures. Thermal analysis demonstrated the thermal stability (200 degrees C) and high heat enthalpy (1999 J/g). Further, this multilayered assembly was able to entrap both hydrophilic and hydrophobic components simultaneously, suggesting the potential industrial application of this material.

  16. Fluorescent cellulose nanocrystals via supramolecular assembly of terpyridine-modified cellulose nanocrystals and terpyridine-modified perylene

    International Nuclear Information System (INIS)

    Hassan, Mohammad L.; Moorefield, Charles M.; Elbatal, Hany S.; Newkome, George R.; Modarelli, David A.; Romano, Natalie C.

    2012-01-01

    Highlights: ► Surfaces of cellulose nanocrystals were modified with terpyridine ligands. ► Fluorescent nanocrystals could be obtained via self-assembly of terpyridine-modified perylene dye onto the terpyridine-modified cellulose nanocrystals. ► Further self-assembly of azide-functionalized terpyridine onto the fluorescent cellulose nanocrystals was possible to obtain nanocellulosic material with expected use in bioimaging. - Abstract: Due to their natural origin, biocompatibility, and non-toxicity, cellulose nanocrystals are promising candidates for applications in nanomedicine. Highly fluorescent nanocellulosic material was prepared via surface modification of cellulose nanocrystals with 2,2′:6′,2″-terpyridine side chains followed by supramolecular assembly of terpyridine-modified perylene dye onto the terpyridine-modified cellulose nanocrystals (CTP) via Ru III /Ru II reduction. The prepared terpyridine-modified cellulose-Ru II -terpyridine-modified perylene (CTP-Ru II -PeryTP) fluorescent nanocrystals were characterized using cross-polarized/magic angle spin 13 C nuclear magnetic resonance (CP/MAS 13 C NMR), Fourier transform infrared (FTIR), UV–visible, and fluorescence spectroscopy. In addition, further self-assembly of terpyridine units with azide functional groups onto CTP-Ru II -PeryTP was possible via repeating the Ru III /Ru II reduction protocol to prepare supramolecular fluorescent nanocrystals with azide functionality (CTP-Ru II -PeryTP-Ru II -AZTP). The prepared derivative may have potential application in bio-imaging since the terminal azide groups can be easily reacted with antigens via “Click” chemistry reaction.

  17. 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...

  18. The influence of aquaporin-4 isoform interaction on supramolecular water channel assembly in astrocytoma cells

    OpenAIRE

    Deville, Sarah

    2012-01-01

    Traumatic brain injury (TBI) is often complicated by the development of brain edema. Despite its clinical importance, the underlying pathological mechanisms are poorly understood. Nevertheless, a central role for aquaporin-4 (AQP4) has been suggested. AQP4 is the predominant water channel of the central nervous system, where it forms supramolecular structures named orthogonal arrays of particles (OAP). This organization is essential for channel opening. OAP formation is regulated by the diffe...

  19. Investigation of Supramolecular Coordination Self-Assembly and Polymerization Confined on Metal Surfaces Using Scanning Tunneling Microscopy

    Science.gov (United States)

    Lin, Tao

    Organic molecules are envisioned as the building blocks for design and fabrication of functional devices in future, owing to their versatility, low cost and flexibility. Although some devices such as organic light-emitting diode (OLED) have been already applied in our daily lives, the field is still in its infancy and numerous challenges still remain. In particular, fundamental understanding of the process of organic material fabrication at a molecular level is highly desirable. This thesis focuses on the design and fabrication of supramolecular and macromolecular nanostructures on a Au(111) surface through self-assembly, polymerization and a combination of two. We used scanning tunneling microscopy (STM) as an experimental tool and Monte Carlo (MC) and kinetic Monte Carlo (KMC) simulations as theoretical tools to characterize the structures of these systems and to investigate the mechanisms of the self-assembly and polymerization processes at a single-molecular level. The results of this thesis consist of four parts as below: Part I addresses the mechanisms of two-dimensional multicomponent supramolecular self-assembly via pyridyl-Fe-terpyridyl coordination. Firstly, we studied four types of self-assembled metal-organic systems exhibiting different dimensionalities using specifically-designed molecular building blocks. We found that the two-dimensional system is under thermodynamic controls while the systems of lower dimension are under kinetic controls. Secondly, we studied the self-assembly of a series of cyclic supramolecular polygons. Our results indicate that the yield of on-surface cyclic polygon structures is very low independent of temperature and concentration and this phenomenon can be attributed to a subtle competition between kinetic and thermodynamic controls. These results shed light on thermodynamic and kinetic controls in on-surface coordination self-assembly. Part II addresses the two-dimensional supramolecular self-assembly of porphyrin

  20. Design of supramolecular nanomaterials : from molecular recognition to hierarchical self-assembly

    OpenAIRE

    El Idrissi, Mohamed

    2017-01-01

    In the present thesis, are reported new strategies for the design of nanostructures to partly address environmental issues. The work carried out has been divided into three parts: the design of cyclodextrin (CD)-based polymeric materials, the molecular engineering of a pyrene derivative for the formation of self-assembled nanostructures and the design of smart nanocarriers. Considerable efforts have been devoted to the design of molecular receptors capable of specific recognition of a wid...

  1. Lensless coherent imaging of proteins and supramolecular assemblies: Efficient phase retrieval by the charge flipping algorithm.

    Science.gov (United States)

    Dumas, Christian; van der Lee, Arie; Palatinus, Lukáš

    2013-05-01

    Diffractive imaging using the intense and coherent beam of X-ray free-electron lasers opens new perspectives for structural studies of single nanoparticles and biomolecules. Simulations were carried out to generate 3D oversampled diffraction patterns of non-crystalline biological samples, ranging from peptides and proteins to megadalton complex assemblies, and to recover their molecular structure from nanometer to near-atomic resolutions. Using these simulated data, we show here that iterative reconstruction methods based on standard and variant forms of the charge flipping algorithm, can efficiently solve the phase retrieval problem and extract a unique and reliable molecular structure. Contrary to the case of conventional algorithms, where the estimation and the use of a compact support is imposed, our approach does not require any prior information about the molecular assembly, and is amenable to a wide range of biological assemblies. Importantly, the robustness of this ab initio approach is illustrated by the fact that it tolerates experimental noise and incompleteness of the intensity data at the center of the speckle pattern. Copyright © 2013 Elsevier Inc. All rights reserved.

  2. Supramolecular Nanocomposites Under Confinement: Chiral Optically Active Nanoparticle Assemblies and Beyond

    Science.gov (United States)

    Bai, Peter; Yang, Sui; Bao, Wei; Salmeron, Miquel; Zhang, Xiang; Xu, Ting

    2015-03-01

    Block copolymer-based supramolecules provide a versatile platform to direct the self-assembly of nanoparticles (NPs) into precisely controlled nanostructures in bulk and thin film geometries. A supramolecule, PS-b-P4VP(PDP), composed of the small molecule 3-pentadecylphenol (PDP) hydrogen bonded to a diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), was subjected to 2-D volume confinement in cylindrical anodic aluminum oxide (AAO) membrane pores. TEM and 3-D TEM tomography reveal that the morphologies accessible by the supramolecule and supramolecule/NP composites, such as NP clusters, arrays, stacked rings, and single and double helical ribbons, are significantly different from those in the bulk or thin film. Furthermore, single molecule dark field scattering measurements demonstrate strong chiral optical response of single helical Au NP ribbon nanostructures in the near infrared wavelength regime. These studies demonstrate 2-D confinement to be an effective means to tailor self-assembled NP structure within supramolecule nanocomposites and pave the way for this assembly approach to be applied towards next generation chiral metamaterials and optoelectronic devices.

  3. Liaison based assembly design

    Energy Technology Data Exchange (ETDEWEB)

    Ames, A.; Kholwadwala, D.; Wilson, R.H.

    1996-12-01

    Liaison Based Assembly Design extends the current information infrastructure to support design in terms of kinematic relationships between parts, or liaisons. These liaisons capture information regarding contact, degrees-of-freedom constraints and containment relationships between parts in an assembly. The project involved defining a useful collection of liaison representations, investigating their properties, and providing for maximum use of the data in downstream applications. We tested our ideas by implementing a prototype system involving extensions to Pro/Engineer and the Archimedes assembly planner. With an expanded product model, the design system is more able to capture design intent. When a product update is attempted, increased knowledge availability improves our ability to understand the effect of design changes. Manufacturing and analysis disciplines benefit from having liaison information available, so less time is wasted arguing over incomplete design specifications and our enterprise can be more completely integrated.

  4. Supramolecular assembly of borate with quaternary ammonium: Crystal structure and tunable luminescent properties

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Jie; Wang, Yong-gang [Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Wang, Ying-xia, E-mail: wangyx@pku.edu.cn [Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Liao, Fu-hui [Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Lin, Jian-hua, E-mail: jhlin@pku.edu.cn [Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China)

    2013-04-15

    A new borate [C{sub 6}H{sub 16}N][B{sub 5}O{sub 6}(OH){sub 4}] (1) is synthesized hydrothermally by the reaction of isopropyltrimethylammonium hydroxide with boric acid. It crystallizes in the triclinic space group P-1 with the parameters a=9.1578(10) Å, b=9.372(9) Å, c=9.9812(10) Å, α=66.508(2)°, β=74.751(2)°, γ=81.893(2)°. The [B{sub 5}O{sub 6}(OH){sub 4}]{sup −} anions are interlinked via hydrogen bonding forming a 3D supramolecular network containing large cavities, where reside the (CH{sub 3}){sub 3}(i-C{sub 3}H{sub 7}) N{sup +} cations. This borate shows tunable luminescent properties with temperature, heating-treatment, exciting-light, and solvents. The fluorescent intensity of 1 enhances 6-fold with decreasing the temperature from 25 K to 78 K. By treatment under different temperatures, the luminescence of 1 shifted from blue to white and the sample treated at 230 °C emits bright white light to naked eyes. The hybrid borate can disperse in different solvents, and shows a red-shifted and intense emission in polar solvents. - Graphical abstract: The new quaternary ammonium borate [C{sub 6}H{sub 17}N][B{sub 5}O{sub 6}(OH){sub 4}] contains a 3D supramolecular network formed by hydrogen bond linked [B{sub 5}O{sub 6}(OH){sub 4}]{sup −} anions and shows tunable luminescent properties with temperature, excitation light, and solvents. Highlights: ► A novel quaternary ammonium borate was synthesized. ► It possesses a supramolecular network fomed by H-bonded [B{sub 5}O{sub 6}(OH){sub 4}]{sup −} anions. ► This borate shows tunable luminescent properties with temperature, heating treatment, excitation light, and solvents.

  5. Conformational dynamics data bank: a database for conformational dynamics of proteins and supramolecular protein assemblies.

    Science.gov (United States)

    Kim, Do-Nyun; Altschuler, Josiah; Strong, Campbell; McGill, Gaël; Bathe, Mark

    2011-01-01

    The conformational dynamics data bank (CDDB, http://www.cdyn.org) is a database that aims to provide comprehensive results on the conformational dynamics of high molecular weight proteins and protein assemblies. Analysis is performed using a recently introduced coarse-grained computational approach that is applied to the majority of structures present in the electron microscopy data bank (EMDB). Results include equilibrium thermal fluctuations and elastic strain energy distributions that identify rigid versus flexible protein domains generally, as well as those associated with specific functional transitions, and correlations in molecular motions that identify molecular regions that are highly coupled dynamically, with implications for allosteric mechanisms. A practical web-based search interface enables users to easily collect conformational dynamics data in various formats. The data bank is maintained and updated automatically to include conformational dynamics results for new structural entries as they become available in the EMDB. The CDDB complements static structural information to facilitate the investigation and interpretation of the biological function of proteins and protein assemblies essential to cell function.

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

    Science.gov (United States)

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

    2017-10-04

    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 assemblies (ZSAs). Four porous Co-based ZSAs having the same underlying gis topology, but differing only with respect to the capping and bridging linkers, were successfully isolated and fully characterized. In this series, each MOS in ZSA-3-ZSA-6 possess an ideal square geometry and is connected to four neighboring MOS via a total of 16 hydrogen bonds to give a 3-periodic porous network.To systematically assess the effect of the pore system (size and functionality) on the gas adsorption properties, we evaluated the MOSs for their affinity for different probe molecules such as CO 2 and light hydrocarbons. ZSA-3-ZSA-6 showed high thermal stability (up to 300 °C) and was proven highly porous as evidenced by gas adsorption studies. Notably, alkyl-functionalized MOSs were found to offer potential for selective separation of CO 2 , C 3 H 6 , and C 3 H 8 from CH 4 and H 2 containing gas stream, such as natural gas and refinery-off gases.

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

    KAUST Repository

    Wang, Shuang

    2017-07-11

    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 assemblies (ZSAs). Four porous Co-based ZSAs having the same underlying gis topology, but differing only with respect to the capping and bridging linkers, were successfully isolated and fully characterized. In this series, each MOS in ZSA-3-ZSA-6 possess an ideal square geometry and is connected to four neighboring MOS via a total of 16 hydrogen bonds to give a 3-periodic porous network.To systematically assess the effect of the pore system (size and functionality) on the gas adsorption properties, we evaluated the MOSs for their affinity for different probe molecules such as CO2 and light hydrocarbons. ZSA-3-ZSA-6 showed high thermal stability (up to 300 °C) and was proven highly porous as evidenced by gas adsorption studies. Notably, alkyl-functionalized MOSs were found to offer potential for selective separation of CO2, C3H6, and C3H8 from CH4 and H2 containing gas stream, such as natural gas and refinery-off gases.

  8. Dimensional Control and Morphological Transformations of Supramolecular Polymeric Nanofibers Based on Cofacially-Stacked Planar Amphiphilic Platinum(II) Complexes.

    Science.gov (United States)

    Robinson, Matthew E; Nazemi, Ali; Lunn, David J; Hayward, Dominic W; Boott, Charlotte E; Hsiao, Ming-Siao; Harniman, Robert L; Davis, Sean A; Whittell, George R; Richardson, Robert M; De Cola, Luisa; Manners, Ian

    2017-09-26

    Square-planar platinum(II) complexes often stack cofacially to yield supramolecular fiber-like structures with interesting photophysical properties. However, control over fiber dimensions and the resulting colloidal stability is limited. We report the self-assembly of amphiphilic Pt(II) complexes with solubilizing ancillary ligands based on polyethylene glycol [PEG n , where n = 16, 12, 7]. The complex with the longest solubilizing PEG ligand, Pt-PEG 16 , self-assembled to form polydisperse one-dimensional (1D) nanofibers (diameters fibers of length up to ca. 400 nm. The fiber lengths were dependent on the Pt-PEG 16 complex to seed mass ratio in a manner analogous to a living covalent polymerization of molecular monomers. Moreover, the fiber lengths were unchanged in solution after 1 week and were therefore "static" with respect to interfiber exchange processes on this time scale. In contrast, similarly formed near-uniform fibers of Pt-PEG 12 exhibited dynamic behavior that led to broadening of the length distribution within 48 h. After aging for 4 weeks in solution, Pt-PEG 12 fibers partially evolved into 2D platelets. Furthermore, self-assembly of Pt-PEG 7 yielded only transient fibers which rapidly evolved into 2D platelets. On addition of further fiber-forming Pt complex (Pt-PEG 16 ), the platelets formed assemblies via the growth of fibers selectively from their short edges. Our studies demonstrate that when interfiber dynamic exchange is suppressed, dimensional control and hierarchical structure formation are possible for supramolecular polymers through the use of kinetically controlled seeded growth methods.

  9. 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

  10. 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.

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

    Science.gov (United States)

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

    2014-06-21

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

  12. Self-Healing Supramolecular Hydrogels Based on Reversible Physical Interactions

    Directory of Open Access Journals (Sweden)

    Satu Strandman

    2016-04-01

    Full Text Available Dynamic and reversible polymer networks capable of self-healing, i.e., restoring their mechanical properties after deformation and failure, are gaining increasing research interest, as there is a continuous need towards extending the lifetime and improving the safety and performance of materials particularly in biomedical applications. Hydrogels are versatile materials that may allow self-healing through a variety of covalent and non-covalent bonding strategies. The structural recovery of physical gels has long been a topic of interest in soft materials physics and various supramolecular interactions can induce this kind of recovery. This review highlights the non-covalent strategies of building self-repairing hydrogels and the characterization of their mechanical properties. Potential applications and future prospects of these materials are also discussed.

  13. Supramolecular Assemblies from Poly(styrene-block-poly(4-vinylpyridine Diblock Copolymers Mixed with 6-Hydroxy-2-naphthoic Acid

    Directory of Open Access Journals (Sweden)

    Jean-François Gohy

    2013-06-01

    Full Text Available Supramolecular assemblies involving interaction of a small organic molecule, 2-hydroxy-6-Naphthoic acid (HNA, with poly(styrene-block-poly(4-vinylpyridine (PS-b-P4VP diblock copolymers are utilized to obtain micellar structures in solution, nanostructured thin films on flat substrates and, finally, nanoporous thin films. The formation of hydrogen bonds between HNA and the poly(4-vinylpyridine (P4VP blocks is confirmed by spectroscopic measurements. The accordingly P4VP/HNA hydrogen-bonded complexes are poorly soluble in 1,4-dioxane, resulting in the formation of micellar structures with a P4VP/HNA core and a polystyrene (PS corona. Those micelles have been spin-coated onto silicon wafers, resulting in nanostructured thin films consisting of P4VP/HNA dot-like features embedded in a PS matrix. The morphology of those films has been tuned by solvent annealing. Selective dissolution of HNA by methanol results in the formation of a nanoporous thin film. The P4VP/HNA nanodomains have been also cross-linked by borax, and the thin films have been further dissolved in a good solvent for PS, leading to micelles with a structure reminiscent of the thin films.

  14. Sol-gel transition accelerated by the co-assembly of two components in supramolecular hydrogels.

    Science.gov (United States)

    Matsumoto, Keigo; Shundo, Atsuomi; Ohno, Masashi; Saruhashi, Kowichiro; Miyachi, Nobuhide; Tsuruzoe, Nobutomo; Tanaka, Keiji

    2015-10-28

    N-Palmitoyl-Gly-His (PalGH) and glycerol 1-monopalmitate (GMP) in water co-assembled into fibrils with twisted ribbon structures and formed a homogeneous network, resulting in gel formation. Shaking the gel easily broke the fibril network leading to a sol in which high and low fibril density regions exist. After a period at room temperature, the higher density regions became interconnected. The spontaneous sol-gel transition did not take place for a gel made from only PalGH. Also, during the transition, the aggregation state of the co-assembly remained unchanged at a molecular level, unlike the fibril network. Thus, it can be claimed that the sol-gel transition is not associated with the assembled molecular configuration, but with the change in the fibril network. This knowledge might be useful for understanding and controlling sol-gel transition, thereby leading to the design and functionalization of hydrogels.

  15. Structural characterization of supramolecular assemblies by {sup 13}C spin dilution and 3D solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Habenstein, Birgit; Loquet, Antoine; Giller, Karin; Becker, Stefan; Lange, Adam, E-mail: adla@nmr.mpibpc.mpg.de [Max Planck Institute for Biophysical Chemistry, Department of NMR-based Structural Biology (Germany)

    2013-01-15

    {sup 13}C spin diluted protein samples can be produced using [1-{sup 13}C] and [2-{sup 13}C]-glucose (Glc) carbon sources in the bacterial growth medium. The {sup 13}C spin dilution results in favorable {sup 13}C spectral resolution and polarization transfer behavior. We recently reported the combined use of [1-{sup 13}C]- and [2-{sup 13}C]-Glc labeling to facilitate the structural analysis of insoluble and non-crystalline biological systems by solid-state NMR (ssNMR), including sequential assignment, detection of long-range contacts and structure determination of macromolecular assemblies. In solution NMR the beneficial properties of sparsely labeled samples using [2-{sup 13}C]-glycerol ({sup 13}C labeled C{alpha} sites on a {sup 12}C diluted background) have recently been exploited to provide a bi-directional assignment method (Takeuchi et al. in J Biomol NMR 49(1):17-26, 2011 ). Inspired by this approach and our own recent results using [2-{sup 13}C]-Glc as carbon sources for the simplification of ssNMR spectra, we present a strategy for a bi-directional sequential assignment of solid-state NMR resonances and additionally the detection of long-range contacts using the combination of {sup 13}C spin dilution and 3D NMR spectroscopy. We illustrate our results with the sequential assignment and the collection of distance restraints on an insoluble and non-crystalline supramolecular assembly, the Salmonella typhimurium type III secretion system needle.

  16. Diverse supramolecular structures formed by self‐assembling proteins of the B acillus subtilis spore coat

    Science.gov (United States)

    Jiang, Shuo; Wan, Qiang; Krajcikova, Daniela; Tang, Jilin; Tzokov, Svetomir B.; Barak, Imrich

    2015-01-01

    Summary Bacterial spores (endospores), such as those of the pathogens C lostridium difficile and B acillus anthracis, are uniquely stable cell forms, highly resistant to harsh environmental insults. B acillus subtilis is the best studied spore‐former and we have used it to address the question of how the spore coat is assembled from multiple components to form a robust, protective superstructure. B . subtilis coat proteins (CotY, CotE, CotV and CotW) expressed in E scherichia coli can arrange intracellularly into highly stable macro‐structures through processes of self‐assembly. Using electron microscopy, we demonstrate the capacity of these proteins to generate ordered one‐dimensional fibres, two‐dimensional sheets and three‐dimensional stacks. In one case (CotY), the high degree of order favours strong, cooperative intracellular disulfide cross‐linking. Assemblies of this kind could form exquisitely adapted building blocks for higher‐order assembly across all spore‐formers. These physically robust arrayed units could also have novel applications in nano‐biotechnology processes. PMID:25872412

  17. 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.

  18. Integrated effect of supramolecular self-assembled sandwich-like melamine cyanurate/MoS{sub 2} hybrid sheets on reducing fire hazards of polyamide 6 composites

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Xiaming [State Key Laboratory of Fire Science, University of Science and Technology of China, Anhui 230026 (China); Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, Suzhou, Jiangsu 215123 (China); Wang, Xin, E-mail: wxcmx@ustc.edu.cn [State Key Laboratory of Fire Science, University of Science and Technology of China, Anhui 230026 (China); Cai, Wei; Hong, Ningning [State Key Laboratory of Fire Science, University of Science and Technology of China, Anhui 230026 (China); Hu, Yuan, E-mail: yuanhu@ustc.edu.cn [State Key Laboratory of Fire Science, University of Science and Technology of China, Anhui 230026 (China); Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, Suzhou, Jiangsu 215123 (China); Liew, Kim Meow [Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, Suzhou, Jiangsu 215123 (China); Department of Architectural and Civil Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon (Hong Kong)

    2016-12-15

    A novel strategy of using supramolecular self-assembly for preparing sandwich-like melamine cyanurate/MoS{sub 2} sheets as the hybrid flame retardants for polyamide 6 (PA6) is reported for the first time. The introduction of MoS{sub 2} sheets function not only as a template to induce the formation of two-dimensional melamine cyanurate capping layers but also as a synergist to generate integrated flame-retarding effect of hybrid sheets, as well as a high-performance smoke suppressor to reduce fire hazards of PA6 materials. Once incorporating this well-designed structures (4 wt%) into PA6 matrix, there resulted in a remarkable drop (40%) in the peak heat release rate and a 25% reduction in total heat release. Moreover, the smoke production and pyrolysis gaseous products were efficiently suppressed by the addition of sandwich-like hybrid sheets. The integrated functions consisting of inherent flame retarding effect, physical barrier performance and catalytic activity are believed to the crucial guarantee for the reduced fire hazards of PA6 nanocomposites. Furthermore, this novel strategy with facile and scalable features may provide reference for developing various kinds of MoS{sub 2} based hybrid sheets for diverse applications.

  19. 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.

  20. 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.

  1. Driving Forces of the Self-Assembly of Supramolecular Systems: Partially Ordered Mesophases

    Science.gov (United States)

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

    2018-06-01

    The main aspects are considered of the self-organization of a new class of liquid crystalline compounds, rigid sector-shaped and cone-shaped dendrons. Theoretical approaches to the self-assembly of different amphiphilic compounds (lipids, bolaamphiphiles, block copolymers, and polyelectrolytes) are described. Particular attention is given to the mesophase structures that emerge during the self-organization of mesophases characterized by intermediate degrees of ordering, e.g., plastic crystals, the rotation-crystalline phase in polymers, ordered and disordered two-dimensional columnar phases, and bicontinuous cubic phases of different symmetry.

  2. 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.

  3. Cholesterol-conjugated supramolecular assemblies of low generations polyamidoamine dendrimers for enhanced EGFP plasmid DNA transfection

    Energy Technology Data Exchange (ETDEWEB)

    Golkar, Nasim; Samani, Soliman Mohammadi; Tamaddon, Ali Mohammad, E-mail: amtamadon@gmail.com [Shiraz University of Medical Sciences, Department of Pharmaceutics, School of Pharmacy (Iran, Islamic Republic of)

    2016-05-15

    Aimed to prepare an enhanced gene delivery system with low cytotoxicity and high transfection efficiency, various cholesterol-conjugated derivates of low generation polyamidoamine (PAMAM) dendrimers were prepared. The conjugates were characterized by TNBS assay, FTIR, and {sup 1}H-NMR spectroscopy. Self-assembly of the dendrimer conjugates (G1-Chol, G2-Chol, and G3-Chol) was investigated by pyrene assay. Following formation of the complexes between enhanced green fluorescence protein plasmid and the dendrimer conjugates at various N (primary amine)/P (phosphate) mole ratios, plasmid condensation, biologic stability, cytotoxicity, and protein expression were investigated. The conjugates self-assembled into micellar dispersions with the critical micelle concentration values (<50 µg/ml) depending on the dendrimer generation and cholesterol/amine mole ratio. Cholesterol conjugation resulted in higher resistance of the condensed plasmid DNA in a competition assay with heparin sulfate. Also, the transfection efficiency was determined higher for the cholesterol conjugates than unmodified dendrimers in HepG2 cells, showing the highest for G2-Chol at 40 % degree of cholesterol modification (G2-Chol{sub 40 %}) among various dendrimer generations. Interestingly, such conjugate showed a complete protection of plasmid against serum nucleases. Our results confirmed that the cholesterol conjugation to PAMAM dendrimers of low generations bearing little cytotoxicity improves their several physicochemical and biological characteristics required for an enhanced delivery of plasmid DNA into cells.

  4. 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).

  5. 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.

  6. 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.

  7. Supramolecular Self-Assembly of a Model Hydrogelator: Characterization of Fiber Formation and Morphology

    Directory of Open Access Journals (Sweden)

    Yuan Gao

    2016-10-01

    Full Text Available Hydrogels are of intense recent interest in connection with biomedical applications ranging from 3-D cell cultures and stem cell differentiation to regenerative medicine, controlled drug delivery, and tissue engineering. This prototypical form of soft matter has many emerging material science applications outside the medical field. The physical processes underlying this type of solidification are incompletely understood, and this limits design efforts aimed at optimizing these materials for applications. We address this general problem by applying multiple techniques (e.g., NMR, dynamic light scattering, small angle neutron scattering, rheological measurements to the case of a peptide derivative hydrogelator (molecule 1, NapFFKYp over a broad range of concentration and temperature to characterize both the formation of individual nanofibers and the fiber network. We believe that a better understanding of the hierarchical self-assembly process and control over the final morphology of this kind of material should have broad significance for biological and medicinal applications utilizing hydrogels.

  8. Integrative self-assembly of functional hybrid nanoconstructs by inorganic wrapping of single biomolecules, biomolecule arrays and organic supramolecular assemblies.

    Science.gov (United States)

    Patil, Avinash J; Li, Mei; Mann, Stephen

    2013-08-21

    Synthesis of functional hybrid nanoscale objects has been a core focus of the rapidly progressing field of nanomaterials science. In particular, there has been significant interest in the integration of evolutionally optimized biological systems such as proteins, DNA, virus particles and cells with functional inorganic building blocks to construct mesoscopic architectures and nanostructured materials. However, in many cases the fragile nature of the biomolecules seriously constrains their potential applications. As a consequence, there is an on-going quest for the development of novel strategies to modulate the thermal and chemical stabilities, and performance of biomolecules under adverse conditions. This feature article highlights new methods of "inorganic molecular wrapping" of single or multiple protein molecules, individual double-stranded DNA helices, lipid bilayer vesicles and self-assembled organic dye superstructures using inorganic building blocks to produce bio-inorganic nanoconstructs with core-shell type structures. We show that spatial isolation of the functional biological nanostructures as "armour-plated" enzyme molecules or polynucleotide strands not only maintains their intact structure and biochemical properties, but also enables the fabrication of novel hybrid nanomaterials for potential applications in diverse areas of bionanotechnology.

  9. Integrative self-assembly of functional hybrid nanoconstructs by inorganic wrapping of single biomolecules, biomolecule arrays and organic supramolecular assemblies

    Science.gov (United States)

    Patil, Avinash J.; Li, Mei; Mann, Stephen

    2013-07-01

    Synthesis of functional hybrid nanoscale objects has been a core focus of the rapidly progressing field of nanomaterials science. In particular, there has been significant interest in the integration of evolutionally optimized biological systems such as proteins, DNA, virus particles and cells with functional inorganic building blocks to construct mesoscopic architectures and nanostructured materials. However, in many cases the fragile nature of the biomolecules seriously constrains their potential applications. As a consequence, there is an on-going quest for the development of novel strategies to modulate the thermal and chemical stabilities, and performance of biomolecules under adverse conditions. This feature article highlights new methods of ``inorganic molecular wrapping'' of single or multiple protein molecules, individual double-stranded DNA helices, lipid bilayer vesicles and self-assembled organic dye superstructures using inorganic building blocks to produce bio-inorganic nanoconstructs with core-shell type structures. We show that spatial isolation of the functional biological nanostructures as ``armour-plated'' enzyme molecules or polynucleotide strands not only maintains their intact structure and biochemical properties, but also enables the fabrication of novel hybrid nanomaterials for potential applications in diverse areas of bionanotechnology.

  10. Supramolecular Self-Assembly of Histidine-Capped-Dialkoxy-Anthracene: A Visible Light Triggered Platform for facile siRNA Delivery

    KAUST Repository

    Patil, Sachin

    2016-06-29

    Supramolecular self-assembly of histidine-capped-dialkoxy-anthracene (HDA) results in the formation of light responsive nanostructures.Single-crystal X-ray diffraction analysis of HDA shows two types of hydrogen bonding. The first hydrogen bond is established between the imidazole moieties while the second involves the oxygen atom of one amide group and the hydrogen atom of a second amide group. When protonated in acidic aqueous media, HDA successfully complexes siRNA yielding spherical nanostructures. This biocompatible platform controllably delivers siRNA with high efficacy upon visible light irradiation leading up to 90% of gene silencing in live cells.

  11. Explosive decomposition of a melamine-cyanuric acid supramolecular assembly for fabricating defect-rich nitrogen-doped carbon nanotubes with significantly promoted catalysis.

    Science.gov (United States)

    Zhao, Zhongkui; Dai, Yitao; Ge, Guifang; Wang, Guiru

    2015-05-26

    A facile and scalable approach for fabricating structural defect-rich nitrogen-doped carbon nanotubes (MCSA-CNTs) through explosive decomposition of melamine-cyanuric acid supramolecular assembly is presented. In comparison to pristine carbon nanotubes, MCSA-CNT exhibits significantly enhanced catalytic performance in oxidant- and steam-free direct dehydrogenation of ethylbenzene, demonstrating the potential for metal-free clean and energy-saving styrene production. This finding also opens a new horizon for preparing highly-efficient carbocatalysts rich in structural defect sites for diverse transformations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. 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.

  13. Probing the influence of N-donor capping ligands on supramolecular assembly in molecular uranyl materials

    Energy Technology Data Exchange (ETDEWEB)

    Carter, Korey P.; Kalaj, Mark; Cahill, Christopher L. [Department of Chemistry, The George Washington University, Washington, DC (United States)

    2016-01-15

    The syntheses and crystal structures of six new compounds containing the UO{sub 2}{sup 2+} cation, 3,5-dichlorobenzoic acid, and a chelating N-donor [2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dimethylphen), 2,2{sup '}:6{sup '},2''-terpyridine (terpy), 4{sup '}-chloro-2,2{sup '}:6{sup '},2''-terpyridine (Cl-terpy), or 2,4,6-tris(2-pyridyl)-s-triazine (TPTZ)] are reported. Single-crystal X-ray diffraction analysis of these materials enabled the exploration of the structural relationship between the benzoic acids and the chelating N-donor as well as providing a platform to evaluate the effects of ligand choice on uranyl hydrolysis and subsequent oligomerization. At an unadjusted pH (ca. 3), a mix of uranyl monomers and dimers are observed, dimer formation resulting from both bridging carboxylate linkers and hydroxo bridges. Assembly by halogen- and hydrogen-bonding interactions as well as π-π interactions was observed depending on the experimental conditions utilized. Further, spectroscopic characterization (both vibrational and luminescence) of complexes 1, 4, and 5 to explore the effects of the electron-donating ability of the capping ligand on the corresponding uranyl luminescence and vibrational spectra suggests that there is a relationship between the observed bathochromic shifts and the electron-donating ability of the capping ligands. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Probing the influence of N-donor capping ligands on supramolecular assembly in molecular uranyl materials

    International Nuclear Information System (INIS)

    Carter, Korey P.; Kalaj, Mark; Cahill, Christopher L.

    2016-01-01

    The syntheses and crystal structures of six new compounds containing the UO 2 2+ cation, 3,5-dichlorobenzoic acid, and a chelating N-donor [2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dimethylphen), 2,2 ' :6 ' ,2''-terpyridine (terpy), 4 ' -chloro-2,2 ' :6 ' ,2''-terpyridine (Cl-terpy), or 2,4,6-tris(2-pyridyl)-s-triazine (TPTZ)] are reported. Single-crystal X-ray diffraction analysis of these materials enabled the exploration of the structural relationship between the benzoic acids and the chelating N-donor as well as providing a platform to evaluate the effects of ligand choice on uranyl hydrolysis and subsequent oligomerization. At an unadjusted pH (ca. 3), a mix of uranyl monomers and dimers are observed, dimer formation resulting from both bridging carboxylate linkers and hydroxo bridges. Assembly by halogen- and hydrogen-bonding interactions as well as π-π interactions was observed depending on the experimental conditions utilized. Further, spectroscopic characterization (both vibrational and luminescence) of complexes 1, 4, and 5 to explore the effects of the electron-donating ability of the capping ligand on the corresponding uranyl luminescence and vibrational spectra suggests that there is a relationship between the observed bathochromic shifts and the electron-donating ability of the capping ligands. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. 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

  16. 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

  17. 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

  18. A bioartificial environment for kidney epithelial cells based on a supramolecular polymer basement membrane mimic and an organotypical culture system.

    Science.gov (United States)

    Mollet, Björne B; Bogaerts, Iven L J; van Almen, Geert C; Dankers, Patricia Y W

    2017-06-01

    Renal applications in healthcare, such as renal replacement therapies and nephrotoxicity tests, could potentially benefit from bioartificial kidney membranes with fully differentiated and functional human tubular epithelial cells. A replacement of the natural environment of these cells is required to maintain and study cell functionality cell differentiation in vitro. Our approach was based on synthetic supramolecular biomaterials to mimic the natural basement membrane (BM) on which these cells grow and a bioreactor to provide the desired organotypical culture parameters. The BM mimics were constructed from ureidopyrimidinone (UPy)-functionalized polymer and bioactive peptides by electrospinning. The resultant membranes were shown to have a hierarchical fibrous BM-like structure consisting of self-assembled nanofibres within the electrospun microfibres. Human kidney-2 (HK-2) epithelial cells were cultured on the BM mimics under organotypical conditions in a custom-built bioreactor. The bioreactor facilitated in situ monitoring and functionality testing of the cultures. Cell viability and the integrity of the epithelial cell barrier were demonstrated inside the bioreactor by microscopy and transmembrane leakage of fluorescently labelled inulin, respectively. Furthermore, HK-2 cells maintained a polarized cell layer and showed modulation of both gene expression of membrane transporter proteins and metabolic activity of brush border enzymes when subjected to a continuous flow of culture medium inside the new bioreactor for 21 days. These results demonstrated that both the culture and study of renal epithelial cells was facilitated by the bioartificial in vitro environment that is formed by synthetic supramolecular BM mimics in our custom-built bioreactor. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

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

    Science.gov (United States)

    Broer, Dirk J; Bastiaansen, Cees M W; Debije, Michael G; Schenning, Albertus P H J

    2012-07-16

    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 well-defined nanostructured materials. We have chosen the illustrative example of photopolymerizable hydrogen-bonding mesogens to show that a wide variety of functional materials can be made from a relatively simple set of building blocks. Upon mixing these compounds with other reactive mesogens, nematic, chiral nematic, and smectic or columnar liquid-crystalline phases can be formed that can be applied as actuators, sensors and responsive reflectors, and nanoporous membranes, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. 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.

  1. Inhibition of protein aggregation: supramolecular assemblies of arginine hold the key.

    Directory of Open Access Journals (Sweden)

    Utpal Das

    Full Text Available BACKGROUND: Aggregation of unfolded proteins occurs mainly through the exposed hydrophobic surfaces. Any mechanism of inhibition of this aggregation should explain the prevention of these hydrophobic interactions. Though arginine is prevalently used as an aggregation suppressor, its mechanism of action is not clearly understood. We propose a mechanism based on the hydrophobic interactions of arginine. METHODOLOGY: We have analyzed arginine solution for its hydrotropic effect by pyrene solubility and the presence of hydrophobic environment by 1-anilino-8-naphthalene sulfonic acid fluorescence. Mass spectroscopic analyses show that arginine forms molecular clusters in the gas phase and the cluster composition is dependent on the solution conditions. Light scattering studies indicate that arginine exists as clusters in solution. In the presence of arginine, the reverse phase chromatographic elution profile of Alzheimer's amyloid beta 1-42 (Abeta(1-42 peptide is modified. Changes in the hydrodynamic volume of Abeta(1-42 in the presence of arginine measured by size exclusion chromatography show that arginine binds to Abeta(1-42. Arginine increases the solubility of Abeta(1-42 peptide in aqueous medium. It decreases the aggregation of Abeta(1-42 as observed by atomic force microscopy. CONCLUSIONS: Based on our experimental results we propose that molecular clusters of arginine in aqueous solutions display a hydrophobic surface by the alignment of its three methylene groups. The hydrophobic surfaces present on the proteins interact with the hydrophobic surface presented by the arginine clusters. The masking of hydrophobic surface inhibits protein-protein aggregation. This mechanism is also responsible for the hydrotropic effect of arginine on various compounds. It is also explained why other amino acids fail to inhibit the protein aggregation.

  2. Hydrogen bonded supramolecular materials

    CERN Document Server

    Li, Zhan-Ting

    2015-01-01

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

  3. Hydrogen Bonded Supramolecular Polymers in Both Apolar and Aqueous Media: Self-Assembly and Reversible Conversion of Vesicles and Gels%Hydrogen Bonded Supramolecular Polymers in Both Apolar and Aqueous Media: Self-Assembly and Reversible Conversion of Vesicles and Gels

    Institute of Scientific and Technical Information of China (English)

    杜平; 孔军; 王贵涛; 赵新; 李光玉; 蒋锡夔; 黎占亭

    2011-01-01

    In a preliminary letter (Tetrahedron Lett. 2010, 51, 188), we reported two new hydrazide-based quadruple hydrogen-bonding motifs, this is, two monopodal (la and lb) and five dipodal (2a, 2b and 3a--3c) aromatic hydrazide derivatives, and the formation of supramolecular polymers and vesicles from the dipodal motifs in hydrocarbons. In this paper, we present a full picture on the properties of these hydrogen-bonding motifs with an emphasis on their self-assembling behaviors in aqueous media. SEM, AFM, TEM and fluorescent micrographs indicate that all the dipodal compounds also form vesicles in polar methanol and water-methanol (up to 50% of water) mixtures. Control experiments show that lb does not form vesicles in same media. Addition of lb to the solution of the dipodal compounds inhibits the latter's capacity of forming vesicles. At high concentrations, 3b and 3c also gelate discrete solvents, including hydrocarbons, esters, methanol, and methanol-water mixture. Concentration-dependent SEM investigations reveal that the vesicles of 3b and 3c fuse to form gels and the gel of 3c can de-aggregate to form the vesicles reversibly.

  4. 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.

  5. Supramolecular water oxidation with rubda-based catalysts

    KAUST Repository

    Richmond, Craig J.; Matheu, Roc; Poater, Albert; Falivene, Laura; Benet-Buchholz, Jordi; Sala, Xavier; Cavallo, Luigi; Llobet, Antoni A.

    2014-01-01

    Extremely slow and extremely fast new water oxidation catalysts based on the Rubda (bda = 2,2′-bipyri-dine-6,6′-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycless"1, respectively. Detailed analyses

  6. Supramolecular water oxidation with Ru-bda-based catalysts.

    Science.gov (United States)

    Richmond, Craig J; Matheu, Roc; Poater, Albert; Falivene, Laura; Benet-Buchholz, Jordi; Sala, Xavier; Cavallo, Luigi; Llobet, Antoni

    2014-12-22

    Extremely slow and extremely fast new water oxidation catalysts based on the Ru-bda (bda=2,2'-bipyridine-6,6'-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycles s(-1) , respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system π-stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Supramolecular water oxidation with rubda-based catalysts

    KAUST Repository

    Richmond, Craig J.

    2014-11-05

    Extremely slow and extremely fast new water oxidation catalysts based on the Rubda (bda = 2,2′-bipyri-dine-6,6′-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycless"1, respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system p-stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts.

  8. 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)

  9. The Effect of Intermolecular Halogen Bond on 19F DNP Enhancement in 1, 4-Diiodotetrafluorobenzene/4-OH-TEMPO Supramolecular Assembly

    Directory of Open Access Journals (Sweden)

    GAO Shan

    2017-12-01

    Full Text Available Halogen bond, as hydrogen bond, is a non-covalent bond. Dynamic nuclear polarization (DNP technique has been used previously to study hydrogen bonds-mediated intermolecular interactions. However, no study has been carried out so far to study the halogen bond-mediated intermolecular interactions with DNP. In this work, 19F DNP polarization efficiency of the halogen bonds existing in supramolecular assembling by 4-OH-TEMPO and 1,4-diiodotetrafluorobenzene (DITFB was studied on a home-made DNP system. The formation of intermolecular halogen bonds appeared to increase 19F DNP polarization efficiency, suggesting that the spin-spin interactions among electrons were weakened by the halogen bonds, resulting in an increased T2e and a larger saturation factor.

  10. Data Mining as a Guide for the Construction of Crosslinked Nanoparticles with Low Immunotoxicity via Controlling Polymer Chemistry and Supramolecular Assembly

    Science.gov (United States)

    Elsabahy, Mahmoud; Wooley, Karen L.

    2015-01-01

    CONSPECTUS The potential immunotoxicity of nanoparticles that are currently being approved or in different phases of clinical trials or under rigorous in vitro and in vivo characterizations in several laboratories has recently raised special attention. Products with no apparent in vitro or in vivo toxicity may still trigger the various components of the immune system, unintentionally, and lead to serious adverse reactions. Cytokines are one of the useful biomarkers to predict the effect of biotherapeutics on modulating the immune system and for screening the immunotoxicity of nanoparticles, both in vitro and in vivo, and were found recently to partially predict the in vivo pharmacokinetics and biodistribution of nanomaterials. Control of polymer chemistry and supramolecular assembly provides a great opportunity for construction of biocompatible nanoparticles for biomedical clinical applications. However, the sources of data collected regarding immunotoxicities of nanomaterials are diverse and experiments are usually conducted using different assays and under specific conditions, making direct comparisons nearly impossible and, thus, tailoring properties of nanomaterials based on the available data is challenging. In this account, the effects of chemical structure, crosslinking, degradability, morphology, concentration and surface chemistry on the immunotoxicity of an expansive array of polymeric nanomaterials will be highlighted, with focus being given on assays conducted using the same in vitro and in vivo models and experimental conditions. Furthermore, numerical descriptive values have been utilized, uniquely, to stand for induction of cytokines by nanoparticles. This treatment of available data provides a simple and easy way to compare the immunotoxicity of various nanomaterials, and the values were found to correlate-well with published data. Based on the investigated polymeric systems in this study, valuable information has been collected that aids in the

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-09-19

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

  12. 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

  13. Self-assembling peptide-based building blocks in medical applications

    Energy Technology Data Exchange (ETDEWEB)

    Acar, Handan; Srivastava, Samanvaya; Chung, Eun Ji; Schnorenberg, Mathew R.; Barrett, John C.; LaBelle, James L.; Tirrell, Matthew

    2017-02-01

    Peptides and peptide-conjugates, comprising natural and synthetic building blocks, are an increasingly popular class of biomaterials. Self-assembled nanostructures based on peptides and peptide-conjugates offer advantages such as precise selectivity and multifunctionality that can address challenges and limitations in the clinic. In this review article, we discuss recent developments in the design and self-assembly of various nanomaterials based on peptides and peptide-conjugates for medical applications, and categorize them into two themes based on the driving forces of molecular self-assembly. First, we present the self-assembled nanostructures driven by the supramolecular interactions between the peptides, with or without the presence of conjugates. The studies where nanoassembly is driven by the interactions between the conjugates of peptide-conjugates are then presented. Particular emphasis is given to in vivo studies focusing on therapeutics, diagnostics, immune modulation and regenerative medicine. Finally, challenges and future perspectives are presented.

  14. 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

  15. 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

  16. 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.

  17. 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...

  18. 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

  19. 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.

  20. Hirshfeld surface analyses and crystal structures of supramolecular self-assembly thiourea derivatives directed by non-covalent interactions

    Science.gov (United States)

    Gumus, Ilkay; Solmaz, Ummuhan; Binzet, Gun; Keskin, Ebru; Arslan, Birdal; Arslan, Hakan

    2018-04-01

    The novel N-(bis(3,5-dimethoxybenzyl)carbamothioyl)-4-R-benzamide (R: H, Cl, CH3 and OCH3) compounds have been synthesized and characterized by FT-IR, 1H NMR and 13C NMR spectroscopy. Their crystal structures were also determined by single-crystal X-ray diffraction studies. Hirshfeld surfaces analysis and their associated two dimensional fingerprint plots of compounds were used as theoretical approach to assess driving force for crystal structure formation via the intermolecular interactions in the crystal lattices of synthesized compounds. The study of X-ray single crystal diffraction and Hirshfeld surfaces analysis of the prepared compounds shows that hydrogen bonding and other weaker interactions such as Nsbnd H⋯S, weak Csbnd H⋯S, Csbnd H⋯O, Csbnd H⋯N and Csbnd H···π intermolecular interactions and π-π stacking, among molecules of synthesized compounds participate in a cooperative way to stabilize the supramolecular structures.

  1. Supramolecular self-assembly of graphene oxide and metal nanoparticles into stacked multilayers by means of a multitasking protein ring.

    Science.gov (United States)

    Ardini, Matteo; Golia, Giordana; Passaretti, Paolo; Cimini, Annamaria; Pitari, Giuseppina; Giansanti, Francesco; Di Leandro, Luana; Ottaviano, Luca; Perrozzi, Francesco; Santucci, Sandro; Morandi, Vittorio; Ortolani, Luca; Christian, Meganne; Treossi, Emanuele; Palermo, Vincenzo; Angelucci, Francesco; Ippoliti, Rodolfo

    2016-03-28

    Graphene oxide (GO) is rapidly emerging worldwide as a breakthrough precursor material for next-generation devices. However, this requires the transition of its two-dimensional layered structure into more accessible three-dimensional (3D) arrays. Peroxiredoxins (Prx) are a family of multitasking redox enzymes, self-assembling into ring-like architectures. Taking advantage of both their symmetric structure and function, 3D reduced GO-based composites are hereby built up. Results reveal that the "double-faced" Prx rings can adhere flat on single GO layers and partially reduce them by their sulfur-containing amino acids, driving their stacking into 3D multi-layer reduced GO-Prx composites. This process occurs in aqueous solution at a very low GO concentration, i.e. 0.2 mg ml(-1). Further, protein engineering allows the Prx ring to be enriched with metal binding sites inside its lumen. This feature is exploited to both capture presynthesized gold nanoparticles and grow in situ palladium nanoparticles paving the way to straightforward and "green" routes to 3D reduced GO-metal composite materials.

  2. Supramolecular Influence on Keto-Enol Tautomerism and Thermochromic Properties of o-Hydroxy Schiff Bases

    Directory of Open Access Journals (Sweden)

    Marija Zbačnik

    2016-06-01

    Full Text Available This work presents a study on thermo-optical properties of three Schiff bases (imines in the solid state. The Schiff bases were obtained by means of mechanochemical synthesis using monosubstituted o-hydroxy aromatic aldehydes and monosubstituted aromatic amines. The keto-enol tautomerism and proton transfer via intramolecular O∙∙∙N hydrogen bond of the reported compounds was found to be influenced more by supramolecular interactions than by a temperature change. All products were characterised by powder X-ray diffraction (PXRD, FT-IR spectroscopy, thermogravimetric (TG analysis and differential scanning calorimetry (DSC. Molecular and crystal structures of compounds 1, 2 and 3 were determined by single crystal X-ray diffraction (SCXRD. The molecules of 1 appear to be present as the enol-imine, the molecules of 2 as the keto-amine tautomer and the molecules of 3 exhibit keto-enol tautomeric equilibrium in the solid state. An analysis of Cambridge structural database (CSD data on similar imines has been used for structural comparison. This work is licensed under a Creative Commons Attribution 4.0 International License.

  3. 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+.

  4. High-definition self-assemblies driven by the hydrophobic effect: synthesis and properties of a supramolecular nanocapsule.

    Science.gov (United States)

    Liu, Simin; Gibb, Bruce C

    2008-08-28

    High definition self-assemblies, those that possess order at the molecular level, are most commonly made from subunits possessing metals and metal coordination sites, or groups capable of partaking in hydrogen bonding. In other words, enthalpy is the driving force behind the free energy of assembly. The hydrophobic effect engenders the possibility of (nominally) relying not on enthalpy but entropy to drive assembly. Towards this idea, we describe how template molecules can trigger the dimerization of a cavitand in aqueous solution, and in doing so are encapsulated within the resulting capsule. Although not held together by (enthalpically) strong and directional non-covalent forces, these capsules possess considerable thermodynamic and kinetic stability. As a result, they display unusual and even unique properties. We discuss some of these, including the use of the capsule as a nanoscale reaction chamber and how they can bring about the separation of hydrocarbon gases.

  5. Metal-organic and supramolecular networks driven by 5-chloronicotinic acid: Hydrothermal self-assembly synthesis, structural diversity, luminescent and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Zhu-Qing, E-mail: zqgao2008@163.com [School of Chemical and Biological Engineering, Taiyuan University of Science and Technology, Taiyuan 030021 (China); Li, Hong-Jin [School of Chemical and Biological Engineering, Taiyuan University of Science and Technology, Taiyuan 030021 (China); Gu, Jin-Zhong, E-mail: gujzh@lzu.edu.cn [College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Zhang, Qing-Hua [School of Chemical and Biological Engineering, Taiyuan University of Science and Technology, Taiyuan 030021 (China); Kirillov, Alexander M. [Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049–001 Lisbon (Portugal)

    2016-09-15

    Four new crystalline solids, namely [Co{sub 2}(µ{sub 2}-5-Clnic){sub 2}(µ{sub 3}-5-Clnic){sub 2}(µ{sub 2}-H{sub 2}O)]{sub n} (1), [Co(5-Clnic){sub 2}(H{sub 2}O){sub 4}]·2(5-ClnicH) (2), [Pb(µ{sub 2}-5-Clnic){sub 2}(phen)]{sub n} (3), and [Cd(5-Clnic){sub 2}(phen){sub 2}]·3H{sub 2}O (4) were generated by hydrothermal self-assembly methods from the corresponding metal(II) chlorides, 5-chloronicotinic acid (5-ClnicH) as a principal building block, and 1,10-phenanthroline (phen) as an ancillary ligand (optional). All the products 1–4 were characterized by IR spectroscopy, elemental analysis, thermogravimetric (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. Their structures range from an intricate 3D metal-organic network 1 with the 3,6T7 topology to a ladder-like 1D coordination polymer 3 with the 2C1 topology, whereas compounds 2 and 4 are the discrete 0D monomers. The structures of 2 and 4 are further extended (0D→2D or 0D→3D) by hydrogen bonds, generating supramolecular networks with the 3,8L18 and ins topologies, respectively. Synthetic aspects, structural features, thermal stability, magnetic (for 1) and luminescent (for 3 and 4) properties were also investigated and discussed. - Graphical abstract: A new series of crystalline solids was self-assembled and fully characterized; their structural, topological, luminescent and magnetic features were investigated. Display Omitted.

  6. Using supramolecular binding motifs to provide precise control over the ratio and distribution of species in multiple component films grafted on surfaces: demonstration using electrochemical assembly from aryl diazonium salts.

    Science.gov (United States)

    Gui, Alicia L; Yau, Hon Man; Thomas, Donald S; Chockalingam, Muthukumar; Harper, Jason B; Gooding, J Justin

    2013-04-16

    Supramolecular interactions between two surface modification species are explored to control the ratio and distribution of these species on the resultant surface. A binary mixture of aryl diazonium salts bearing oppositely charged para-substituents (either -SO3(-) or -N(+)(Me)3), which also reduce at different potentials, has been examined on glassy carbon surfaces using cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). Striking features were observed: (1) the two aryl diazonium salts in the mixed solution undergo reductive adsorption at the same potential which is distinctively less negative than the potential required for the reduction of either of the two aryl diazonium salts alone; (2) the surface ratio of the two phenyl derivatives is consistently 1:1 regardless of the ratio of the two aryl diazonium salts in the modification solutions. Homogeneous distribution of the two oppositely charged phenyl species on the modified surface has also been suggested by XPS survey spectra. Diffusion coefficient measurements by DOSY NMR and DFT based computation have indicated the association of the two aryl diazonium species in the solution, which has led to changes in the molecular orbital energies of the two species. This study highlights the potential of using intermolecular interactions to control the assembly of multicomponent thin layers.

  7. Probabilistic reasoning for assembly-based 3D modeling

    KAUST Repository

    Chaudhuri, Siddhartha; Kalogerakis, Evangelos; Guibas, Leonidas; Koltun, Vladlen

    2011-01-01

    Assembly-based modeling is a promising approach to broadening the accessibility of 3D modeling. In assembly-based modeling, new models are assembled from shape components extracted from a database. A key challenge in assembly-based modeling

  8. Octanol-assisted liposome assembly on chip

    NARCIS (Netherlands)

    Deshpande, S.R.; Caspi, Y.; Meijering, A.E.C.; Dekker, C.

    2016-01-01

    Liposomes are versatile supramolecular assemblies widely used in basic and applied sciences. Here we present a novel microfluidics-based method, octanol-assisted liposome assembly (OLA), to form monodisperse, cell-sized (5–20 μm), unilamellar liposomes with excellent encapsulation efficiency. Akin

  9. 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)...

  10. 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

  11. 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.

  12. Accelerated Development of Supramolecular Corneal Stromal-Like Assemblies from Corneal Fibroblasts in the Presence of Macromolecular Crowders.

    Science.gov (United States)

    Kumar, Pramod; Satyam, Abhigyan; Fan, Xingliang; Rochev, Yury; Rodriguez, Brian J; Gorelov, Alexander; Joshi, Lokesh; Raghunath, Michael; Pandit, Abhay; Zeugolis, Dimitrios I

    2015-07-01

    Tissue engineering by self-assembly uses the cells' secretome as a regeneration template and biological factory of trophic factors. Despite the several advantages that have been witnessed in preclinical and clinical settings, the major obstacle for wide acceptance of this technology remains the tardy extracellular matrix formation. In this study, we assessed the influence of macromolecular crowding (MMC)/excluding volume effect, a biophysical phenomenon that accelerates thermodynamic activities and biological processes by several orders of magnitude, in human corneal fibroblast (HCF) culture. Our data indicate that the addition of negatively charged galactose derivative (carrageenan) in HCF culture, even at 0.5% serum, increases by 12-fold tissue-specific matrix deposition, while maintaining physiological cell morphology and protein/gene expression. Gene analysis indicates that a glucose derivative (dextran sulfate) may drive corneal fibroblasts toward a myofibroblast lineage. Collectively, these results indicate that MMC may be suitable not only for clinical translation and commercialization of tissue engineering by self-assembly therapies, but also for the development of in vitro pathophysiology models.

  13. Self-assembled nanomaterials based on beta (β"3) tetrapeptides

    International Nuclear Information System (INIS)

    Seoudi, Rania S; Hinds, Mark G; Wilson, David J D; Adda, Christopher G; Mechler, Adam; Del Borgo, Mark; Aguilar, Marie-Isabel; Perlmutter, Patrick

    2016-01-01

    β "3-amino acid based polypeptides offer a unique starting material for the design of self-assembled nanostructures such as fibres and hierarchical dendritic assemblies, due to their well-defined helical geometry in which the peptide side chains align at 120° due to the 3.0–3.1 residue pitch of the helix. In a previous work we have described the head-to-tail self-assembly of N-terminal acetylated β "3-peptides into infinite helical nanorods that was achieved by designing a bioinspired supramolecular self-assembly motif. Here we describe the effect of consecutively more polar side chains on the self-assembly characteristics of β "3-tetrapeptides Ac-β "3Ala-β "3Leu-β "3Ile-β "3Ala (Ac-β"3[ALIA]), Ac-β "3Ser-β "3Leu-β "3Ile-β "3Ala (Ac-β"3[SLIA]) and Ac-β "3Lys-β "3Leu-β "3Ile-β "3Glu (Ac-β"3[KLIE]). β "3-tetrapeptides complete 1 1/3 turns of the helix: thus in the oligomeric form the side chain positions shift 120° with each added monomer, forming a regular periodic pattern along the nanorod. Dynamic light scattering (DLS) measurements confirmed that these peptides self-assemble even in highly polar solvents such as water and DMSO, while diffusion-ordered NMR spectroscopy revealed the presence of a substantial monomeric population. Temperature dependence of the size distribution in DLS measurements suggests a dynamic equilibrium between monomers and oligomers. Solution casting produced distinct fibrillar deposits after evaporating the solvent. In the case of the apolar Ac-β "3[ALIA] the longitudinal helix morphology gives rise to geometrically defined (∼70°) junctions between fibres, forming a mesh that opens up possibilities for applications e.g. in tissue scaffolding. The deposits of polar Ac-β "3[SLIA] and Ac-β "3[KLIE] exhibit fibres in regular parallel alignment over surface areas in the order of 10 μm. (paper)

  14. Location of 3-hydroxyproline residues in collagen types I, II, III, and V/XI implies a role in fibril supramolecular assembly.

    Science.gov (United States)

    Weis, Mary Ann; Hudson, David M; Kim, Lammy; Scott, Melissa; Wu, Jiann-Jiu; Eyre, David R

    2010-01-22

    Collagen triple helices are stabilized by 4-hydroxyproline residues. No function is known for the much less common 3-hydroxyproline (3Hyp), although genetic defects inhibiting its formation cause recessive osteogenesis imperfecta. To help understand the pathogenesis, we used mass spectrometry to identify the sites and local sequence motifs of 3Hyp residues in fibril-forming collagens from normal human and bovine tissues. The results confirm a single, essentially fully occupied 3Hyp site (A1) at Pro(986) in A-clade chains alpha1(I), alpha1(II), and alpha2(V). Two partially modified sites (A2 and A3) were found at Pro(944) in alpha1(II) and alpha2(V) and Pro(707) in alpha2(I) and alpha2(V), which differed from A1 in sequence motif. Significantly, the distance between sites 2 and 3, 237 residues, is close to the collagen D-period (234 residues). A search for additional D-periodic 3Hyp sites revealed a fourth site (A4) at Pro(470) in alpha2(V), 237 residues N-terminal to site 3. In contrast, human and bovine type III collagen contained no 3Hyp at any site, despite a candidate proline residue and recognizable A1 sequence motif. A conserved histidine in mammalian alpha1(III) at A1 may have prevented 3-hydroxylation because this site in chicken type III was fully hydroxylated, and tyrosine replaced histidine. All three B-clade type V/XI collagen chains revealed the same three sites of 3Hyp but at different loci and sequence contexts from those in A-clade collagen chains. Two of these B-clade sites were spaced apart by 231 residues. From these and other observations we propose a fundamental role for 3Hyp residues in the ordered self-assembly of collagen supramolecular structures.

  15. Helically structured metal–organic frameworks fabricated by using supramolecular assemblies as templates† †Electronic supplementary information (ESI) available: Detailed TEM images and other extensive figures. See DOI: 10.1039/c4sc03278k Click here for additional data file.

    Science.gov (United States)

    Wang, Hui; Zhu, Wei; Li, Jian; Tian, Tian; Lan, Yue; Gao, Ning; Wang, Chen; Zhang, Meng; Faul, Charl F. J.

    2015-01-01

    The controlled formation of MOF-based superstructures with well-defined nanoscale sizes and exquisite morphologies represents a big challenge, but can trigger a new set of properties distinct from their bulk counterparts. Here we report on the use of a self-assembled organic object to template the first example of a nanoscale metal–organic framework (MOF) with a helical morphology. Two prototypical MOFs (HKUST-1 and MIL-100) were used to exemplify the growth of such materials on supramolecular assemblies. Interestingly, it was found that, dependent on the nature of the precursors, not only could well-defined helical MOF nanotubes be facilely fabricated, but novel helical bundle nanostructures could also be formed. These resultant MOF superstructures show additional optical properties and could be used as precursors for the preparation of chiral nanocarbons. PMID:28757993

  16. 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.

  17. 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.

  18. Self-assembly mechanism of 1,3:2,4-di(3,4-dichlorobenzylidene)-D-sorbitol and control of the supramolecular chirality.

    Science.gov (United States)

    Li, Jingjing; Fan, Kaiqi; Guan, Xidong; Yu, Yingzhe; Song, Jian

    2014-11-11

    Dibenzylidene-D-sorbitol (DBS) and its derivatives are known to form gels in organic solvents; however, the mechanism of the gel formation has been a subject of much debate. The present work is undertaken to elucidate the organization mechanism of a DBS derivative, 1,3:2,4-di(3,4-dichlorobenzylidene)-D-sorbitol (DCDBS), by taking into account the solvent effects and comparing the experiment data with theoretical calculation. These molecules form smooth nonhelical fibers with a rest circular dichroism (CD) signal in polar solvents, in contrast to rope-liked left-helical fibers with a strong negative CD signal observed in nonpolar solvents. The molecular complexes thus formed were characterized by means of Fourier transform infrared spectra, ultraviolet-visible spectra, X-ray diffraction patterns, static contact angles, and theoretical calculations. It was proposed that the interactions between the gelator and the solvents could subtly change the stacking of the molecules and hence their self-assembled nanostructures. In nonpolar solvents, the gelator molecules appear as a distorted T-shaped structure with the 6-OH forming intermolecular hydrogen bonds with the acetal oxygens of adjacent gelator molecule. In addition, because of differential stacking interactions on both sides of the 10-member ring skeleton of the gelator, the oligomers may assemble in a helix fashion to minimize the energy, leading to helical fibers. In polar solvents, however, the gelator molecules show a rigid planelike structure and thus stack on top of each other because of strong parallel-displaced π interactions. The balanced driving force on both sides of the 10-member ring skeleton made it difficult for the dimers to bend, thus resulting in nonhelical nanostructure. As expected from the mechanisms proposed here, twisted ribbon fibers with a medium strength CD signal were obtained when solvents of different polarities were mixed. Thus, solvent effects revealed in this work represent an

  19. 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.

  20. Anti-cooperative supramolecular polymerization: a new K2-K model applied to the self-assembly of perylene bisimide dye proceeding via well-defined hydrogen-bonded dimers.

    Science.gov (United States)

    Gershberg, Jana; Fennel, Franziska; Rehm, Thomas H; Lochbrunner, Stefan; Würthner, Frank

    2016-03-01

    A perylene bisimide dye bearing amide functionalities at the imide positions derived from amino acid l-alanine and a dialkoxy-substituted benzyl amine self-assembles into tightly bound dimers by π-π-stacking and hydrogen bonding in chloroform. In less polar or unpolar solvents like toluene and methylcyclohexane, and in their mixtures, these dimers further self-assemble into extended oligomeric aggregates in an anti-cooperative process in which even numbered aggregates are highly favoured. The stepwise transition from dimers into oligomers can not be properly described by conventional K 2 - K model, and thus a new K 2 - K aggregation model has been developed, which interpretes the present anti-cooperative supramolecular polymerization more appropriately. The newly developed K 2 - K model will be useful to describe self-assembly processes of a plethora of other π-conjugated molecules that are characterized by a favored dimer species.

  1. Two supramolecular complexes based on polyoxometalates and Co-EDTA units via covalent connection or non-covalent interaction

    Energy Technology Data Exchange (ETDEWEB)

    Teng, Chunlin; Xiao, Hanxi [Key Laboratory of Theoretical Organic Chemistry and Functional Molecule for Ministry of Education, Hunan University of Science and Technology, Xiangtan 411201 (China); Cai, Qing [Chemistry Department, City University of New York, New York, NY 10016 (United States); Tang, Jianting; Cai, Tiejun [Key Laboratory of Theoretical Organic Chemistry and Functional Molecule for Ministry of Education, Hunan University of Science and Technology, Xiangtan 411201 (China); Deng, Qian, E-mail: dengqian10502@163.com [Key Laboratory of Theoretical Organic Chemistry and Functional Molecule for Ministry of Education, Hunan University of Science and Technology, Xiangtan 411201 (China)

    2016-11-15

    Two new 3D network organic-inorganic hybrid supramolecular complexes ([Na{sub 6}(CoEDTA){sub 2}(H{sub 2}O){sub 13}]·(H{sub 2}SiW{sub 12}O{sub 40})·xH{sub 2}O)n (1) and [CoH{sub 4}EDTA(H{sub 2}O)]{sub 2}(SiW{sub 12}O{sub 40})·15H{sub 2}O (2) (H{sub 4}EDTA=Ethylenediamine tetraacetic acid) have been successfully synthesized by solution method, and characterized by infrared spectrum (IR), thermogravimetric-differential thermal analysis (TG-DTA), cyclic voltammetry (CV) and single{sup −}crystal X-ray diffraction (XRD). Both of the complexes are the supramolecules, but with different liking mode, they are two representative models of supramolecule. complex (1) is a 3D infinite network supramolecular coordination polymer with a rare multi-metal sturcture of sodium-cobalt-containing, which is mainly linked through coordinate-covalent bonds. While complex (2) is normal supramolecule, which linked by non-covalent interactions, such as H-bonding interaction, electrostatic interaction and van der waals force. Both of complex (1) and (2) exhibit good catalytic activities for catalytic oxidation of methanol, when the initial concentration of methanol is 3.0 g m{sup −3}, flow rate is 10 mL min{sup −1}, and the quality of catalyst is 0.2 g, for complex (1) and complex (2) the maximum elimination rates of methanol are 85% (150 °C) and 92% (120 °C), respectively. - Graphical abstract: Two new organic-inorganic hybrid supramolecular complexes based on Co-EDTA, and Keggin polyanions have been successfully synthesized with different pH value by solution method. They are attributed to two representative models of supramolecule. Complex(1) is an infinite coordination polymer with a rare multi-metal sturcture of sodium-cobalt-containing, which is mainly linked through covalent bonds. Complex (2) is a normal supramolecule, which linked by non-covalent interactions of H-bonding interaction, electrostatic interaction and van der waals force. - Highlights: • Two supramolecules

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

    Science.gov (United States)

    Wang, Youmei; Lu, Minghua; Tang, Dianping

    2018-06-30

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

  3. Data Mining as a Guide for the Construction of Cross-Linked Nanoparticles with Low Immunotoxicity via Control of Polymer Chemistry and Supramolecular Assembly.

    Science.gov (United States)

    Elsabahy, Mahmoud; Wooley, Karen L

    2015-06-16

    The potential immunotoxicity of nanoparticles that are currently being approved, in different phases of clinical trials, or undergoing rigorous in vitro and in vivo characterizations in several laboratories has recently raised special attention. Products with no apparent in vitro or in vivo toxicity may still trigger various components of the immune system unintentionally and lead to serious adverse reactions. Cytokines are one of the useful biomarkers for predicting the effect of biotherapeutics on modulation of the immune system and for screening the immunotoxicity of nanoparticles both in vitro and in vivo, and they were recently found to partially predict the in vivo pharmacokinetics and biodistribution of nanomaterials. Control of polymer chemistry and supramolecular assembly provides a great opportunity for the construction of biocompatible nanoparticles for biomedical clinical applications. However, the sources of data collected regarding immunotoxicities of nanomaterials are diverse, and experiments are usually conducted using different assays under specific conditions. As a result, making direct comparisons nearly impossible, and thus, tailoring the properties of nanomaterials on the basis of the available data is challenging. In this Account, the effects of chemical structure, cross-linking, degradability, morphology, concentration, and surface chemistry on the immunotoxicity of an expansive array of polymeric nanomaterials will be highlighted, with a focus on assays conducted using the same in vitro and in vivo models and experimental conditions. Furthermore, numerical descriptive values have been utilized uniquely to stand for induction of cytokines by nanoparticles. This treatment of available data provides a simple way to compare the immunotoxicities of various nanomaterials, and the values were found to correlate well with published data. On the basis of the polymeric systems investigated in this study, valuable information has been collected that

  4. 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.

  5. Dynamic reciprocity in bio-inspired supramolecular materials

    NARCIS (Netherlands)

    Bastings, M.M.C.

    2012-01-01

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

  6. Supramolecular micellar nanoaggregates based on a novel chitosan/vitamin E succinate copolymer for paclitaxel selective delivery

    Directory of Open Access Journals (Sweden)

    Lian H

    2011-12-01

    experiments, conducted by confocal laser scanning microscopy, showed an enhanced cellular uptake efficiency of the CS-VES micelles in MCF-7 cells compared with Taxol. The PTX-micelles exhibited a comparable but delayed cytotoxic effect compared with Taxol against MCF-7 cells, due to the sustained-release characteristics of the nanomicelles. More interestingly, blank nanomicelles based on CS-VES copolymer demonstrated significant cytotoxicity against MCF-7 cells.Conclusion: The supramolecular micellar aggregates based on CS-VES copolymer is a promising nanocarrier and efficacy enhancer when used as an anticancer drug-delivery system.Keywords: nanomicelles, cellular uptake, cytotoxicity

  7. 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.

  8. [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.

  9. Rapid diagnosis of multidrug resistance in cancer by electrochemical sensor based on carbon nanotubes-drug supramolecular nanocomposites.

    Science.gov (United States)

    Zhang, Haijun; Jiang, Hui; Sun, Feifei; Wang, Huangping; Zhao, Juan; Chen, Baoan; Wang, Xuemei

    2011-03-15

    The multidrug resistance (MDR) in cancer is a major chemotherapy obstacle, rendering many currently available chemotherapeutic drugs ineffective. The aim of this study was to explore the new strategy to early diagnose the MDR by electrochemical sensor based on carbon nanotubes-drug supramolecular interaction. The carbon nanotubes modified glassy carbon electrodes (CNTs/GCE) were directly immersed into the cells suspension of the sensitive leukemia cells K562 and/or its MDR cells K562/A02 to detect the response of the electrochemical probe of daunorubicin (DNR) residues after incubated with cells for 1h. The fresh evidence from the electrochemical studies based on CNTs/GCE demonstrated that the homogeneous, label-free strategy could directly measure the function of cell membrane transporters in MDR cancer cells, identify the cell phenotype (sensitive or MDR). When the different ratios of the sensitive leukemia cells K562 and its MDR ones K562/A02 were applied as a model of MDR levels to simulate the MDR occurrence in cancer, the cathodic peak current showed good linear response to the fraction of MDR with a correlation coefficient of 0.995. Therefore, the MDR fraction can be easily predicted based on the calibration curve of the cathodic peak current versus the fraction of MDR. These results indicated that the sensing strategy could provide a powerful tool for assessment of MDR in cancer. The new electrochemical sensor based on carbon nanotubes-drug supramolecular nanocomposites could represent promising approach in the rapid diagnosis of MDR in cancer. Copyright © 2011 Elsevier B.V. All rights reserved.

  10. [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

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

    International Nuclear Information System (INIS)

    Lehn, Jean-Marie

    2004-01-01

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

  12. Tunable blue organic light emitting diode based on aluminum calixarene supramolecular complex

    Science.gov (United States)

    Legnani, C.; Reyes, R.; Cremona, M.; Bagatin, I. A.; Toma, H. E.

    2004-07-01

    In this letter, the results of supramolecular organic light emitting diodes using a calix[4] arene complex thin film as emitter and electron transporting layer are presented. The devices were grown onto glass substrates coated with indium-tin-oxide layer and aluminum thick (150nm) cathode. By applying a dc voltage between the device electrodes in forward bias condition, a blue light emission in the active area of the device was observed. It was found that the electroluminescent emission peak can be tuned between 470 and 510nm changing the applied voltage bias from 4.3 to 5.4V. The observed tunable emission can be associated with an energy transfer from the calixarene compound.

  13. Printable optical sensors based on H-bonded supramolecular cholesteric liquid crystal networks.

    Science.gov (United States)

    Herzer, Nicole; Guneysu, Hilal; Davies, Dylan J D; Yildirim, Derya; Vaccaro, Antonio R; Broer, Dirk J; Bastiaansen, Cees W M; Schenning, Albertus P H J

    2012-05-09

    A printable H-bonded cholesteric liquid crystal (CLC) polymer film has been fabricated that, after conversion to a hygroscopic polymer salt film, responds to temperature and humidity by changing its reflection color. Fast-responding humidity sensors have been made in which the reflection color changes between green and yellow depending on the relative humidity. The change in reflection band is a result of a change in helix pitch in the film due to absorption and desorption of water, resulting in swelling/deswelling of the film material. When the polymer salt was saturated with water, a red-reflecting film was obtained that can potentially act as a time/temperature integrator. Finally, the films were printed on a foil, showing the potential application of supramolecular CLC materials as low-cost, printable, battery-free optical sensors.

  14. 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.

  15. 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

  16. Dinuclear ru-aqua complexes for selective epoxidation catalysis based on supramolecular substrate orientation effects

    KAUST Repository

    Di Giovanni, Carlo; Poater, Albert; Benet-Buchholz, Jordi; Cavallo, Luigi; Solà , Miquel; Llobet, Antoni A.

    2014-01-01

    Ru-aqua complex {[RuII(trpy)(H2O)] 2(μ-pyr-dc)}+ is a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes. High turnover numbers (TNs), up to 17000, and turnover frequencies (TOF), up to 24120 h-1 (6.7 s -1), have been obtained using PhIO as oxidant. This species presents an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides. In addition, it shows different reactivity to cis and trans olefins due to a substrate orientation supramolecular effect transmitted by its ligand scaffold. This effect together with the impressive reaction rates are rationalized using electrochemical techniques and DFT calculations. A new Ru-aqua complex that behaves as a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes is reported. High turnover numbers and frequencies are obtained by using PhIO as oxidant. The complex shows an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides (see figure). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Dinuclear ru-aqua complexes for selective epoxidation catalysis based on supramolecular substrate orientation effects

    KAUST Repository

    Di Giovanni, Carlo

    2014-03-03

    Ru-aqua complex {[RuII(trpy)(H2O)] 2(μ-pyr-dc)}+ is a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes. High turnover numbers (TNs), up to 17000, and turnover frequencies (TOF), up to 24120 h-1 (6.7 s -1), have been obtained using PhIO as oxidant. This species presents an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides. In addition, it shows different reactivity to cis and trans olefins due to a substrate orientation supramolecular effect transmitted by its ligand scaffold. This effect together with the impressive reaction rates are rationalized using electrochemical techniques and DFT calculations. A new Ru-aqua complex that behaves as a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes is reported. High turnover numbers and frequencies are obtained by using PhIO as oxidant. The complex shows an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides (see figure). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Self-Assembly, Supramolecular Organization, and Phase Behavior of L-Alanine Alkyl Esters (n = 9-18) and Characterization of Equimolar L-Alanine Lauryl Ester/Lauryl Sulfate Catanionic Complex.

    Science.gov (United States)

    Sivaramakrishna, D; Swamy, Musti J

    2015-09-08

    A homologous series of l-alanine alkyl ester hydrochlorides (AEs) bearing 9-18 C atoms in the alkyl chain have been synthesized and characterized with respect to self-assembly, supramolecular structure, and phase transitions. The CMCs of AEs bearing 11-18 C atoms were found to range between 0.1 and 10 mM. Differential scanning calorimetric (DSC) studies showed that the transition temperatures (Tt), enthalpies (ΔHt) and entropies (ΔSt) of AEs in the dry state exhibit odd-even alternation, with the odd-chain-length compounds having higher Tt values, but the even-chain-length homologues showing higher values of ΔHt and ΔSt. In DSC measurements on hydrated samples, carried out at pH 5.0 and pH 10.0 (where they exist in cationic and neutral forms, respectively), compounds with 13-18 C atoms in the alkyl chain showed sharp gel-to-liquid crystalline phase transitions, and odd-even alternation was not seen in the thermodynamic parameters. The molecular structure, packing properties, and intermolecular interactions of AEs with 9 and 10 C atoms in the alkyl chain were determined by single crystal X-ray diffraction, which showed that the alkyl chains are packed in a tilted interdigitated bilayer format. d-Spacings obtained from powder X-ray diffraction studies exhibited a linear dependence on the alkyl chain length, suggesting that the other AEs also adopt an interdigitated bilayer structure. Turbidimetric, fluorescence spectroscopic, and isothermal titration calorimetric (ITC) studies established that in aqueous dispersions l-alanine lauryl ester hydrochloride (ALE·HCl) and sodium dodecyl sulfate (SDS) form an equimolar complex. Transmission electron microscopic and DSC studies indicate that the complex exists as unilamellar liposomes, which exhibit a sharp phase transition at ∼39 °C. The aggregates were disrupted at high pH, suggesting that the catanionic complex would be useful to develop a base-labile drug delivery system. ITC studies indicated that ALE·HCl forms

  19. A supramolecular photosensitizer system based on the host-guest complexation between water-soluble pillar[6]arene and methylene blue for durable photodynamic therapy.

    Science.gov (United States)

    Yang, Kui; Wen, Jia; Chao, Shuang; Liu, Jing; Yang, Ke; Pei, Yuxin; Pei, Zhichao

    2018-06-05

    A supramolecular photosensitizer system WP6-MB was synthesized based on water-soluble pillar[6]arene and the photosensitizer methylene blue (MB) via host-guest interaction. MB can complex with WP6 directly with a high complex constant without further modification. In particular, WP6-MB can reduce the dark toxicity of MB remarkably. Furthermore, it can efficiently overcome photobleaching and extend the time for singlet oxygen production of MB upon light irradiation, which is significant for durable photodynamic therapy.

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

    Science.gov (United States)

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

    2018-03-01

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

  1. Synchronous fluorescence based biosensor for albumin determination by cooperative binding of fluorescence probe in a supra-biomolecular host-protein assembly.

    Science.gov (United States)

    Patra, Digambara

    2010-01-15

    A synchronous fluorescence probe based biosensor for estimation of albumin with high sensitivity and selectivity was developed. Unlike conventional fluorescence emission or excitation spectral measurements, synchronous fluorescence measurement offered exclusively a new synchronous fluorescence peak in the shorter wavelength range upon binding of chrysene with protein making it an easy identification tool for albumin determination. The cooperative binding of a fluorescence probe, chrysene, in a supramolecular host-protein assembly during various albumin assessments was investigated. The presence of supramolecular host molecules such as beta-cyclodextrin, curucurbit[6]uril or curucurbit[7]uril have little influence on sensitivity or limit of detection during albumin determination but reduced dramatically interference from various coexisting metal ion quenchers/enhancers. Using the present method the limit of detection for BSA and gamma-Globulin was found to be 0.005 microM which is more sensitive than reported values. Copyright 2009 Elsevier B.V. All rights reserved.

  2. 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.

  3. Two new Ni(II) supramolecular complexes based on ethyl isonicotinate and ethyl nicotinate for removal of acid blue 92 dye

    Science.gov (United States)

    Etaiw, Safaa El-din H.; Marie, Hassan

    2018-03-01

    Two new luminescent supramolecular complexes (SC); [Ni(EIN)4(NCS)2] SC1 and [Ni2(EN)8(NCS)4] SC2, (EIN = ethyl isonicotinate, EN = ethyl nicotinate), have been synthesized by self-assembly method and structurally characterized by X-ray single crystal, FT-IR and UV-Vis spectra, PXRD, elemental and thermogravimetric analyses. Both SC1 and SC2 are monoclinic crystals however, they have different asymmetric units. Ni(II) atoms in both SC are isostructural and have similar hexa-coordinate environment. The structures of SC1 and SC2 consist of parallel polymeric 1D-chains, extended in two and three dimensional supramolecular frameworks by intermolecular hydrogen bonding interactions. SC1 and SC2 are luminescent materials which can be used in applications as molecular sensing systems. SC1 and SC2 were used as heterogeneous catalysts for degradation of acid blue 92 (AB-92) under sun light irradiation. The fluorescence measurements of terephthalic acid technique as a probe molecule were used to determine the •OH radicals. Also the radicals trapping experiments using isopropanol alcohol (IPA) as radical scavenger were discussed. In addition a mechanism of degradation was proposed and discussed.

  4. 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

  5. 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.

  6. 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.

  7. Self-assembling of calcium salt of the new DNA base 5-carboxylcytosine

    Energy Technology Data Exchange (ETDEWEB)

    Irrera, Simona [Department of Chemistry, SAPIENZA University of Rome, Piazzale A. Moro 5, 00185 Rome (Italy); Department of Chemistry, University College London, 20 Grodon Street, WC1H0AJ London (United Kingdom); Ruiz-Hernandez, Sergio E. [School of Chemistry, Cardiff University Main Building, Park Place, CF103AT Cardiff (United Kingdom); Reggente, Melania [Department of Basic and Applied Sciences for Engineering, SAPIENZA University of Rome, Via A. Scarpa 16, 00161 Rome (Italy); Passeri, Daniele, E-mail: daniele.passeri@uniroma1.it [Department of Basic and Applied Sciences for Engineering, SAPIENZA University of Rome, Via A. Scarpa 16, 00161 Rome (Italy); Natali, Marco [Department of Basic and Applied Sciences for Engineering, SAPIENZA University of Rome, Via A. Scarpa 16, 00161 Rome (Italy); Gala, Fabrizio [Department of Basic and Applied Sciences for Engineering, SAPIENZA University of Rome, Via A. Scarpa 16, 00161 Rome (Italy); Department of Medical-Surgical, Techno-Biomedical Sciences and Translational Medicine of SAPIENZA University of Rome, Sant’Andrea Hospital, Rome (Italy); Zollo, Giuseppe [Department of Basic and Applied Sciences for Engineering, SAPIENZA University of Rome, Via A. Scarpa 16, 00161 Rome (Italy); Rossi, Marco [Department of Basic and Applied Sciences for Engineering, SAPIENZA University of Rome, Via A. Scarpa 16, 00161 Rome (Italy); Research Center for Nanotechnology applied to Engineering of SAPIENZA University of Rome (CNIS), Piazzale A. Moro 5, 00185 Rome (Italy); Portalone, Gustavo, E-mail: gustavo.portalone@uniroma1.it [Department of Chemistry, SAPIENZA University of Rome, Piazzale A. Moro 5, 00185 Rome (Italy)

    2017-06-15

    Highlights: • Ca salt of 5-carboxylcytosine has been deposited on HOPG substrate. • Molecules self-assembled in monolayers and filaments. • Height of the features were measured by atomic force microscopy. • Ab-initio calculations confirmed the AFM results. - Abstract: Supramolecular architectures involving DNA bases can have a strong impact in several fields such as nanomedicine and nanodevice manufacturing. To date, in addition to the four canonical nucleobases (adenine, thymine, guanine and cytosine), four other forms of cytosine modified at the 5 position have been identified in DNA. Among these four new cytosine derivatives, 5-carboxylcytosine has been recently discovered in mammalian stem cell DNA, and proposed as the final product of the oxidative epigenetic demethylation pathway on the 5 position of cytosine. In this work, a calcium salt of 5-carboxylcytosine has been synthesized and deposited on graphite surface, where it forms self-assembled features as long range monolayers and up to one micron long filaments. These structures have been analyzed in details combining different theoretical and experimental approaches: X-ray single-crystal diffraction data were used to simulate the molecule-graphite interaction, first using molecular dynamics and then refining the results using density functional theory (DFT); finally, data obtained with DFT were used to rationalize atomic force microscopy (AFM) results.

  8. 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.

  9. Hierarchical Formation of Fibrillar and Lamellar Self-Assemblies from Guanosine-Based Motifs

    Directory of Open Access Journals (Sweden)

    Paolo Neviani

    2010-01-01

    Full Text Available Here we investigate the supramolecular polymerizations of two lipophilic guanosine derivatives in chloroform by light scattering technique and TEM experiments. The obtained data reveal the presence of several levels of organization due to the hierarchical self-assembly of the guanosine units in ribbons that in turn aggregate in fibrillar or lamellar soft structures. The elucidation of these structures furnishes an explanation to the physical behaviour of guanosine units which display organogelator properties.

  10. 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

  11. 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

  12. 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.

  13. One-Dimensional Multichromophor Arrays Based on DNA: From Self-Assembly to Light-Harvesting.

    Science.gov (United States)

    Ensslen, Philipp; Wagenknecht, Hans-Achim

    2015-10-20

    Light-harvesting complexes collect light energy and deliver it by a cascade of energy and electron transfer processes to the reaction center where charge separation leads to storage as chemical energy. The design of artificial light-harvesting assemblies faces enormous challenges because several antenna chromophores need to be kept in close proximity but self-quenching needs to be avoided. Double stranded DNA as a supramolecular scaffold plays a promising role due to its characteristic structural properties. Automated DNA synthesis allows incorporation of artificial chromophore-modified building blocks, and sequence design allows precise control of the distances and orientations between the chromophores. The helical twist between the chromophores, which is induced by the DNA framework, controls energy and electron transfer and thereby reduces the self-quenching that is typically observed in chromophore aggregates. This Account summarizes covalently multichromophore-modified DNA and describes how such multichromophore arrays were achieved by Watson-Crick-specific and DNA-templated self-assembly. The covalent DNA systems were prepared by incorporation of chromophores as DNA base substitutions (either as C-nucleosides or with acyclic linkers as substitutes for the 2'-deoxyribofuranoside) and as DNA base modifications. Studies with DNA base substitutions revealed that distances but more importantly relative orientations of the chromophores govern the energy transfer efficiencies and thereby the light-harvesting properties. With DNA base substitutions, duplex stabilization was faced and could be overcome, for instance, by zipper-like placement of the chromophores in both strands. For both principal structural approaches, DNA-based light-harvesting antenna could be realized. The major disadvantages, however, for covalent multichromophore DNA conjugates are the poor yields of synthesis and the solubility issues for oligonucleotides with more than 5-10 chromophore

  14. 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)

  15. CAD Parts-Based Assembly Modeling by Probabilistic Reasoning

    KAUST Repository

    Zhang, Kai-Ke; Hu, Kai-Mo; Yin, Li-Cheng; Yan, Dongming; Wang, Bin

    2016-01-01

    Nowadays, increasing amount of parts and sub-assemblies are publicly available, which can be used directly for product development instead of creating from scratch. In this paper, we propose an interactive design framework for efficient and smart assembly modeling, in order to improve the design efficiency. Our approach is based on a probabilistic reasoning. Given a collection of industrial assemblies, we learn a probabilistic graphical model from the relationships between the parts of assemblies. Then in the modeling stage, this probabilistic model is used to suggest the most likely used parts compatible with the current assembly. Finally, the parts are assembled under certain geometric constraints. We demonstrate the effectiveness of our framework through a variety of assembly models produced by our prototype system. © 2015 IEEE.

  16. CAD Parts-Based Assembly Modeling by Probabilistic Reasoning

    KAUST Repository

    Zhang, Kai-Ke

    2016-04-11

    Nowadays, increasing amount of parts and sub-assemblies are publicly available, which can be used directly for product development instead of creating from scratch. In this paper, we propose an interactive design framework for efficient and smart assembly modeling, in order to improve the design efficiency. Our approach is based on a probabilistic reasoning. Given a collection of industrial assemblies, we learn a probabilistic graphical model from the relationships between the parts of assemblies. Then in the modeling stage, this probabilistic model is used to suggest the most likely used parts compatible with the current assembly. Finally, the parts are assembled under certain geometric constraints. We demonstrate the effectiveness of our framework through a variety of assembly models produced by our prototype system. © 2015 IEEE.

  17. Black-to-Transmissive Electrochromism with Visible-to-Near-Infrared Switching of a Co(II)-Based Metallo-Supramolecular Polymer for Smart Window and Digital Signage Applications.

    Science.gov (United States)

    Hsu, Chih-Yu; Zhang, Jian; Sato, Takashi; Moriyama, Satoshi; Higuchi, Masayoshi

    2015-08-26

    Black-to-transmissive electrochromism has been obtained with a Co(II)-based metallo-supramolecular polymer (polyCo). Thin films of polyCo, based on bisterpyridine ligand assembled with Co(II) metal ion, were constructed by spray casting the polymer onto ITO glass. With such simple fabricating means to form good-quality films, polyCo films show stable switching at the central metal ion of the Co(II)/Co(I) redox reaction when immersed in aqueous solution. With an increase in the pH of the aqueous electrolyte solution from neutral, the film exhibits a color response due to the interaction between the d-orbital electron and hydroxide ions affecting the d-d* transition. As a result, a nearly transparent-to-black electrochromic performance can be achieved with a transmittance difference at 550 nm of 74.3% (81.9-7.6%) in pH 13 solution. The light absorption of the film can be tuned over light regions from visible to near-infrared with a large attenuation.

  18. A Novel Assembly Line Balancing Method Based on PSO Algorithm

    Directory of Open Access Journals (Sweden)

    Xiaomei Hu

    2014-01-01

    Full Text Available Assembly line is widely used in manufacturing system. Assembly line balancing problem is a crucial question during design and management of assembly lines since it directly affects the productivity of the whole manufacturing system. The model of assembly line balancing problem is put forward and a general optimization method is proposed. The key data on assembly line balancing problem is confirmed, and the precedence relations diagram is described. A double objective optimization model based on takt time and smoothness index is built, and balance optimization scheme based on PSO algorithm is proposed. Through the simulation experiments of examples, the feasibility and validity of the assembly line balancing method based on PSO algorithm is proved.

  19. 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.

  20. 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

  1. 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.

  2. 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

  3. Insight into the electronic structure of the supramolecular “rods-in-belt” Au{sup I}-Cu{sup I} and Au{sup I}-Ag{sup I} self-assembled complexes from X-ray photoelectron and absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Makarova, Anna A. [Department of Physics, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Institut für Festkörperphysik, Technische Universität Dresden, D-01062 Dresden (Germany); Grachova, Elena V.; Krupenya, Dmitry V. [Department of Chemistry, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Vilkov, Oleg [Department of Physics, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Institut für Festkörperphysik, Technische Universität Dresden, D-01062 Dresden (Germany); Fedorov, Alexander [Department of Physics, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Leibniz-Institut für Festkörper- und Werkstoffforschung Dresden, Dresden (Germany); Usachov, Dmitry [Department of Physics, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Generalov, Alexander [Department of Physics, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Institut für Festkörperphysik, Technische Universität Dresden, D-01062 Dresden (Germany); Koshevoy, Igor O. [Department of Chemistry, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Department of Chemistry, University of Eastern Finland, Joensuu 80101 (Finland); Tunik, Sergey P. [Department of Chemistry, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Rühl, Eckart [Physikalische Chemie, Institut für Chemie und Biochemie Freie Universität Berlin (Germany); and others

    2014-01-01

    Highlights: • Electronic structure of rods-in-belt complexes was described via PES and NEXAFS. • With increasing size the molecule becomes more sensitive to X-ray damage effects. • The HOMO consists of a combination of the d-Cu/Ag and π-C≡C states. • HOMOs are positioned at about 2.2 eV for Au-Cu and 2.5 eV BE for Au-Ag complexes. • LUMOs are located on the C-skeleton including π*-C≡C and π*-C=C{sub aromatic} orbitals. - Abstract: The recently discovered “rods-in-belt” supramolecular complexes with Au-Cu or Au-Ag cluster cores exhibit self-assembly behavior, have a very unusual structural motif, and what is most important, show remarkable light emitting properties. The electronic and photophysical characteristics of these unique objects can be relatively easy tuned by modifying the ligand (alkynyl and phosphine) environment. Because of these properties the “rods-in-belt” supramolecules could serve as building blocks for next generation electronics, and in particular, for light-emitting devices and in bioimaging applications. Herein, we report a comprehensive characterization of the electronic structure of two families of alkynyl-diphosphine supramolecular complexes with the heterometallic Au-Cu and Au-Ag cores. Using X-ray photoemission and absorption spectroscopy we disentangled the structure of their occupied and unoccupied electronic states close to the Fermi level. The results obtained suggest that the major contribution to the highest occupied molecular orbitals is made by the triple bonded carbons hosted in the dialkynyl-gold “rods” and the copper (silver) atoms from the central cluster core of the heterometallic Au-Cu (Au-Ag) molecules. The lowest unoccupied molecular orbitals are located on the carbon skeleton of the complexes and include π*-C≡C and π*-C=C{sub aromatic} orbitals. The onset of the valence band in the Au-Ag systems starts at about 0.3 eV lower than that in the Au-Cu complexes, implying a slightly larger energy

  4. 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.

  5. An assembly sequence planning method based on composite algorithm

    Directory of Open Access Journals (Sweden)

    Enfu LIU

    2016-02-01

    Full Text Available To solve the combination explosion problem and the blind searching problem in assembly sequence planning of complex products, an assembly sequence planning method based on composite algorithm is proposed. In the composite algorithm, a sufficient number of feasible assembly sequences are generated using formalization reasoning algorithm as the initial population of genetic algorithm. Then fuzzy knowledge of assembly is integrated into the planning process of genetic algorithm and ant algorithm to get the accurate solution. At last, an example is conducted to verify the feasibility of composite algorithm.

  6. Lamellar Microdomains of Block-Copolymer-Based Ionic Supramolecules Exhibiting a Hierarchical Self-Assembly

    DEFF Research Database (Denmark)

    Ayoubi, Mehran Asad; Almdal, Kristoffer; Zhu, Kaizheng

    2014-01-01

    (Cn; n = 8, 12, and 16) trimethylammonium counterions (i.e., side chains) at various ion (pair) fractions X [i.e., counterion/side-chain grafting density; X = number of alkyl counterions (i.e., side chains) per acidic group of the parent PMAA block] these L-b-AC ionic supramolecules exhibit...... a spherical-in-lamellar hierarchical self-assembly. For these systems, (1) the effective Flory-Huggins interaction parameter between L- and AC-blocks chi'(Cn/x) was extracted, and (2) analysis of the lamellar microdomains showed that when there is an increase in X, alkyl counterion (i.e., side chain) length l......Based on a parent diblock copolymer of poly(styrene)-b-poly(methacrylic acid), PS-b-PMAA, linear-b-amphiphilic comb (L-b-AC) ionic supramolecules [Soft Matter 2013, 9, 1540-1555] are synthesized in which the poly(methacrylate) backbone of the ionic supramolecular AC-block is neutralized by alkyl...

  7. Self-assembling of calcium salt of the new DNA base 5-carboxylcytosine

    Science.gov (United States)

    Irrera, Simona; Ruiz-Hernandez, Sergio E.; Reggente, Melania; Passeri, Daniele; Natali, Marco; Gala, Fabrizio; Zollo, Giuseppe; Rossi, Marco; Portalone, Gustavo

    2017-06-01

    Supramolecular architectures involving DNA bases can have a strong impact in several fields such as nanomedicine and nanodevice manufacturing. To date, in addition to the four canonical nucleobases (adenine, thymine, guanine and cytosine), four other forms of cytosine modified at the 5 position have been identified in DNA. Among these four new cytosine derivatives, 5-carboxylcytosine has been recently discovered in mammalian stem cell DNA, and proposed as the final product of the oxidative epigenetic demethylation pathway on the 5 position of cytosine. In this work, a calcium salt of 5-carboxylcytosine has been synthesized and deposited on graphite surface, where it forms self-assembled features as long range monolayers and up to one micron long filaments. These structures have been analyzed in details combining different theoretical and experimental approaches: X-ray single-crystal diffraction data were used to simulate the molecule-graphite interaction, first using molecular dynamics and then refining the results using density functional theory (DFT); finally, data obtained with DFT were used to rationalize atomic force microscopy (AFM) results.

  8. 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.

  9. 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.

  10. Probabilistic reasoning for assembly-based 3D modeling

    KAUST Repository

    Chaudhuri, Siddhartha

    2011-01-01

    Assembly-based modeling is a promising approach to broadening the accessibility of 3D modeling. In assembly-based modeling, new models are assembled from shape components extracted from a database. A key challenge in assembly-based modeling is the identification of relevant components to be presented to the user. In this paper, we introduce a probabilistic reasoning approach to this problem. Given a repository of shapes, our approach learns a probabilistic graphical model that encodes semantic and geometric relationships among shape components. The probabilistic model is used to present components that are semantically and stylistically compatible with the 3D model that is being assembled. Our experiments indicate that the probabilistic model increases the relevance of presented components. © 2011 ACM.

  11. 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.

  12. 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.

  13. Biomedical Applications of Self-Assembling Peptides

    NARCIS (Netherlands)

    Radmalekshahi, Mazda; Lempsink, Ludwijn; Amidi, Maryam; Hennink, Wim E.; Mastrobattista, Enrico

    2016-01-01

    Self-assembling peptides have gained increasing attention as versatile molecules to generate diverse supramolecular structures with tunable functionality. Because of the possibility to integrate a wide range of functional domains into self-assembling peptides including cell attachment sequences,

  14. 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

  15. Covalent defects restrict supramolecular self-assembly of homopolypeptides: case study of β2-fibrils of poly-L-glutamic acid.

    Directory of Open Access Journals (Sweden)

    Aleksandra Fulara

    Full Text Available Poly-L-glutamic acid (PLGA often serves as a model in studies on amyloid fibrils and conformational transitions in proteins, and as a precursor for synthetic biomaterials. Aggregation of PLGA chains and formation of amyloid-like fibrils was shown to continue on higher levels of superstructural self-assembly coinciding with the appearance of so-called β2-sheet conformation manifesting in dramatic redshift of infrared amide I' band below 1600 cm(-1. This spectral hallmark has been attributed to network of bifurcated hydrogen bonds coupling C = O and N-D (N-H groups of the main chains to glutamate side chains. However, other authors reported that, under essentially identical conditions, PLGA forms the conventional in terms of infrared characteristics β1-sheet structure (exciton-split amide I' band with peaks at ca. 1616 and 1683 cm(-1. Here we attempt to shed light on this discrepancy by studying the effect of increasing concentration of intentionally induced defects in PLGA on the tendency to form β1/β2-type aggregates using infrared spectroscopy. We have employed carbodiimide-mediated covalent modification of Glu side chains with n-butylamine (NBA, as well as electrostatics-driven inclusion of polylysine chains, as two different ways to trigger structural defects in PLGA. Our study depicts a clear correlation between concentration of defects in PLGA and increasing tendency to depart from the β2-structure toward the one less demanding in terms of chemical uniformity of side chains: β1-structure. The varying predisposition to form β1- or β2-type aggregates assessed by infrared absorption was compared with the degree of morphological order observed in electron microscopy images. Our results are discussed in the context of latent covalent defects in homopolypeptides (especially with side chains capable of hydrogen-bonding that could obscure their actual propensities to adopt different conformations, and limit applications in the field of

  16. Covalent Defects Restrict Supramolecular Self-Assembly of Homopolypeptides: Case Study of β2-Fibrils of Poly-L-Glutamic Acid

    Science.gov (United States)

    Fulara, Aleksandra; Hernik, Agnieszka; Nieznańska, Hanna; Dzwolak, Wojciech

    2014-01-01

    Poly-L-glutamic acid (PLGA) often serves as a model in studies on amyloid fibrils and conformational transitions in proteins, and as a precursor for synthetic biomaterials. Aggregation of PLGA chains and formation of amyloid-like fibrils was shown to continue on higher levels of superstructural self-assembly coinciding with the appearance of so-called β2-sheet conformation manifesting in dramatic redshift of infrared amide I′ band below 1600 cm−1. This spectral hallmark has been attributed to network of bifurcated hydrogen bonds coupling C = O and N-D (N-H) groups of the main chains to glutamate side chains. However, other authors reported that, under essentially identical conditions, PLGA forms the conventional in terms of infrared characteristics β1-sheet structure (exciton-split amide I′ band with peaks at ca. 1616 and 1683 cm−1). Here we attempt to shed light on this discrepancy by studying the effect of increasing concentration of intentionally induced defects in PLGA on the tendency to form β1/β2-type aggregates using infrared spectroscopy. We have employed carbodiimide-mediated covalent modification of Glu side chains with n-butylamine (NBA), as well as electrostatics-driven inclusion of polylysine chains, as two different ways to trigger structural defects in PLGA. Our study depicts a clear correlation between concentration of defects in PLGA and increasing tendency to depart from the β2-structure toward the one less demanding in terms of chemical uniformity of side chains: β1-structure. The varying predisposition to form β1- or β2-type aggregates assessed by infrared absorption was compared with the degree of morphological order observed in electron microscopy images. Our results are discussed in the context of latent covalent defects in homopolypeptides (especially with side chains capable of hydrogen-bonding) that could obscure their actual propensities to adopt different conformations, and limit applications in the field of synthetic

  17. Cd (II) and holodirected lead (II) 3D-supramolecular coordination polymers based on nicotinic acid: Structure, fluorescence property and photocatalytic activity

    Science.gov (United States)

    Etaiw, Safaa El-din H.; Abd El-Aziz, Dina M.; Marie, Hassan; Ali, Elham

    2018-05-01

    Two new supramolecular coordination polymers namely {[Cd(NA)2(H2O)]}, SCP 1 and {[Pb(NA)2]}, SCP 2, (NA = nicotinate ligand) were synthesized by self-assembly method and structurally characterized by different analytical and spectroscopic methods. Single-crystal X-ray diffraction showed that SCP 1 extend in three dimensions containing bore structure where the 3D- network is constructed via interweaving zigzag chains. The Cd atom coordinates to (O4N2) atoms forming distorted-octahedral configuration. The structure of SCP 2 extend down the projection of the b-axis creating parallel zigzag 1D-chains connected by μ2-O2 atoms and H-bonds forming a holodirected lead (II) hexagonal bi-pyramid configuration. SCP 2 extend to 3D-network via coordinate and hydrogen bonds. The thermal stability, photoluminescence properties, photocatalytic activity for the degradation of methylene blue dye (MB) under UV-irradiation and sunlight irradiation were also studied.

  18. The electrocatalytic activity of a supramolecular assembly of CoTsPc/FeT4MPyP on multi-walled carbon nanotubes towards L-glutathione, and its determination in human erythrocytes

    International Nuclear Information System (INIS)

    Luz, R.C.S.; Maroneze, C.M.; Tanaka, A.A.; Kubota, L.T.; Gushikem, Y.; Damos, F.S.

    2010-01-01

    The electrocatalytic activity of a supramolecular complex based on cobalt(II) phthalocyanine tetrasulfonate and iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin adsorbed on multi-walled carbon nanotubes for the oxidation of L-glutathione (GSH) was investigated at pH 7.4. Scanning electron microscopy and energy dispersive X-ray spectrometry were used to characterize the morphologies and composition of the materials. The modified electrode displayed efficient electrocatalytic activity in terms of oxidation of GSH at an oxidation potential of 0 V (versus Ag/AgCl). Cyclic voltammetry and amperometry indicated that the oxidation involves 2-electrons, with a heterogeneous rate constant of 4.9 x 10 5 mol -1 L s -1 . The response is linear from 2 to 210 μmol L -1 , the sensitivity is 1570 μA L mmol -1 , the detection limit is 0.03 μmol L -1 , and the relative standard deviation of 110 μmol L -1 GSH was 2.6% (n=10). The modified electrode was applied to the determination of GSH in erythrocytes and the results were in agreement with those obtained by a method reported in the literature. (author)

  19. Magnetic feature and near-infrared absorption of a [Pt(mnt)2]-based H-bond supramolecular crystal

    International Nuclear Information System (INIS)

    Li, Cui-Ping; Nie, Li; Pei, Wen-Bo; Li, Li; Tian, Zheng-Fang; Liu, Jian-Lan; Gao, Xu-Sheng; Ren, Xiao-Ming

    2016-01-01

    A new salt [H 2 DABCO][Pt(mnt) 2 ] 2 (1) (mnt 2- =maleonitriledithiolate and H 2 DABCO 2+ is diprotonated 1,4-diazabicyclo[2.2.2]octane) has been synthesized; its crystal structure, magnetic and near-IR absorption properties have been investigated. Two different [Pt(mnt) 2 ] - anions form the strong π-dimers, labeled as Pt(1)-dimer and Pt(2)-dimer, with quite shorter Pt…Pt and S…S distances and molecular plane-to-plane distance (<3.5 Å) within a dimer. The [Pt(mnt) 2 ] 2 2- π-dimers are connected through the cations in the strong H-bond manner to form three-dimensional H-bond supramolecular crystal. The salt shows weak paramagnetism in 1.99–300 K and this is due to the existence of strong antiferromagnetic coupling within a π-dimer. In addition, a small thermal hysteresis loop is observed at ca. 120 K, indicating that a phase transition probably occurs that is further confirmed by variable-temperature IR spectra. Another fascinating functionality of 1 is the intense near-IR absorption in the region of 750–2500 nm, and this near-IR absorption feature makes it to be a promising optical material. - Graphical abstract: A H-bond supramolecular crystal of [H 2 DABCO][Pt(mnt) 2 ] 2 shows a magnetic phase transition at ca. 120 K with sizable thermal hysteresis loop and intense near-IR absorption in the region of 750–2500 nm.

  20. 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.

  1. 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.

  2. 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...

  3. Polymer complexes.. XXXX. Supramolecular assembly on coordination models of mixed-valence-ligand poly[1-acrylamido-2-(2-pyridyl)ethane] complexes

    Science.gov (United States)

    El-Sonbati, A. Z.; El-Bindary, A. A.; Diab, M. A.

    2003-02-01

    The build-up of polymer metallic supramolecules based on homopolymer (1-acrylamido-2-(2-pyridyl)ethane (AEPH)) and ruthenium, rhodium, palladium as well as platinum complexes has been pursued with great interest. The homopolymer shows three types of coordination behaviour. In the mixed valence paramagnetic trinuclear polymer complexes [( 11)+( 12)] in the paper and in mononuclear polymer complexes ( 1)-( 5) it acts as a neutral bidentate ligand coordinating through the N-pyridine and NH-imino atoms, while in the mixed ligand diamagnetic poly-chelates, which are obtained from the reaction of AEPH with PdX 2 and KPtCl 4 in the presence of N-heterocyclic base consisting of polymer complexes ( 9)+( 10), and in monouclear compounds ( 6)-( 8), it behaves as a monobasic bidentate ligand coordinating through the same donor atoms. In mononuclear compounds ( 13)+( 14) it acts as a monobasic and neutral bidentate ligand coordinating only through the same donor atoms. Monomeric distorted octahedral or trimeric chlorine-bridged, approximately octahedral structures are proposed for these polymer complexes. The poly-chelates are of 1:1, 1:2 and 3:2 (metal-homopolymer) stoichiometry and exhibit six coordination. The values of ligand field parameters were calculated. The homopolymer and their polymer complexes have been characterized physicochemically.

  4. 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

  5. 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.

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

    International Nuclear Information System (INIS)

    Sousa Luz, Roberto A. de; Martins, Marccus Victor A.; Magalhaes, Janildo L.; Siqueira, Jose R.; Zucolotto, Valtencir; Oliveira, Osvaldo N.; Crespilho, Frank N.; Cantanhede da Silva, Welter

    2011-01-01

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

  7. 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...

  8. 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.

  9. [Characteristics of supramolecular imprinting template on liver meridian tropism of traditional Chinese medicine based on molecular connectivity index].

    Science.gov (United States)

    Fan, Shi-Qi; Li, Sen; Liu, Jin-Ling; Yang, Jiao; Hu, Chao; Zhu, Jun-Ping; Xiao, Xiao-Qin; Liu, Wen-Long; He, Fu-Yuan

    2017-01-01

    The molecular connectivity index was adopted to explore the characteristics of supramolecular imprinting template of herbs distributed to liver meridian, in order to provide scientific basis for traditional Chinese medicines(TCMs) distributed to liver meridian. In this paper, with "12th five-year plan" national planning textbooks Science of Traditional Chinese Medicine and Chemistry of Traditional Chinese Medicine as the blueprint, literatures and TCMSP sub-databases in TCM pharmacology of northwest science and technology university of agriculture and forestry were retrieved to collect and summarize active constituents of TCM distributed to liver meridian, and calculate the molecular connectivity index. The average molecular connectivity index of ingredients distributed to liver meridian was 9.47, which was close to flavonoid glycosides' (9.17±2.11) and terpenes (9.30±3.62). Therefore, it is inferred that template molecule of liver meridian is similar to physicochemical property of flavonoid glycosides and terpenes, which could be best matched with imprinting template of liver meridian. Copyright© by the Chinese Pharmaceutical Association.

  10. DNA-Based Self-Assembly of Fluorescent Nanodiamonds.

    Science.gov (United States)

    Zhang, Tao; Neumann, Andre; Lindlau, Jessica; Wu, Yuzhou; Pramanik, Goutam; Naydenov, Boris; Jelezko, Fedor; Schüder, Florian; Huber, Sebastian; Huber, Marinus; Stehr, Florian; Högele, Alexander; Weil, Tanja; Liedl, Tim

    2015-08-12

    As a step toward deterministic and scalable assembly of ordered spin arrays we here demonstrate a bottom-up approach to position fluorescent nanodiamonds (NDs) with nanometer precision on DNA origami structures. We have realized a reliable and broadly applicable surface modification strategy that results in DNA-functionalized and perfectly dispersed NDs that were then self-assembled in predefined geometries. With optical studies we show that the fluorescence properties of the nitrogen-vacancy color centers in NDs are preserved during surface modification and DNA assembly. As this method allows the nanoscale arrangement of fluorescent NDs together with other optically active components in complex geometries, applications based on self-assembled spin lattices or plasmon-enhanced spin sensors as well as improved fluorescent labeling for bioimaging could be envisioned.

  11. 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.

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

    Science.gov (United States)

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

    2015-01-01

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

  13. Neutronics assessment of thorium-based fuel assembly in SCWR

    International Nuclear Information System (INIS)

    Liu, Shichang; Cai, Jiejin

    2013-01-01

    Highlights: • A novel thorium-based fuel assembly for SCWR has been introduced and investigated. • Neutronic properties of three thorium fuels have been studied, compared with UO 2 fuel. • The thorium-based fuel has advantages on fuel utilization and lower MAs generation. -- Abstract: Aiming to take advantage of neutron spectrum of SCWR, a novel thorium-based fuel assembly for SCWR is introduced in this paper. The neutronic characteristics of the introduced fuel assembly with three different thorium fuel types have been investigated using the “dragon” codes. The parameters in different working conditions, such as infinite multiplication factors, radial power peaking factor, temperature coefficient of reactivity and their relation with the operation period have been assessed by comparing with conventional uranium assembly. Moreover, the moderator-to-fuel ratio (MFR) was changed in order to investigate its influence on the neutronic characteristics of fuel assembly. Results show that the thorium-based fuel has advantages on both efficient fuel utilization and lower minor actinide generation, with some similar neutronic properties to the uranium fuel

  14. Assembly work and transport of JT-60SA cryostat base

    International Nuclear Information System (INIS)

    Okano, Fuminori; Masaki, Kei; Yagyu, Jun-ichi; Shibama, Yusuke; Sakasai, Akira; Miyo, Yasuhiko; Kaminaga, Atsushi; Nishiyama, Tomokazu; Suzuki, Sadaaki; Nakamura, Shigetoshi; Shibanuma, Kiyoshi

    2013-11-01

    Japan Atomic Energy Agency started to construct a fully superconducting tokamak experiment device, JT-60SA, to support the ITER since January, 2013 at the Fusion Research and Development Directorate in Naka, Japan. The JT-60SA will be constructed with enhancing the previous JT-60 infrastructures, in the JT-60 torus hall, where the ex-JT-60 machine was disassembled. The JT-60SA Cryostat Base, for base of the entire tokamak structure, were assembly as the first step of this construction. The Cryostat Base (CB, 250tons) is consists of 7 main components made of stainless steel, in 12 m diameter and 3 m height. The CB was built in the Spain and transported to the Naka site, via Hitachi port. After pre-assembly work including preliminary measurements and sole plate adjustments of its height/flatness, the JT-60SA CB was carefully set on the sole plate. JT-60SA CB was assembled with high accuracy by using a laser tracker. The CB was adjusted in the height and flatness against the assembly reference position and determined by the absolute coordinates. This report introduces the concrete result of assembly work and transport of JT-60SA CB. (author)

  15. Supramolecular solvent-based extraction of benzimidazolic fungicides from natural waters prior to their liquid chromatographic/fluorimetric determination.

    Science.gov (United States)

    Moral, Antonia; Sicilia, María Dolores; Rubio, Soledad

    2009-05-01

    A supramolecular solvent made up of vesicles of decanoic acid in the nano- and microscale regimes dispersed in a continuous aqueous phase is proposed for the extraction/preconcentration of benzimidazolic fungicides (BFs) from river and underground water samples prior to their determination by liquid chromatography (LC)/fluorimetry. The solvent is produced from the coacervation of decanoic acid aqueous vesicles by the action of tetrabutylammonium (Bu(4)N(+)). Carbendazim (CB), thiabendazole (TB) and fuberidazole (FB) are extracted on the basis of hydrophobic and pi-cation interactions and the formation of hydrogen bonds. The extraction provides high preconcentration factors (160 for CB and 190 for TB and FB), requires a short time (the procedure takes less than 20 min and several samples can be simultaneously processed) and a low sample volume (20 mL), and avoids the use of toxic organic solvents. Because of the absence of matrix interferences and the low viscosity of the extracts, these can be directly injected into the chromatographic system without the need of cleaning-up or diluting them. Recoveries are not influenced by the presence of salt concentrations up to 1 M. The proposed method provides detection limits for the determination of CB, TB and FB in natural waters of 32, 4 and 0.1 ng L(-1), respectively, and a precision, expressed as relative standard deviation (n=11) of 5.5% for CB (100 ng L(-1)), 4.0% for TB (80 ng L(-1)) and 2.5% for FB (30 ng L(-1)). Recoveries obtained by applying this approach to the analysis of river and underground water samples fortified at the ng L(-1) level are in the intervals 75-83, 95-102 and 97-101% for CB, TB and FB, respectively.

  16. 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 ...

  17. Fabrication of a highly selective cadmium (II) sensor based on 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane as a supramolecular ionophore

    Energy Technology Data Exchange (ETDEWEB)

    Ghaemi, Arezoo, E-mail: arezooghaemi@yahoo.com; Tavakkoli, Haman; Mombeni, Tayebeh

    2014-05-01

    A new cadmium (II) ion selective sensor based on 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane (kryptofix5) as a supramolecular carrier has been developed. The membrane solutions containing polyvinyl chloride (PVC), plasticizer, sodium tetraphenylborate (NaTPB) as a lipophilic ionic additive and kryptofix5 as an ionophore were directly coated on the surface of graphite rods. The best composition of the coated membrane (w/w%) was found to be: 30.0% PVC, 61.0% dioctyl sebacate (DOS), 6.0% NaTPB and 3.0% kryptofix5. The sensor indicates a good linear response for Cd{sup 2+} cation over a wide concentration range from 1.0 × 10{sup −5} to 1.0 × 10{sup −1} M with a Nernstian slope of 29.8 ± 0.1 mV/decade and the detection limit is 8.4 × 10{sup −6} M. The response time of the sensor is 15 s and it can be used for 7 weeks without significant drift in potential. The sensor operates in the wide pH range of 1.0–6.0. This sensor reveals a very good selectivity toward Cd{sup 2+} ion over a wide range of alkali, transition and heavy metal cations. The sensor was used as an indicator electrode for potentiometric titration of Cd{sup 2+} using sodium fluoride and ethylenediaminetetraacetic acid (EDTA) solutions with a sharp potential change that occurred at the end point. In addition, the proposed sensor was successfully used for determination of Cd{sup 2+} cation in real water samples. - Graphical abstract: Fabrication of a highly selective cadmium (II) sensor based on 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane as a supramolecular ionophore. - Highlights: • Fabrication of a novel Cd{sup 2+} selective sensor with high sensitivity and selectivity • Using fabricated sensor in a wide pH range with fast response time • Replacing expensive techniques with this low cost sensor with low detection limit • Excellent capability of this sensor for measuring Cd{sup 2+} in real samples.

  18. Thermal Hydraulic Analysis Of Thorium-Based Annular Fuel Assemblies

    Energy Technology Data Exchange (ETDEWEB)

    Han, Kyu Hyun [Korea Institute of Nuclear Safety, 19, Guseong-dong, Yuseong-gu, Daejeon, 305-338 (Korea, Republic of)

    2008-07-01

    Thermal hydraulic characteristics of thorium-based fuel assemblies loaded with annular seed pins have been analyzed using AMAP combined with MATRA, and compared with those of the existing thorium-based assemblies. MATRA and AMAP showed good agreements for the pressure drops at the internal sub-channels. The pressure drop generally increased in the cases of the assemblies loaded with annular seed pins due to the larger wetted perimeter, but an exception existed. In the inner sub-channels of the seed pins, mass fluxes were high due to the grid form losses in the outer sub-channels. About 43% of the heat generated from the seed pin flowed into the inner sub-channel and the rest into the outer sub-channel, which implies the inner to outer wall heat flux ratio was approximately 1.2. The maximum temperatures of the annular seed pins were slightly above 500 deg. C. The MDNBRs of the assemblies loaded with annular seed pins were higher than those of the existing assemblies. Due to the fact that inter-channel mixing cannot occur in the inner sub-channels, temperatures and enthalpies were higher in the inner sub-channels. (author)

  19. Self-assembly behaviour of conjugated terthiophene surfactants in water

    NARCIS (Netherlands)

    van Rijn, Patrick; Janeliunas, Dainius; Brizard, Aurelie M.; Stuart, Marc C. A.; Koper, Ger J. M.; Eelkema, Rienk; van Esch, Jan H.

    2011-01-01

    Conjugated self-assembled systems in water are of great interest because of their potential application in biocompatible supramolecular electronics, but so far their supramolecular chemistry remains almost unexplored. Here we present amphiphilic terthiophenes as a general self-assembling platform

  20. The Orange Side of Disperse Red 1: Humidity-Driven Color Switching in Supramolecular Azo-Polymer Materials Based on Reversible Dye Aggregation.

    Science.gov (United States)

    Schoelch, Simon; Vapaavuori, Jaana; Rollet, Frédéric-Guillaume; Barrett, Christopher J

    2017-01-01

    Humidity detection, and the quest for low-cost facile humidity-sensitive indicator materials is of great interest for many fields, including semi-conductor processing, food transport and storage, and pharmaceuticals. Ideal humidity-detection materials for a these applications might be based on simple clear optical readout with no power supply, i.e.: a clear color change observed by the naked eye of any untrained observer, since it doesn't require any extra instrumentation or interpretation. Here, the introduction of a synthesis-free one-step procedure, based on physical mixing of easily available commercial materials, for producing a humidity memory material which can be easily painted onto a wide variety of surfaces and undergoes a remarkable color change (approximately 100 nm blue-shift of λ MAX ) upon exposure to various thresholds of levels of ambient humidity is reported. This strong color change, easily visible to as a red-to-orange color switch, is locked in until inspection, but can then be restored reversibly if desired, after moderate heating. By taking advantage of spontaneously-forming reversible 'soft' supramolecular bonds between a red-colored azo dye and a host polymer matrix, a reversible dye 'migration' aggregation appearing orange, and dis-aggregation back to red can be achieved, to function as the sensor. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Soft Assembling Project-Based Learning and Leadership in Japan

    Science.gov (United States)

    Knight, Kevin; Murphey, Tim

    2017-01-01

    In this article, we initially focus on how the conceptualization of leadership by Knight (2013a) in his leadership seminars became the basis for choosing a project-based learning (PBL) approach. We then consider how soft assembling can enhance the leadership project activities of student teams and group-work in general classes. Soft assembling…

  2. Penta-fibrillar assembly: A Building block collagen based materials

    Indian Academy of Sciences (India)

    There is a smartness in the way the penta-fibrils behave in collagen based biomaterials. It is one of the intriguing nano material with a size of about 4 nano meter diagonal size. There are several intermolecular forces that participate in the penta fibrillar assembly, which derive importance in smart behavior of collagen.

  3. 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

  4. 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,

  5. Development of training simulator based on critical assemblies test bench

    International Nuclear Information System (INIS)

    Narozhnyi, A.T.; Vorontsov, S.V.; Golubeva, O.A.; Dyudyaev, A.M.; Il'in, V.I.; Kuvshinov, M.I.; Panin, A.V.; Peshekhonov, D.P.

    2007-01-01

    When preparing critical mass experiment, multiplying system (MS) parts are assembled manually. This work is connected with maximum professional risk to personnel. Personnel training and keeping the skill of working experts is the important factor of nuclear safety maintenance. For this purpose authors develop a training simulator based on functioning critical assemblies test bench (CATB), allowing simulation of the MS assemblage using training mockups made of inert materials. The control program traces the current status of MS under simulation. A change in the assembly neutron physical parameters is mapped in readings of the regular devices. The simulator information support is provided by the computer database on physical characteristics of typical MS components The work in the training mode ensures complete simulation of real MS assemblage on the critical test bench. It makes it possible to elaborate the procedures related to CATB operation in a standard mode safely and effectively and simulate possible abnormal situations. (author)

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

    Directory of Open Access Journals (Sweden)

    Jurriaan Huskens

    2011-10-01

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

  7. Molecular self-assembly advances and applications

    CERN Document Server

    Dequan, Alex Li

    2012-01-01

    In the past several decades, molecular self-assembly has emerged as one of the main themes in chemistry, biology, and materials science. This book compiles and details cutting-edge research in molecular assemblies ranging from self-organized peptide nanostructures and DNA-chromophore foldamers to supramolecular systems and metal-directed assemblies, even to nanocrystal superparticles and self-assembled microdevices

  8. Inversion of Supramolecular Chirality by Sonication-Induced Organogelation

    Science.gov (United States)

    Maity, Sibaprasad; Das, Priyadip; Reches, Meital

    2015-01-01

    Natural helical structures have inspired the formation of well-ordered peptide-based chiral nanostructures in vitro. These structures have drawn much attention owing to their diverse applications in the area of asymmetric catalysts, chiral photonic materials, and nanoplasmonics. The self-assembly of two enantiomeric fluorinated aromatic dipeptides into ordered chiral fibrillar nanostructures upon sonication is described. These fibrils form organogels. Our results clearly indicate that fluorine-fluorine interactions play an important role in self-assembly. Circular dichroism analysis revealed that both peptides (peptides 1 and 2), containing two fluorines, depicted opposite cotton effects in their monomeric form compared with their aggregated form. This shows that supramolecular chirality inversion took place during the stimuli-responsive self-aggregation process. Conversely, peptide 3, containing one fluorine, did not exhibit chirality inversion in sonication-induced organogelation. Therefore, our results clearly indicate that fluorination plays an important role in the organogelation process of these aromatic dipeptides. Our findings may have broad implications regarding the design of chiral nanostructures for possible applications such as chiroptical switches, asymmetric catalysis, and chiral recognitions. PMID:26553508

  9. Spectro-microscopic study of the formation of supramolecular networks

    Science.gov (United States)

    Sadowski, Jerzy T.

    2015-03-01

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

  10. [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.

  11. DNA fragments assembly based on nicking enzyme system.

    Directory of Open Access Journals (Sweden)

    Rui-Yan Wang

    Full Text Available A couple of DNA ligation-independent cloning (LIC methods have been reported to meet various requirements in metabolic engineering and synthetic biology. The principle of LIC is the assembly of multiple overlapping DNA fragments by single-stranded (ss DNA overlaps annealing. Here we present a method to generate single-stranded DNA overlaps based on Nicking Endonucleases (NEases for LIC, the method was termed NE-LIC. Factors related to cloning efficiency were optimized in this study. This NE-LIC allows generating 3'-end or 5'-end ss DNA overlaps of various lengths for fragments assembly. We demonstrated that the 10 bp/15 bp overlaps had the highest DNA fragments assembling efficiency, while 5 bp/10 bp overlaps showed the highest efficiency when T4 DNA ligase was added. Its advantage over Sequence and Ligation Independent Cloning (SLIC and Uracil-Specific Excision Reagent (USER was obvious. The mechanism can be applied to many other LIC strategies. Finally, the NEases based LIC (NE-LIC was successfully applied to assemble a pathway of six gene fragments responsible for synthesizing microbial poly-3-hydroxybutyrate (PHB.

  12. Automated and model-based assembly of an anamorphic telescope

    Science.gov (United States)

    Holters, Martin; Dirks, Sebastian; Stollenwerk, Jochen; Loosen, Peter

    2018-02-01

    Since the first usage of optical glasses there has been an increasing demand for optical systems which are highly customized for a wide field of applications. To meet the challenge of the production of so many unique systems, the development of new techniques and approaches has risen in importance. However, the assembly of precision optical systems with lot sizes of one up to a few tens of systems is still dominated by manual labor. In contrast, highly adaptive and model-based approaches may offer a solution for manufacturing with a high degree of automation and high throughput while maintaining high precision. In this work a model-based automated assembly approach based on ray-tracing is presented. This process runs autonomously, and accounts for a wide range of functionality. It firstly identifies the sequence for an optimized assembly and secondly, generates and matches intermediate figures of merit to predict the overall optical functionality of the optical system. This process also takes into account the generation of a digital twin of the optical system, by mapping key-performance-indicators like the first and the second momentum of intensity into the optical model. This approach is verified by the automatic assembly of an anamorphic telescope within an assembly cell. By continuous measuring and mapping the key-performance-indicators into the optical model, the quality of the digital twin is determined. Moreover, by measuring the optical quality and geometrical parameters of the telescope, the precision of this approach is determined. Finally, the productivity of the process is evaluated by monitoring the speed of the different steps of the process.

  13. 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

  14. Functional chiral hydrogen-bonded assemblies

    NARCIS (Netherlands)

    Mateos timoneda, Miguel

    2005-01-01

    In this thesis different aspects of functional hydrogen-bonded (double and tetrarosette) assemblies are described. The functions were inspired by naturally occurring mechanisms such as molecular recognition, supramolecular chirality and its origin, and biostrategies for the correct folding of

  15. Multivalent protein assembly using monovalent self-assembling building blocks

    NARCIS (Netherlands)

    Petkau - Milroy, K.; Sonntag, M.H.; Colditz, A.; Brunsveld, L.

    2013-01-01

    Discotic molecules, which self-assemble in water into columnar supramolecular polymers, emerged as an alternative platform for the organization of proteins. Here, a monovalent discotic decorated with one single biotin was synthesized to study the self-assembling multivalency of this system in regard

  16. PLC based control system for RAM assembly test facility

    International Nuclear Information System (INIS)

    Kulkarni, S.S.; Kumar, Vinaya; Chandra, Umesh

    1994-01-01

    The flexibility, expandability, ease of programming and diagnostic features makes the programmable logic controller (PLC) suitable for a variety of control applications in engineering system test facilities. A PLC based control system for RAM assembly test facility (RATF) and for testing the related hydraulic components is being developed and installed at BARC. This paper describes the approach taken for meeting the control requirements and illustrates the PLC software that has been developed. (author). 1 fig

  17. Quantitative self-assembly prediction yields targeted nanomedicines

    Science.gov (United States)

    Shamay, Yosi; Shah, Janki; Işık, Mehtap; Mizrachi, Aviram; Leibold, Josef; Tschaharganeh, Darjus F.; Roxbury, Daniel; Budhathoki-Uprety, Januka; Nawaly, Karla; Sugarman, James L.; Baut, Emily; Neiman, Michelle R.; Dacek, Megan; Ganesh, Kripa S.; Johnson, Darren C.; Sridharan, Ramya; Chu, Karen L.; Rajasekhar, Vinagolu K.; Lowe, Scott W.; Chodera, John D.; Heller, Daniel A.

    2018-02-01

    Development of targeted nanoparticle drug carriers often requires complex synthetic schemes involving both supramolecular self-assembly and chemical modification. These processes are generally difficult to predict, execute, and control. We describe herein a targeted drug delivery system that is accurately and quantitatively predicted to self-assemble into nanoparticles based on the molecular structures of precursor molecules, which are the drugs themselves. The drugs assemble with the aid of sulfated indocyanines into particles with ultrahigh drug loadings of up to 90%. We devised quantitative structure-nanoparticle assembly prediction (QSNAP) models to identify and validate electrotopological molecular descriptors as highly predictive indicators of nano-assembly and nanoparticle size. The resulting nanoparticles selectively targeted kinase inhibitors to caveolin-1-expressing human colon cancer and autochthonous liver cancer models to yield striking therapeutic effects while avoiding pERK inhibition in healthy skin. This finding enables the computational design of nanomedicines based on quantitative models for drug payload selection.

  18. Hydrogels Based on Ag+ -Modulated Assembly of 5'-Adenosine Monophosphate for Enriching Biomolecules.

    Science.gov (United States)

    Hu, Yuanyuan; Xie, Dong; Wu, Yang; Lin, Nangui; Song, Aixin; Hao, Jingcheng

    2017-11-07

    Supramolecular hydrogels obtained by combining 5'-adenosine monophosphate (AMP) with Ag + were fabricated in this work. Their gelation capability was enhanced by increasing the concentration of Ag + or decreasing the pH. The gels are very sensitive to light, which endows them with potential applications as visible-light photosensitive materials. Coordination between the nucleobase of AMP and Ag + , as well as π-π stacking of nucleobases, are considered to be the main driving forces for self-assembly. The hydrogels successfully achieved the encapsulation and enrichment of biomolecules. Hydrogen bonding between the amino group of guest molecules and silver nanoparticles along the nanofibers drives the enrichment and is considered to be a crucial interaction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. The btp [2,6-bis(1,2,3-triazol-4-yl)pyridine] binding motif: a new versatile terdentate ligand for supramolecular and coordination chemistry.

    Science.gov (United States)

    Byrne, Joseph P; Kitchen, Jonathan A; Gunnlaugsson, Thorfinnur

    2014-08-07

    Ligands containing the btp [2,6-bis(1,2,3-triazol-4-yl)pyridine] motif have appeared with increasing regularity over the last decade. This class of ligands, formed in a one pot ‘click’ reaction, has been studied for various purposes, such as for generating d and f metal coordination complexes and supramolecular self-assemblies, and in the formation of dendritic and polymeric networks, etc. This review article introduces btp as a novel and highly versatile terdentate building block with huge potential in inorganic supramolecular chemistry. We will focus on the coordination chemistry of btp ligands with a wide range of metals, and how it compares with other classical pyridyl and polypyridyl based ligands, and then present a selection of applications including use in catalysis, enzyme inhibition, photochemistry, molecular logic and materials, e.g. polymers, dendrimers and gels. The photovoltaic potential of triazolium derivatives of btp and its interactions with anions will also be discussed.

  20. Optimizing DNA assembly based on statistical language modelling.

    Science.gov (United States)

    Fang, Gang; Zhang, Shemin; Dong, Yafei

    2017-12-15

    By successively assembling genetic parts such as BioBrick according to grammatical models, complex genetic constructs composed of dozens of functional blocks can be built. However, usually every category of genetic parts includes a few or many parts. With increasing quantity of genetic parts, the process of assembling more than a few sets of these parts can be expensive, time consuming and error prone. At the last step of assembling it is somewhat difficult to decide which part should be selected. Based on statistical language model, which is a probability distribution P(s) over strings S that attempts to reflect how frequently a string S occurs as a sentence, the most commonly used parts will be selected. Then, a dynamic programming algorithm was designed to figure out the solution of maximum probability. The algorithm optimizes the results of a genetic design based on a grammatical model and finds an optimal solution. In this way, redundant operations can be reduced and the time and cost required for conducting biological experiments can be minimized. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

  1. 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.

  2. Research on Outfitting Virtual Assembly based on Ergonomics

    Directory of Open Access Journals (Sweden)

    Jiang Zuhua

    2018-01-01

    Full Text Available To improve the present situation where the assembly work of ship outfitting depends on manual experiential operation, the thesis, taking outfitting assembly operation as the research object and optimal assembly path as the target, puts forward the simulation method and procedure of outfitting virtual assembly considering operational posture, operational load, reachability and visibility and other ergonomic factors, taking pipe assembly operation of ship section as the application example. The results show that the method can obtain better assembly operation path, avoid interference of workers’ operation process and improve the efficiency of assembly operation.

  3. 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.

  4. Research on Key Technologies of Unit-Based CNC Machine Tool Assembly Design

    Directory of Open Access Journals (Sweden)

    Zhongqi Sheng

    2014-01-01

    Full Text Available Assembly is the part that produces the maximum workload and consumed time during product design and manufacturing process. CNC machine tool is the key basic equipment in manufacturing industry and research on assembly design technologies of CNC machine tool has theoretical significance and practical value. This study established a simplified ASRG for CNC machine tool. The connection between parts, semantic information of transmission, and geometric constraint information were quantified to assembly connection strength to depict the assembling difficulty level. The transmissibility based on trust relationship was applied on the assembly connection strength. Assembly unit partition based on assembly connection strength was conducted, and interferential assembly units were identified and revised. The assembly sequence planning and optimization of parts in each assembly unit and between assembly units was conducted using genetic algorithm. With certain type of high speed CNC turning center, as an example, this paper explored into the assembly modeling, assembly unit partition, and assembly sequence planning and optimization and realized the optimized assembly sequence of headstock of CNC machine tool.

  5. 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.

  6. 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.

  7. Electrochemical aptasensor for highly sensitive determination of cocaine using a supramolecular aptamer and rolling circle amplification

    International Nuclear Information System (INIS)

    Shen, Bo; Yan, Yurong; Tang, Renkuan; Li, Yongguo; Li, Jianbo; Cheng, Wei; Ju, Huangxian; Ding, Shijia

    2015-01-01

    We report on a novel strategy for the electrochemical detection of cocaine. It is based on the use of a supramolecular aptamer, rolling circle amplification (RCA), and multiplex binding of a biotin-strepavidin system. The aptamer fragments were assembled to a supramolecular aptamer which, in the presence of cocaine, conjugates to streptavidin for anchoring of biotinylated circular DNA. This initiates RCA and enables sensitive electrochemical-enzymatic readout. A significant signal amplification was obtained by using streptavidin linked to alkaline phosphatase that binds to the remaining biotinylated detection probes and catalyzes the hydrolysis of the synthetic enzyme substrate α-naphthylphosphate. This dual amplification strategy tremendously increases the detection limit of the aptasensor. Under optimal conditions and using differential pulse voltammetry, cocaine can be detected in the concentration range between 2 and 500 nM with a detection limit as low as 1.3 nM (at S/N = 3). The method is specific and acceptably reproducible. It was successfully applied to the detection of cocaine in (spiked) urine samples. The data were in good agreement with those obtained by the GC-MS reference method. (author)

  8. Supra-molecular networks for CO2 capture

    Science.gov (United States)

    Sadowski, Jerzy; Kestell, John

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

  9. 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.

  10. 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

  11. Supramolecular interactions of oxidative stress biomarker glutathione with fluorone black

    Science.gov (United States)

    Hepel, Maria; Stobiecka, Magdalena

    2018-03-01

    which is likely based on an intermediate formation of a similar type of supramolecular ensembles.

  12. 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.

  13. Dynamic peptide libraries for the discovery of supramolecular nanomaterials

    Science.gov (United States)

    Pappas, Charalampos G.; Shafi, Ramim; Sasselli, Ivan R.; Siccardi, Henry; Wang, Tong; Narang, Vishal; Abzalimov, Rinat; Wijerathne, Nadeesha; Ulijn, Rein V.

    2016-11-01

    Sequence-specific polymers, such as oligonucleotides and peptides, can be used as building blocks for functional supramolecular nanomaterials. The design and selection of suitable self-assembling sequences is, however, challenging because of the vast combinatorial space available. Here we report a methodology that allows the peptide sequence space to be searched for self-assembling structures. In this approach, unprotected homo- and heterodipeptides (including aromatic, aliphatic, polar and charged amino acids) are subjected to continuous enzymatic condensation, hydrolysis and sequence exchange to create a dynamic combinatorial peptide library. The free-energy change associated with the assembly process itself gives rise to selective amplification of self-assembling candidates. By changing the environmental conditions during the selection process, different sequences and consequent nanoscale morphologies are selected.

  14. Supramolecular Switches Based on the Guanine–Cytosine (GC) Watson–Crick Pair: Effect of Neutral and Ionic Substituents

    NARCIS (Netherlands)

    Guerra, C.F.; van der Wijst, T.; Bickelhaupt, F.M.

    2006-01-01

    We have theoretically analyzed Watson–Crick guanine–cytosine (GC) base pairs in which purine-C8 and/or pyrimidine-C6 positions carry a substituent X = NH−, NH2, NH3+ (N series), O−, OH, or OH2+ (O series), using the generalized gradient approximation (GGA) of density functional theory at the

  15. Particle self-assembly at ionic liquid-based interfaces.

    Science.gov (United States)

    Frost, Denzil S; Nofen, Elizabeth M; Dai, Lenore L

    2014-04-01

    This review presents an overview of the nature of ionic liquid (IL)-based interfaces and self-assembled particle morphologies of IL-in-water, oil- and water-in-IL, and novel IL-in-IL Pickering emulsions with emphasis on their unique phenomena, by means of experimental and computational studies. In IL-in-water Pickering emulsions, particles formed monolayers at ionic liquid-water interfaces and were close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. Interestingly, other than equilibrating at the ionic liquid-water interfaces, microparticles with certain surface chemistries were extracted into the ionic liquid phase with a high efficiency. These experimental findings were supported by potential of mean force calculations, which showed large energy drops as hydrophobic particles crossed the interface into the IL phase. In the oil- and water-in-IL Pickering emulsions, microparticles with acidic surface chemistries formed monolayer bridges between the internal phase droplets rather than residing at the oil/water-ionic liquid interfaces, a significant deviation from traditional Pickering emulsion morphology. Molecular dynamics simulations revealed aspects of the mechanism behind this bridging phenomenon, including the role of the droplet phase, surface chemistry, and inter-particle film. Novel IL-in-IL Pickering emulsions exhibited an array of self-assembled morphologies including the previously observed particle absorption and bridging phenomena. The appearance of these morphologies depended on the particle surface chemistry as well as the ILs used. The incorporation of particle self-assembly with ionic liquid science allows for new applications at the intersection of these two fields, and have the potential to be numerous due to the tunability of the ionic liquids and particles incorporated, as well as the particle morphology by combining certain groups of particle surface chemistry, IL type (protic or aprotic), and whether oil

  16. 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.

  17. 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

  18. 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

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. Advances in modeling trait-based plant community assembly.

    Science.gov (United States)

    Laughlin, Daniel C; Laughlin, David E

    2013-10-01

    In this review, we examine two new trait-based models of community assembly that predict the relative abundance of species from a regional species pool. The models use fundamentally different mathematical approaches and the predictions can differ considerably. Maxent obtains the most even probability distribution subject to community-weighted mean trait constraints. Traitspace predicts low probabilities for any species whose trait distribution does not pass through the environmental filter. Neither model maximizes functional diversity because of the emphasis on environmental filtering over limiting similarity. Traitspace can test for the effects of limiting similarity by explicitly incorporating intraspecific trait variation. The range of solutions in both models could be used to define the range of natural variability of community composition in restoration projects. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. 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.

  6. Multifunctional Materials Based on Self Assembly of Molecular Nanostructures

    National Research Council Canada - National Science Library

    Stupp, Samuel

    2001-01-01

    .... The objective was to integrate self assembly, encoded in the triblock structure, luminescent properties, and the properties characteristic of materials that have macroscopically polar structure...

  7. 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.

  8. 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.

  9. 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.

  10. Supramolecular Complexes Formed by the Self-assembly of Hydrophobic Bis(Zn(2+)-cyclen) Complexes, Copper, and Di- or Triimide Units for the Hydrolysis of Phosphate Mono- and Diesters in Two-Phase Solvent Systems (Cyclen=1,4,7,10-Tetraazacyclododecane).

    Science.gov (United States)

    Hisamatsu, Yosuke; Miyazawa, Yuya; Yoneda, Kakeru; Miyauchi, Miki; Zulkefeli, Mohd; Aoki, Shin

    2016-01-01

    We previously reported on supramolecular complexes 4 and 5, formed by the 4 : 4 : 4 or 2 : 2 : 2 assembly of a dimeric zinc(II) complex (Zn2L(1)) having 2,2'-bipyridyl linker, dianion of cyanuric acid (CA) or 5,5-diethylbarbituric acid (Bar), and copper(II) ion (Cu(2+)) in an aqueous solution. The supermolecule 4 possesses Cu2(μ-OH)2 centers and catalyzes hydrolysis of phosphate monoester dianion, mono(4-nitrophenyl)phosphate (MNP), at neutral pH. In this manuscript, we report on design and synthesis of hydrophobic supermolecules 9 and 10 by 4 : 4 : 4 and 2 : 2 : 2 self-assembly of hydrophobic Zn2L(2) and Zn2L(3) containing long alkyl chains, CA or Bar, and Cu(2+) and their phosphatase activity for the hydrolysis of MNP and bis(4-nitrophenyl)phosphate (BNP) in two-phase solvent systems. We assumed that the Cu2(μ-OH)2 active sites of 9 and 10 would be more stable in organic solvent than in aqueous solution and that product inhibition of the supermolecules might be avoided by the release of HPO4(2-) into the aqueous layer. The findings indicate that 9 and 10 exhibit phosphatase activity in the two-phase solvent system, although catalytic turnover was not observed. Furthermore, the hydrolysis of BNP catalyzed by the hydrophobic 2 : 2 : 2 supermolecules in the two-phase solvent system is described.

  11. Predominantly ligand guided non-covalently linked assemblies of ...

    Indian Academy of Sciences (India)

    JUBARAJ B BARUAH

    2018-05-12

    May 12, 2018 ... Abstract. Various non-covalently linked inorganic self-assemblies formed by the supramolecular interacting .... metal-organic frameworks.59 Inorganic chemists rou- ...... two-dimensional organic–inorganic layered perovskite.

  12. Supercapacitors based on self-assembled graphene organogel.

    Science.gov (United States)

    Sun, Yiqing; Wu, Qiong; Shi, Gaoquan

    2011-10-14

    Self-assembled graphene organogel (SGO) with 3-dimensional (3D) macrostructure was prepared by solvothermal reduction of a graphene oxide (GO) dispersion in propylene carbonate (PC). This SGO was used as an electrode material for fabricating supercapacitors with a PC electrolyte. The supercapacitor can be operated in a wide voltage range of 0-3 V and exhibits a high specific capacitance of 140 F g(-1) at a discharge current density of 1 A g(-1). Furthermore, it can still keep a specific capacitance of 90 F g(-1) at a high current density of 30 A g(-1). The maximum energy density of the SGO based supercapacitor was tested to be 43.5 Wh kg(-1), and this value is higher than those of the graphene based supercapacitors with aqueous or PC electrolytes reported previously. Furthermore, at a high discharge current density of 30 A g(-1), the energy and power densities of the supercapacitor were measured to be 15.4 Wh kg(-1) and 16,300 W kg(-1), respectively. These results indicate that the supercapacitor has a high specific capacitance and power density, and excellent rate capability.

  13. 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.

  14. An efficient approach to BAC based assembly of complex genomes.

    Science.gov (United States)

    Visendi, Paul; Berkman, Paul J; Hayashi, Satomi; Golicz, Agnieszka A; Bayer, Philipp E; Ruperao, Pradeep; Hurgobin, Bhavna; Montenegro, Juan; Chan, Chon-Kit Kenneth; Staňková, Helena; Batley, Jacqueline; Šimková, Hana; Doležel, Jaroslav; Edwards, David

    2016-01-01

    There has been an exponential growth in the number of genome sequencing projects since the introduction of next generation DNA sequencing technologies. Genome projects have increasingly involved assembly of whole genome data which produces inferior assemblies compared to traditional Sanger sequencing of genomic fragments cloned into bacterial artificial chromosomes (BACs). While whole genome shotgun sequencing using next generation sequencing (NGS) is relatively fast and inexpensive, this method is extremely challenging for highly complex genomes, where polyploidy or high repeat content confounds accurate assembly, or where a highly accurate 'gold' reference is required. Several attempts have been made to improve genome sequencing approaches by incorporating NGS methods, to variable success. We present the application of a novel BAC sequencing approach which combines indexed pools of BACs, Illumina paired read sequencing, a sequence assembler specifically designed for complex BAC assembly, and a custom bioinformatics pipeline. We demonstrate this method by sequencing and assembling BAC cloned fragments from bread wheat and sugarcane genomes. We demonstrate that our assembly approach is accurate, robust, cost effective and scalable, with applications for complete genome sequencing in large and complex genomes.

  15. Metallo-supramolecular block copolymer micelles

    NARCIS (Netherlands)

    Gohy, J.M.W.

    2009-01-01

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

  16. 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...

  17. Improvement of the Threespine Stickleback Genome Using a Hi-C-Based Proximity-Guided Assembly.

    Science.gov (United States)

    Peichel, Catherine L; Sullivan, Shawn T; Liachko, Ivan; White, Michael A

    2017-09-01

    Scaffolding genomes into complete chromosome assemblies remains challenging even with the rapidly increasing sequence coverage generated by current next-generation sequence technologies. Even with scaffolding information, many genome assemblies remain incomplete. The genome of the threespine stickleback (Gasterosteus aculeatus), a fish model system in evolutionary genetics and genomics, is not completely assembled despite scaffolding with high-density linkage maps. Here, we first test the ability of a Hi-C based proximity-guided assembly (PGA) to perform a de novo genome assembly from relatively short contigs. Using Hi-C based PGA, we generated complete chromosome assemblies from a distribution of short contigs (20-100 kb). We found that 96.40% of contigs were correctly assigned to linkage groups (LGs), with ordering nearly identical to the previous genome assembly. Using available bacterial artificial chromosome (BAC) end sequences, we provide evidence that some of the few discrepancies between the Hi-C assembly and the existing assembly are due to structural variation between the populations used for the 2 assemblies or errors in the existing assembly. This Hi-C assembly also allowed us to improve the existing assembly, assigning over 60% (13.35 Mb) of the previously unassigned (~21.7 Mb) contigs to LGs. Together, our results highlight the potential of the Hi-C based PGA method to be used in combination with short read data to perform relatively inexpensive de novo genome assemblies. This approach will be particularly useful in organisms in which it is difficult to perform linkage mapping or to obtain high molecular weight DNA required for other scaffolding methods. © The American Genetic Association 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  18. Development of gold based solder candidates for flip chip assembly

    DEFF Research Database (Denmark)

    Chidambaram, Vivek; Hald, John; Hattel, Jesper Henri

    2009-01-01

    Flip chip technology is now rapidly replacing the traditional wire bonding interconnection technology in the first level packaging applications due to the miniaturization drive in the microelectronics industry. Flip chip assembly currently involves the use of high lead containing solders...

  19. Multifunctional, supramolecular, continuous artificial nacre fibres

    Science.gov (United States)

    Hu, Xiaozhen; Xu, Zhen; Gao, Chao

    2012-10-01

    Nature has created amazing materials during the process of evolution, inspiring scientists to studiously mimic them. Nacre is of particular interest, and it has been studied for more than half-century for its strong, stiff, and tough attributes resulting from the recognized ``brick-and-mortar'' (B&M) layered structure comprised of inorganic aragonite platelets and biomacromolecules. The past two decades have witnessed great advances in nacre-mimetic composites, but they are solely limited in films with finite size (centimetre-scale). To realize the adream target of continuous nacre-mimics with perfect structures is still a great challenge unresolved. Here, we present a simple and scalable strategy to produce bio-mimic continuous fibres with B&M structures of alternating graphene sheets and hyperbranched polyglycerol (HPG) binders via wet-spinning assembly technology. The resulting macroscopic supramolecular fibres exhibit excellent mechanical properties comparable or even superior to nacre and bone, and possess fine electrical conductivity and outstanding corrosion-resistance.

  20. 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

  1. Self-assembled containers based on extended tetrathiafulvalene.

    Science.gov (United States)

    Bivaud, Sébastien; Goeb, Sébastien; Croué, Vincent; Dron, Paul I; Allain, Magali; Sallé, Marc

    2013-07-10

    Two original self-assembled containers constituted each by six electroactive subunits are described. They are synthesized from a concave tetratopic π-extended tetrathiafulvalene ligand bearing four pyridyl units and cis-M(dppf)(OTf)2 (M = Pd or Pt; dppf = 1,1'-bis(diphenylphosphino)ferrocene; OTf = trifluoromethane-sulfonate) complexes. Both fully characterized assemblies present an oblate spheroidal cavity that can incorporate one perylene molecule.

  2. Pulsed neutron source based on accelerator-subcritical-assembly

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, Makoto; Noda, Akira; Iwashita, Yoshihisa; Okamoto, Hiromi; Shirai, Toshiyuki [Kyoto Univ., Uji (Japan). Inst. for Chemical Research

    1997-03-01

    A new pulsed neutron source which consists of a 300MeV proton linac and a nuclear fuel subcritical assembly is proposed. The proton linac produces pulsed spallation neutrons, which are multipied by the subcritical assembly. A prototype proton linac that accelerates protons up to 7MeV has been developed and a high energy section of a DAW structure is studied with a power model. Halo formations in high intensity beam are also being studied. (author)

  3. Two-channel dansyl/tryptophan emitters with a cholic acid bridge as reporters for local hydrophobicity within supramolecular systems based on bile salts.

    Science.gov (United States)

    Gomez-Mendoza, M; Marin, M Luisa; Miranda, Miguel A

    2014-11-14

    The aim of the present work is to develop two-channel emitters to probe local hydrophobicity by means of fluorescence quenching within different biomimetic supramolecular environments. To achieve this goal, the dansyl (Dns) and tryptophan (Trp) fluorophores have been covalently attached to cholic acid (CA) in order to ensure simultaneous incorporation of the two emitting units into the same compartment. In principle, the two fluorophores of the synthesized Dns-CA-Trp probes could either exhibit an orthogonal behavior or display excited state interactions. The fluorescence spectra of 3β-Dns-CA-Trp showed a residual Trp emission band at ca. 350 nm and an enhanced Dns maximum in the 500-550 nm region. This reveals a partial intramolecular energy transfer, which is consistent with the Dns and Trp singlet energies. Thus, the two photoactive units are not orthogonal; nevertheless, 3β-Dns-CA-Trp seems appropriate as a two-channel reporter for the supramolecular systems of interest. Fluorescence quenching of 3β-Dns-CA-Trp by iodide (which remains essentially in bulk water) was examined within sodium cholate, sodium taurocholate, sodium deoxycholate and mixed micelles. Interestingly, a decrease in the emission intensity of the two bands was observed with increasing iodide concentrations. The most remarkable effect was observed for mixed micelles, where the quenching rate constants were one order of magnitude lower than in solution. As anticipated, the quenching efficiency by iodide decreased with increasing hydrophobicity of the microenvironment, a trend that can be correlated with the relative accessibility of the probe to the ionic quencher.

  4. Complexing DNA Origami Frameworks through Sequential Self-Assembly Based on Directed Docking.

    Science.gov (United States)

    Suzuki, Yuki; Sugiyama, Hiroshi; Endo, Masayuki

    2018-06-11

    Ordered DNA origami arrays have the potential to compartmentalize space into distinct periodic domains that can incorporate a variety of nanoscale objects. Herein, we used the cavities of a preassembled 2D DNA origami framework to incorporate square-shaped DNA origami structures (SQ-origamis). The framework was self-assembled on a lipid bilayer membrane from cross-shaped DNA origami structures (CR-origamis) and subsequently exposed to the SQ-origamis. High-speed AFM revealed the dynamic adsorption/desorption behavior of the SQ-origamis, which resulted in continuous changing of their arrangements in the framework. These dynamic SQ-origamis were trapped in the cavities by increasing the Mg 2+ concentration or by introducing sticky-ended cohesions between extended staples, both from the SQ- and CR-origamis, which enabled the directed docking of the SQ-origamis. Our study offers a platform to create supramolecular structures or systems consisting of multiple DNA origami components. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. A Novel Assembly Line Scheduling Algorithm Based on CE-PSO

    Directory of Open Access Journals (Sweden)

    Xiaomei Hu

    2015-01-01

    Full Text Available With the widespread application of assembly line in enterprises, assembly line scheduling is an important problem in the production since it directly affects the productivity of the whole manufacturing system. The mathematical model of assembly line scheduling problem is put forward and key data are confirmed. A double objective optimization model based on equipment utilization and delivery time loss is built, and optimization solution strategy is described. Based on the idea of solution strategy, assembly line scheduling algorithm based on CE-PSO is proposed to overcome the shortcomings of the standard PSO. Through the simulation experiments of two examples, the validity of the assembly line scheduling algorithm based on CE-PSO is proved.

  11. Bioinspired Supramolecular Enzymatic Systems

    Science.gov (United States)

    2012-09-28

    in this bistable [2]rotaxane upon exposure to light or molecular oxygen , respectively. 2.11 Solution-Phase Mechanistic Study and Solid-State...Am. Chem. Soc. 2008, 130, 804-805. 6. Dieringer, J. A.; Lettan, R. B., II; Scheidt, K. A.; Van Duyne, R. P. “ Isotope Labeled Single Molecule...Lytton- Jean , A. K. R.; Hurst, S.; Mirkin, C. A. “Silver Nanoparticle Oligonucleotide Conjugates Based on Triple Cyclic Disulfide Moieties,” Nano

  12. 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....

  13. Fuzzy-Based Adaptive Hybrid Burst Assembly Technique for Optical Burst Switched Networks

    Directory of Open Access Journals (Sweden)

    Abubakar Muhammad Umaru

    2014-01-01

    Full Text Available The optical burst switching (OBS paradigm is perceived as an intermediate switching technology for future all-optical networks. Burst assembly that is the first process in OBS is the focus of this paper. In this paper, an intelligent hybrid burst assembly algorithm that is based on fuzzy logic is proposed. The new algorithm is evaluated against the traditional hybrid burst assembly algorithm and the fuzzy adaptive threshold (FAT burst assembly algorithm via simulation. Simulation results show that the proposed algorithm outperforms the hybrid and the FAT algorithms in terms of burst end-to-end delay, packet end-to-end delay, and packet loss ratio.

  14. 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.

  15. 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

  16. Supramolecular interactions of oxidative stress biomarker glutathione with fluorone black.

    Science.gov (United States)

    Hepel, Maria; Stobiecka, Magdalena

    2018-03-05

    which is likely based on an intermediate formation of a similar type of supramolecular ensembles. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Multifunctional hybrid networks based on self assembling peptide sequences

    Science.gov (United States)

    Sathaye, Sameer

    The overall aim of this dissertation is to achieve a comprehensive correlation between the molecular level changes in primary amino acid sequences of amphiphilic beta-hairpin peptides and their consequent solution-assembly properties and bulk network hydrogel behavior. This has been accomplished using two broad approaches. In the first approach, amino acid substitutions were made to peptide sequence MAX1 such that the hydrophobic surfaces of the folded beta-hairpins from the peptides demonstrate shape specificity in hydrophobic interactions with other beta-hairpins during the assembly process, thereby causing changes to the peptide nanostructure and bulk rheological properties of hydrogels formed from the peptides. Steric lock and key complementary hydrophobic interactions were designed to occur between two beta-hairpin molecules of a single molecule, LNK1 during beta-sheet fibrillar assembly of LNK1. Experimental results from circular dichroism, transmission electron microscopy and oscillatory rheology collectively indicate that the molecular design of the LNK1 peptide can be assigned the cause of the drastically different behavior of the networks relative to MAX1. The results indicate elimination or significant reduction of fibrillar branching due to steric complementarity in LNK1 that does not exist in MAX1, thus supporting the original hypothesis. As an extension of the designed steric lock and key complementarity between two beta-hairpin molecules of the same peptide molecule. LNK1, three new pairs of peptide molecules LP1-KP1, LP2-KP2 and LP3-KP3 that resemble complementary 'wedge' and 'trough' shapes when folded into beta-hairpins were designed and studied. All six peptides individually and when blended with their corresponding shape complement formed fibrillar nanostructures with non-uniform thickness values. Loose packing in the assembled structures was observed in all the new peptides as compared to the uniform tight packing in MAX1 by SANS analysis. This

  18. Optimal Search Strategy of Robotic Assembly Based on Neural Vibration Learning

    Directory of Open Access Journals (Sweden)

    Lejla Banjanovic-Mehmedovic

    2011-01-01

    Full Text Available This paper presents implementation of optimal search strategy (OSS in verification of assembly process based on neural vibration learning. The application problem is the complex robot assembly of miniature parts in the example of mating the gears of one multistage planetary speed reducer. Assembly of tube over the planetary gears was noticed as the most difficult problem of overall assembly. The favourable influence of vibration and rotation movement on compensation of tolerance was also observed. With the proposed neural-network-based learning algorithm, it is possible to find extended scope of vibration state parameter. Using optimal search strategy based on minimal distance path between vibration parameter stage sets (amplitude and frequencies of robots gripe vibration and recovery parameter algorithm, we can improve the robot assembly behaviour, that is, allow the fastest possible way of mating. We have verified by using simulation programs that search strategy is suitable for the situation of unexpected events due to uncertainties.

  19. DNAzyme-Based Logic Gate-Mediated DNA Self-Assembly.

    Science.gov (United States)

    Zhang, Cheng; Yang, Jing; Jiang, Shuoxing; Liu, Yan; Yan, Hao

    2016-01-13

    Controlling DNA self-assembly processes using rationally designed logic gates is a major goal of DNA-based nanotechnology and programming. Such controls could facilitate the hierarchical engineering of complex nanopatterns responding to various molecular triggers or inputs. Here, we demonstrate the use of a series of DNAzyme-based logic gates to control DNA tile self-assembly onto a prescribed DNA origami frame. Logic systems such as "YES," "OR," "AND," and "logic switch" are implemented based on DNAzyme-mediated tile recognition with the DNA origami frame. DNAzyme is designed to play two roles: (1) as an intermediate messenger to motivate downstream reactions and (2) as a final trigger to report fluorescent signals, enabling information relay between the DNA origami-framed tile assembly and fluorescent signaling. The results of this study demonstrate the plausibility of DNAzyme-mediated hierarchical self-assembly and provide new tools for generating dynamic and responsive self-assembly systems.

  20. Stereoselective assembly of amino acid-based metal-biomolecule nanofibers.

    Science.gov (United States)

    Wu, Hong; Tian, Chunyong; Zhang, Yufei; Yang, Chen; Zhang, Songping; Jiang, Zhongyi

    2015-04-14

    A series of amino acid-based metal-biomolecule nanofibers are fabricated through a coordination-directed assembly process. The chirality and carbon chain length of the amino acids exert a pronounced influence on the assembly process. This study may be extended to design diverse kinds of 1-D metal-biomolecule frameworks (MBioFs).

  1. A Neural Assembly-Based View on Word Production: The Bilingual Test Case

    Science.gov (United States)

    Strijkers, Kristof

    2016-01-01

    I will propose a tentative framework of how words in two languages could be organized in the cerebral cortex based on neural assembly theory, according to which neurons that fire synchronously are bound into large-scale distributed functional units (assemblies), which represent a mental event as a whole ("gestalt"). For language this…

  2. Compliance of the Stokes-Einstein model and breakdown of the Stokes-Einstein-Debye model for a urea-based supramolecular polymer of high viscosity.

    Science.gov (United States)

    Świergiel, Jolanta; Bouteiller, Laurent; Jadżyn, Jan

    2014-11-14

    Impedance spectroscopy was used for the study of the static and dynamic behavior of the electrical conductivity of a hydrogen-bonded supramolecular polymer of high viscosity. The experimental data are discussed in the frame of the Stokes-Einstein and Stokes-Einstein-Debye models. It was found that the translational movement of the ions is due to normal Brownian diffusion, which was revealed by a fulfillment of Ohm's law by the electric current and a strictly exponential decay of the current after removing the electric stimulus. The dependence of the dc conductivity on the viscosity of the medium fulfills the Stokes-Einstein model quite well. An extension of the model, by including in it the conductivity relaxation time, is proposed in this paper. A breakdown of the Stokes-Einstein-Debye model is revealed by the relations of the dipolar relaxation time to the viscosity and to the dc ionic conductivity. The importance of the C=O···H-N hydrogen bonds in that breakdown is discussed.

  3. 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.

  4. 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

  5. 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

  6. Supramolecular nano-engineered lipidic carriers based on diflunisal-phospholipid complex for transdermal delivery: QbD based optimization, characterization and preclinical investigations for management of rheumatoid arthritis.

    Science.gov (United States)

    Kaur, Amanpreet; Bhoop, Bhupinder Singh; Chhibber, Sanjay; Sharma, Gajanand; Gondil, Vijay Singh; Katare, Om Prakash

    2017-11-25

    Diflunisal (DIF) is used for treatment of rheumatoid arthritis, osteoarthritis etc. DIF-phospholipid complex (DIF-PL complex) was prepared by solvent-evaporation method and characterized by molecular docking studies, SEM, FTIR, DSC, PXRD studies. Further, the DIF-PL complex was incorporated into supramolecular nano-engineered lipidic carriers (SNLCs) for transdermal delivery. The optimization exercise was done using Face centered cubic design (FCCD) after screening of variables by L8 Taguchi orthogonal array design. The optimized SNLC formulation depicted average particle size (188.1nm), degree of entrapment (86.77±3.33%), permeation flux (5.47±0.48μg/cm 2 /h) and skin retention (17.72±0.68μg/cm 2 ). The dermatokinetic studies revealed the higher concentration of DIF in dermis. The Confocal laser scanning microscopy (CSLM) studies revealed penetration of SNLCs into the deeper layers of skin. The results of mice ear edema depicted significant inhibition of ear edema (76.37±12.52%; prheumatoid arthritis model, the inhibition of paw edema was significantly higher (73.85±14.5%). The levels of TNF-α were reduced in synovial fluid (146.74±1.69pg/mL) and serum (132.43±2.70pg/mL). Furthermore, the licking and biting time was reduced in formalin induced hyperalgesia model. Hence, it can be concluded that dual formulation strategy based SNLCs were promising in treatment of pain and inflammation associated with rheumatoid arthritis. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Chitosan Based Self-Assembled Nanoparticles in Drug Delivery

    Directory of Open Access Journals (Sweden)

    Javier Pérez Quiñones

    2018-02-01

    Full Text Available Chitosan is a cationic polysaccharide that is usually obtained by alkaline deacetylation of chitin poly(N-acetylglucosamine. It is biocompatible, biodegradable, mucoadhesive, and non-toxic. These excellent biological properties make chitosan a good candidate for a platform in developing drug delivery systems having improved biodistribution, increased specificity and sensitivity, and reduced pharmacological toxicity. In particular, chitosan nanoparticles are found to be appropriate for non-invasive routes of drug administration: oral, nasal, pulmonary and ocular routes. These applications are facilitated by the absorption-enhancing effect of chitosan. Many procedures for obtaining chitosan nanoparticles have been proposed. Particularly, the introduction of hydrophobic moieties into chitosan molecules by grafting to generate a hydrophobic-hydrophilic balance promoting self-assembly is a current and appealing approach. The grafting agent can be a hydrophobic moiety forming micelles that can entrap lipophilic drugs or it can be the drug itself. Another suitable way to generate self-assembled chitosan nanoparticles is through the formation of polyelectrolyte complexes with polyanions. This paper reviews the main approaches for preparing chitosan nanoparticles by self-assembly through both procedures, and illustrates the state of the art of their application in drug delivery.

  8. 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.

  9. 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

  10. 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)

  11. 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.

  12. Improving Phrap-based assembly of the rat using "reliable" overlaps.

    Directory of Open Access Journals (Sweden)

    Michael Roberts

    2008-03-01

    Full Text Available The assembly methods used for whole-genome shotgun (WGS data have a major impact on the quality of resulting draft genomes. We present a novel algorithm to generate a set of "reliable" overlaps based on identifying repeat k-mers. To demonstrate the benefits of using reliable overlaps, we have created a version of the Phrap assembly program that uses only overlaps from a specific list. We call this version PhrapUMD. Integrating PhrapUMD and our "reliable-overlap" algorithm with the Baylor College of Medicine assembler, Atlas, we assemble the BACs from the Rattus norvegicus genome project. Starting with the same data as the Nov. 2002 Atlas assembly, we compare our results and the Atlas assembly to the 4.3 Mb of rat sequence in the 21 BACs that have been finished. Our version of the draft assembly of the 21 BACs increases the coverage of finished sequence from 93.4% to 96.3%, while simultaneously reducing the base error rate from 4.5 to 1.1 errors per 10,000 bases. There are a number of ways of assessing the relative merits of assemblies when the finished sequence is available. If one views the overall quality of an assembly as proportional to the inverse of the product of the error rate and sequence missed, then the assembly presented here is seven times better. The UMD Overlapper with options for reliable overlaps is available from the authors at http://www.genome.umd.edu. We also provide the changes to the Phrap source code enabling it to use only the reliable overlaps.

  13. Activation of ice recrystallization inhibition activity of poly(vinyl alcohol) using a supramolecular trigger

    OpenAIRE

    Phillips, Daniel J.; Congdon, Thomas; Gibson, Matthew I.

    2016-01-01

    Antifreeze (glyco)proteins (AF(G)Ps) have potent ice recrystallisation inhibition (IRI) activity – a desirable phenomenon in applications such as cryopreservation, frozen food and more. In Nature AF(G)P activity is regulated by protein expression levels in response to an environmental stimulus; temperature. However, this level of regulation is not possible in synthetic systems. Here, a synthetic macromolecular mimic is introduced, using supramolecular assembly to regulate activity. Catechol-t...

  14. Activation of Ice Recrystallization Inhibition Activity of Poly(vinyl alcohol) using a Supramolecular Trigger†

    OpenAIRE

    Phillips, Daniel J.; Congdon, Thomas R.; Gibson, Matthew I.

    2016-01-01

    Antifreeze (glyco)proteins (AF(G)Ps) have potent ice recrystallisation inhibition (IRI) activity – a desirable phenomenon in applications such as cryopreservation, frozen food and more. In Nature AF(G)P activity is regulated by protein expression levels in response to an environmental stimulus; temperature. However, this level of regulation is not possible in synthetic systems. Here, a synthetic macromolecular mimic is introduced, using supramolecular assembly to regulate ac...

  15. Vortex-Induced Alignment of a Water Soluble Supramolecular Nanofiber Composed of an Amphiphilic Dendrimer

    Directory of Open Access Journals (Sweden)

    Akihiko Tsuda

    2013-06-01

    Full Text Available We have synthesized a novel amphiphilic naphthalene imide bearing a cationic dendrimer wedge (NID. NID molecules in water self-assemble to form a two-dimensional ribbon, which further coils to give a linear supramolecular nanofiber. The sample solution showed linear dichroism (LD upon stirring of the solution, where NID nanofibers dominantly align at the center of vortex by hydrodynamic interaction with the downward torsional flows.

  16. CH3NH3PbI3 and CsPbI3 Supramolecular Clusters in 1D: Do They Evolve with the Same Principle of Cooperative Binding?

    Science.gov (United States)

    Varadwaj, Arpita; Varadwaj, Pradeep R.; Yamashita, Koichi

    Development of novel semiconductor-based photo-catalytic and -voltaic systems is a major area of research in nanoscience and technologies, and engineering. The process can be either direct or indirect in converting the light energy into electricity. Some of the photovoltaics include the organic, dye-sensitized, and halide perovskite solar cells, among others. Methylammonium lead iodide (CH3NH3PbI3) inorganic-organic hybrid perovskite is one among the many highly valued semiconductors reported till date, comparable with the inorganic cesium lead iodide (CsPbI3) perovskite. These are competitive candidates in the solar energy race. Nevertheless, this study was concentrated on the fundamental understanding of the rational designs of the CH3NH3PbI3 and CsPbI3 supramolecular materials using first-principles calculations, emerged though the self-assembly of the respective building blocks. It therefore addresses the question whether the (CH3NH3PbI3)n and (CsPbI3)n (n =1-10) supramolecular clusters are the consequences of additivity, or non-additive cooperative binding? For addressing this question, the supramolecular properties such as the polarizability, the intermolecular charge transfer, and the binding energy, etc., all w.r.t the cluster size n, are exploited. CREST-JST, 7 Gobancho, Chiyoda-ku, Tokyo, Japan 102-0076.

  17. 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)

  18. 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.

  19. Probe based manipulation and assembly of nanowires into organized mesostructures

    Science.gov (United States)

    Reynolds, K.; Komulainen, J.; Kivijakola, J.; Lovera, P.; Iacopino, D.; Pudas, M.; Vähäkangas, J.; Röning, J.; Redmond, G.

    2008-12-01

    A convenient approach to patterning inorganic and organic nanowires using a novel probe manipulator is presented. The system utilizes an electrochemically etched tungsten wire probe mounted onto a 3D actuator that is directed by a 3D controller. When it is engaged by the user, the movement of the probe and the forces experienced by the tip are simultaneously reported in real time. Platinum nanowires are manipulated into organized mesostructures on silicon chip substrates. In particular, individual nanowires are systematically removed from aggregates, transferred to a chosen location, and manipulated into complex structures in which selected wires occupy specific positions with defined orientations. Rapid prototyping of complex mesostructures, by pushing, rotating and bending conjugated polymer, i.e., polyfluorene, nanowires into various configurations, is also achieved. By exploiting the strong internal axial alignment of polymer chains within the polyfluorene nanowires, mesostructures tailored to exhibit distinctly anisotropic optical properties, such as birefringence and photoluminescence dichroism, are successfully assembled on fused silica substrates.

  20. Probe based manipulation and assembly of nanowires into organized mesostructures

    International Nuclear Information System (INIS)

    Reynolds, K; Lovera, P; Iacopino, D; Redmond, G; Komulainen, J; Pudas, M; Vaehaekangas, J; Kivijakola, J; Roening, J

    2008-01-01

    A convenient approach to patterning inorganic and organic nanowires using a novel probe manipulator is presented. The system utilizes an electrochemically etched tungsten wire probe mounted onto a 3D actuator that is directed by a 3D controller. When it is engaged by the user, the movement of the probe and the forces experienced by the tip are simultaneously reported in real time. Platinum nanowires are manipulated into organized mesostructures on silicon chip substrates. In particular, individual nanowires are systematically removed from aggregates, transferred to a chosen location, and manipulated into complex structures in which selected wires occupy specific positions with defined orientations. Rapid prototyping of complex mesostructures, by pushing, rotating and bending conjugated polymer, i.e., polyfluorene, nanowires into various configurations, is also achieved. By exploiting the strong internal axial alignment of polymer chains within the polyfluorene nanowires, mesostructures tailored to exhibit distinctly anisotropic optical properties, such as birefringence and photoluminescence dichroism, are successfully assembled on fused silica substrates.

  1. DNA origami-based nanoribbons: assembly, length distribution, and twist

    Energy Technology Data Exchange (ETDEWEB)

    Jungmann, Ralf; Scheible, Max; Kuzyk, Anton; Pardatscher, Guenther; Simmel, Friedrich C [Lehrstuhl fuer Bioelektronik, Physik-Department and ZNN/WSI, Technische Universitaet Muenchen, Am Coulombwall 4a, 85748 Garching (Germany); Castro, Carlos E, E-mail: simmel@ph.tum.de [Labor fuer Biomolekulare Nanotechnologie, Physik-Department and ZNN/WSI, Technische Universitaet Muenchen, Am Coulombwall 4a, 85748 Garching (Germany)

    2011-07-08

    A variety of polymerization methods for the assembly of elongated nanoribbons from rectangular DNA origami structures are investigated. The most efficient method utilizes single-stranded DNA oligonucleotides to bridge an intermolecular scaffold seam between origami monomers. This approach allows the fabrication of origami ribbons with lengths of several micrometers, which can be used for long-range ordered arrangement of proteins. It is quantitatively shown that the length distribution of origami ribbons obtained with this technique follows the theoretical prediction for a simple linear polymerization reaction. The design of flat single layer origami structures with constant crossover spacing inevitably results in local underwinding of the DNA helix, which leads to a global twist of the origami structures that also translates to the nanoribbons.

  2. DNA origami-based nanoribbons: assembly, length distribution, and twist

    International Nuclear Information System (INIS)

    Jungmann, Ralf; Scheible, Max; Kuzyk, Anton; Pardatscher, Guenther; Simmel, Friedrich C; Castro, Carlos E

    2011-01-01

    A variety of polymerization methods for the assembly of elongated nanoribbons from rectangular DNA origami structures are investigated. The most efficient method utilizes single-stranded DNA oligonucleotides to bridge an intermolecular scaffold seam between origami monomers. This approach allows the fabrication of origami ribbons with lengths of several micrometers, which can be used for long-range ordered arrangement of proteins. It is quantitatively shown that the length distribution of origami ribbons obtained with this technique follows the theoretical prediction for a simple linear polymerization reaction. The design of flat single layer origami structures with constant crossover spacing inevitably results in local underwinding of the DNA helix, which leads to a global twist of the origami structures that also translates to the nanoribbons.

  3. Study on Parameter Identification of Assembly Robot based on Screw Theory

    Science.gov (United States)

    Yun, Shi; Xiaodong, Zhang

    2017-11-01

    The kinematic model of assembly robot is one of the most important factors affecting repetitive precision. In order to improve the accuracy of model positioning, this paper first establishes the exponential product model of ER16-1600 assembly robot on the basis of screw theory, and then based on iterative least squares method, using ER16-1600 model robot parameter identification. By comparing the experiment before and after the calibration, it is proved that the method has obvious improvement on the positioning accuracy of the assembly robot.

  4. Robust Mesoporous CoMo/γ-Al2O3 Catalysts from Cyclodextrin-Based Supramolecular Assemblies for Hydrothermal Processing of Microalgae: Effect of the Preparation Method.

    Science.gov (United States)

    Bleta, Rudina; Schiavo, Benedetto; Corsaro, Natale; Costa, Paula; Giaconia, Alberto; Interrante, Leonardo; Monflier, Eric; Pipitone, Giuseppe; Ponchel, Anne; Sau, Salvatore; Scialdone, Onofrio; Tilloy, Sébastien; Galia, Alessandro

    2018-04-18

    Hydrothermal liquefaction (HTL) is a promising technology for the production of biocrude oil from microalgae. Although this catalyst-free technology is efficient under high-temperature and high-pressure conditions, the biocrude yield and quality can be further improved by using heterogeneous catalysts. The design of robust catalysts that preserve their performance under hydrothermal conditions will be therefore very important in the development of biorefinery technologies. In this work, we describe two different synthetic routes (i.e., impregnation and cyclodextrin-assisted one-pot colloidal approach), for the preparation in aqueous phase of six high surface area CoMo/γ-Al 2 O 3 catalysts. Catalytic tests performed on the HTL of Nannochloropsis gaditana microalga indicate that solids prepared by the one-pot colloidal approach show higher hydrothermal stability and enhanced biocrude yield with respect to the catalyst-free test. The positive effect of the substitution of the block copolymer Tetronic T90R4 for Pluronic F127 in the preparation procedure was evidenced by diffuse reflectance UV-visible spectroscopy, X-ray diffraction, N 2 -adsorption-desorption, and H 2 -temperature-programmed reduction measurements and confirmed by the higher quality of the obtained biocrude, which exhibited lower oxygen content and higher-energy recovery equal to 62.5% of the initial biomass.

  5. "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

  6. Polo-like kinase phosphorylation determines Caenorhabditis elegans centrosome size and density by biasing SPD-5 toward an assembly-competent conformation

    Directory of Open Access Journals (Sweden)

    Oliver Wueseke

    2016-10-01

    Full Text Available Centrosomes are major microtubule-organizing centers composed of centrioles surrounded by an extensive proteinacious layer called the pericentriolar material (PCM. In Caenorhabditis elegans embryos, the mitotic PCM expands by Polo-like kinase 1 (PLK-1 phosphorylation-accelerated assembly of SPD-5 molecules into supramolecular scaffolds. However, how PLK-1 phosphorylation regulates SPD-5 assembly is not known. We found that a mutant version of SPD-5 that is insensitive to PLK-1 phosphorylation (SPD-54A could localize to PCM but was unable to rescue the reduction in PCM size and density when wild-type SPD-5 levels were decreased. In vitro, purified SPD-54A self-assembled into functional supramolecular scaffolds over long time scales, suggesting that phosphorylation only controls the rate of SPD-5 scaffold assembly. Furthermore, the SPD-5 scaffold, once assembled, remained intact and supported microtubule nucleation in the absence of PLK-1 activity in vivo. We conclude that PLK-1 is required for rapid assembly of the PCM scaffold but not for scaffold maintenance or function. Based on this idea, we developed a theoretical model that adequately predicted PCM growth rates in different mutant conditions in vivo. We propose that PLK-1 phosphorylation-dependent conversion of SPD-5 into an assembly-competent form underlies PCM formation in vivo and that the rate of this conversion determines final PCM size and density.

  7. Supramolecular Gold Metallogelators: The Key Role of Metallophilic Interactions

    Directory of Open Access Journals (Sweden)

    João Carlos Lima

    2014-12-01

    Full Text Available Gold metallogelators is an emerging area of research. The number of results published in the literature is still scarce. The majority of these gels is observed in organic solvents, and the potential applications are still to be explored. In this work, we present an overview about gold metallogelators divided in two different groups depending on the type of solvent used in the gelation process (organogelators and hydrogelators. A careful analysis of the data shows that aurophilic interactions are a common motif directly involved in gelation involving Au(I complexes. There are also some Au(III derivatives able to produce gels but in this case the organic ligands determine the aggregation process. A last section is included about the potential applications that have been reported until now with this new and amazing class of supramolecular assemblies.

  8. Judgement on the data for fuel assembly outlet temperatures of WWER fuel assemblies in power reactors based on measurements with experimental fuel assemblies

    International Nuclear Information System (INIS)

    Krause, F.

    1986-01-01

    In the period from 1980 to 1985, in the Rheinsberg nuclear power plant experimental fuel assemblies were used on lattices at the periphery of the core. These particular fuel assemblies dispose of an extensive in-core instrumentation with different sensors. Besides this, they are fit out with a device to systematically thottle the coolant flow. The large power gradient present at the core position of the experimental fuel assembly causes a temperature profile along the fuel assemblies which is well provable at the measuring points of the outlet temperature. Along the direction of flow this temperature profile in the coolant degrades only slowly. This effect is to be taken into account when measuring the fuel assembly outlet temperature of WWER fuel assemblies. Besides this, the results of the measurements hinted both at a γ-heating of the temperature measuring points and at tolerances in the calculation of the micro power density distribution. (author)

  9. 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.

  10. 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.

  11. 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.

  12. Steering Self-Assembly of Amphiphilic Molecular Nanostructures via Halogen Exchange

    NARCIS (Netherlands)

    Kriete, Björn; Bondarenko, Anna S.; Jumde, Varsha R.; Franken, Linda E.; Minnaard, Adriaan J.; Jansen, Thomas L. C.; Knoester, Jasper; Pshenichnikov, Maxim S.

    2017-01-01

    In the field of self-assembly, the quest for gaining control over the supramolecular architecture without affecting the functionality of the individual molecular building blocks is intrinsically challenging. By using a combination of synthetic chemistry, cryogenic transmission electron microscopy,

  13. Natural supramolecular building blocks: from virus coat proteins to viral nanoparticles.

    Science.gov (United States)

    Liu, Zhi; Qiao, Jing; Niu, Zhongwei; Wang, Qian

    2012-09-21

    Viruses belong to a fascinating class of natural supramolecular structures, composed of multiple copies of coat proteins (CPs) that assemble into different shapes with a variety of sizes from tens to hundreds of nanometres. Because of their advantages including simple/economic production, well-defined structural features, unique shapes and sizes, genetic programmability and robust chemistries, recently viruses and virus-like nanoparticles (VLPs) have been used widely in biomedical applications and materials synthesis. In this critical review, we highlight recent advances in the use of virus coat proteins (VCPs) and viral nanoparticles (VNPs) as building blocks in self-assembly studies and materials development. We first discuss the self-assembly of VCPs into VLPs, which can efficiently incorporate a variety of different materials as cores inside the viral protein shells. Then, the self-assembly of VNPs at surfaces or interfaces is summarized. Finally, we discuss the co-assembly of VNPs with different functional materials (178 references).

  14. Dual responsive supramolecular hydrogel with electrochemical activity.

    Science.gov (United States)

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

    2011-08-02

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

  15. 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.

  16. Amphiphilic building blocks for self-assembly: from amphiphiles to supra-amphiphiles.

    Science.gov (United States)

    Wang, Chao; Wang, Zhiqiang; Zhang, Xi

    2012-04-17

    The process of self-assembly spontaneously creates well-defined structures from various chemical building blocks. Self-assembly can include different levels of complexity: it can be as simple as the dimerization of two small building blocks driven by hydrogen bonding or as complicated as a cell membrane, a remarkable supramolecular architecture created by a bilayer of phospholipids embedded with functional proteins. The study of self-assembly in simple systems provides a fundamental understanding of the driving forces and cooperativity behind these processes. Once the rules are understood, these guidelines can facilitate the research of highly complex self-assembly processes. Among the various components for self-assembly, an amphiphilic molecule, which contains both hydrophilic and hydrophobic parts, forms one of the most powerful building blocks. When amphiphiles are dispersed in water, the hydrophilic component of the amphiphile preferentially interacts with the aqueous phase while the hydrophobic portion tends to reside in the air or in the nonpolar solvent. Therefore, the amphiphiles aggregate to form different molecular assemblies based on the repelling and coordinating forces between the hydrophilic and hydrophobic parts of the component molecules and the surrounding medium. In contrast to conventional amphiphiles, supra-amphiphiles are constructed on the basis of noncovalent interactions or dynamic covalent bonds. In supra-amphiphiles, the functional groups can be attached to the amphiphiles by noncovalent synthesis, greatly speeding their construction. The building blocks for supra-amphiphiles can be either small organic molecules or polymers. Advances in the development of supra-amphiphiles will not only enrich the family of conventional amphiphiles that are based on covalent bonds but will also provide a new kind of building block for the preparation of complex self-assemblies. When polymers are used to construct supra-amphiphiles, the resulting

  17. Supramolecular assemblies in [Cu(L-Arg){sub 2}(H{sub 2}O)]C{sub 2}O{sub 4}·6H{sub 2}O complex – Structural, spectroscopic, magnetic and thermal behavior

    Energy Technology Data Exchange (ETDEWEB)

    Wojciechowska, Agnieszka, E-mail: agnieszka.wojciechowska@pwr.edu.pl [Faculty of Chemistry, Wroclaw University of Technology, Wybrzeze Wyspiańskiego 27, 50-370, Wrocław (Poland); Kochel, Andrzej [Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383, Wrocław (Poland); Duczmal, Marek [Faculty of Chemistry, Wroclaw University of Technology, Wybrzeze Wyspiańskiego 27, 50-370, Wrocław (Poland)

    2016-10-01

    The reaction of L-arginine and oxalate ions with copper(II) salts yields a new complex with formula of [Cu(L-Arg){sub 2}(H{sub 2}O)]·C{sub 2}O{sub 4}·6H{sub 2}O (1) (where L-Arg = L-arginine). Single crystals of 1 were synthesized by crystallization from aqueous solution. The complex properties were characterized by X-ray diffraction, spectroscopy (FT-IR, FT-Raman, NIR-Vis-UV and EPR) as well as thermal and magnetic methods. The square pyramidal (SP) geometry around Cu(II) ions in [Cu(L-Arg){sub 2}(H{sub 2}O)]{sup 2+} cation complex is formed by two cis-chelated L-arginine zwitterions and a water molecule coordinated in the apex of square pyramid. The trigonality distortion of SP geometry is relatively small, τ = 0.0087. The solid state EPR spectrum showed broad hyperfine splitting with g{sub ⊥} = 2.061 at 77 K. The copper centres distanced at 7.558(5) Å are joined in a single zig-zag structure via a chain based on the combination of Cu−O(5)−H(29)⋯O(2)−C1−O1−Cu hydrogen bonds along the b axis (d (O2⋯O5) = 2.812 Å). Taking into account the structural features, the magnetic susceptibility data were best-fitted, giving the exchange parameter J = −0.16 cm{sup −1}. Complex 1 is thermally stable up to 66 °C, where it was observed to lose the crystallization water molecules with an 11.7% mass loss (calc. 11.5%). - Highlights: • Crystal and molecular structure of [Cu(L-Arg){sub 2}(H{sub 2}O)]C{sub 2}O{sub 4}·6H{sub 2}O crystals have been studied. • The magnetic interactions of Cu(II) centres are assisted by the formation of single zig-zag chain. • Role of oxalate ions in completed relatively small square pyramid distortion is described. • The cis-fashioned L-arginine created the stronger ligand field than trans-configuration.

  18. A simulation-based approach for solving assembly line balancing problem

    Science.gov (United States)

    Wu, Xiaoyu

    2017-09-01

    Assembly line balancing problem is directly related to the production efficiency, since the last century, the problem of assembly line balancing was discussed and still a lot of people are studying on this topic. In this paper, the problem of assembly line is studied by establishing the mathematical model and simulation. Firstly, the model of determing the smallest production beat under certain work station number is anysized. Based on this model, the exponential smoothing approach is applied to improve the the algorithm efficiency. After the above basic work, the gas stirling engine assembly line balancing problem is discussed as a case study. Both two algorithms are implemented using the Lingo programming environment and the simulation results demonstrate the validity of the new methods.

  19. Three-Dimensional Assembly Tolerance Analysis Based on the Jacobian-Torsor Statistical Model

    Directory of Open Access Journals (Sweden)

    Peng Heping

    2017-01-01

    Full Text Available The unified Jacobian-Torsor model has been developed for deterministic (worst case tolerance analysis. This paper presents a comprehensive model for performing statistical tolerance analysis by integrating the unified Jacobian-Torsor model and Monte Carlo simulation. In this model, an assembly is sub-divided into surfaces, the Small Displacements Torsor (SDT parameters are used to express the relative position between any two surfaces of the assembly. Then, 3D dimension-chain can be created by using a surface graph of the assembly and the unified Jacobian-Torsor model is developed based on the effect of each functional element on the whole functional requirements of products. Finally, Monte Carlo simulation is implemented for the statistical tolerance analysis. A numerical example is given to demonstrate the capability of the proposed method in handling three-dimensional assembly tolerance analysis.

  20. Light induced assembly and self-sorting of silica microparticles

    NARCIS (Netherlands)

    Vilanova Garcia, N.; De Feijter, I.; Teunissen, A.J.P.; Voets, I.K.

    2018-01-01

    To tailor the properties of colloidal materials, precise control over the self-assembly of their constituents is a prerequisite. Here, we govern the assembly of silica particles by functionalization with supramolecular moieties which interact with each other via directional and reversible hydrogen

  1. Self-assembly of perylenediimide based semiconductor on polymer substrate

    Energy Technology Data Exchange (ETDEWEB)

    Wiatrowski, Michal, E-mail: Michal.Wiatrowski@p.lodz.p [Department of Molecular Physics, Technical University of Lodz, Zeromskiego 116, 90-924 Lodz (Poland); Dobruchowska, Ewa [Department of Molecular Physics, Technical University of Lodz, Zeromskiego 116, 90-924 Lodz (Poland); Maniukiewicz, Waldemar [Institute of General and Ecological Chemistry, Technical University of Lodz, Zeromskiego 116, 90-924 Lodz (Poland); Pietsch, Ulrich [FB7- Physik , Universitaet Siegen, 57068 Siegen (Germany); Kowalski, Jacek [Division of Non-Metallic Materials, Faculty of Mechanical Engineering, Technical University of Lodz, Stefanowskiego1/15, 90-924 Lodz (Poland); Szamel, Zbigniew; Ulanski, Jacek [Department of Molecular Physics, Technical University of Lodz, Zeromskiego 116, 90-924 Lodz (Poland)

    2010-02-01

    The continuous bi-layer composites consisting of top, ordered crystalline layer of perylenediimide derivative (2,9-di(pent-3-yl)-anthra[,1,9-def:6,5,10-d'e'f'] diisoquinoline-1,3,8,10-tetrone) - PTCDI-C5(3) and bottom poly(3-hexylthiophene-2,5-diyl) (P3HT) support were obtained from one solution, with a use of so called 'two-step reticulate doping' method. Optical, atomic force and scanning electron microscopy images show that the top crystalline layer is made of relatively large, anisotropic domains composed of long, parallel crystals. The crystalline character of the surface layer of PTCDI-C5(3) grown on the P3HT film was confirmed by wide angle X-ray scattering measurements. Furthermore, the grazing-incidence angle X-ray diffraction experiments revealed that the self-assembly of PTCDI-C5(3) molecules on P3HT is dominated by {pi}-{pi} interaction between the conjugated perylene cores, and the stacks are parallel to the long axis of the crystals and to the polymer surface. The surface conductivity, measured along the long axis of the crystals was estimated to be ca. 2.4 10{sup -8} {Omega}{sup -1} square{sup -}1 at 285 K. Temperature dependence of the conductivity in the range 140-285 K reveal semiconductor-like behaviour with activation energy ca. 150 meV.

  2. 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.

  3. Modelling Polar Self Assembly

    Science.gov (United States)

    Olvera de La Cruz, Monica; Sayar, Mehmet; Solis, Francisco J.; Stupp, Samuel I.

    2001-03-01

    Recent experimental studies in our group have shown that self assembled thin films of noncentrosymmetric supramolecular objects composed of triblock rodcoil molecules exhibit finite polar order. These aggregates have both long range dipolar and short range Ising-like interactions. We study the ground state of a simple model with these competing interactions. We find that the competition between Ising-like and dipolar forces yield a periodic domain structure, which can be controlled by adjusting the force constants and film thickness. When the surface forces are included in the potential, the system exhibits a finite macroscopic polar order.

  4. 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.

  5. Recent Advances in Supramolecular Assemblies with Nucleic Acids

    Science.gov (United States)

    2007-08-29

    xavier.moreau@up.univ-mrs.fr 28 Name Contact Information Laurence Navailles Centre de Recherche Paul Pascal, 115, Avenue Albert Schweitzer 33600...Switzerland Email : peter.walde@mat.ethz.ch 29 Name Contact Information Cécile Zakri Centre de Recherche Paul Pascal, 115, Avenue Albert ... Schweitzer 33600 Pessac, France Email : zakri@crpp-bordeaux.cnrs.fr Guy Zuber Laboratoire de Chimie Génétique, CNRS UMR 7175- LC1- Faculté de

  6. Assembling a Lasing Hybrid Material With Supramolecular Polymers and Nanocrystals

    National Research Council Canada - National Science Library

    Li, Leiming

    2003-01-01

    .... In the system containing ZnO nanocrystals as the inorganic component, both phases are oriented in the hybrid material forming an ultraviolet lasing medium with a lower threshold relative to pure ZnO nanocrystals.

  7. J-like supramolecular assemblies of polyaniline in water

    Czech Academy of Sciences Publication Activity Database

    Omelchenko, Olga; Tomšík, Elena; Zhigunov, Alexander; Guskova, O.; Gribkova, O.; Gospodinova, Natalia

    2013-01-01

    Roč. 214, č. 23 (2013), s. 2739-2743 ISSN 1022-1352 R&D Projects: GA ČR(CZ) GA13-00270S Institutional support: RVO:61389013 Keywords : conjugated polymers * J-aggregates * molecular dynamics Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.451, year: 2013

  8. Symposium Supramolecular Assemblies on Surface: Nanopatterning, Functionality and Reactivity

    Science.gov (United States)

    2016-05-19

    formed and we relate these observations to recent reports of de- wetting of C60 on alkali halide surfaces. The hBN flakes, which are prepared by... annealing will be discussed while for dicarbonitrile polyphenyl derivatives the adsorption behavior on Au(111) will be compared to the one on graphene

  9. Supramolecular assemblies of pyridyl porphyrin and diazadithia phthalocyanine

    Directory of Open Access Journals (Sweden)

    OZER BEKAROGLU

    1999-08-01

    Full Text Available In this paper we report for the first time on a mixed complex between the cationic porphyrin 5, 10, 15, 20-tetra-N- -methyl-pyrydinium-p-il porphyrin (TMPyP and a new metal phthalocyanine with four 16-membered diazadithia macrocycles (denoted here as Pc16, in order to obtain an active complex with an intense absorption on the lower energy side of the visible spectrum and with a higher sensitivity in photodynamic therapy of cancer. The dimerization constant for Pc16 and also the ratio between the oscillator strengths for monomeric and dimeric forms of this compound, were evaluated. The ratio between these oscillator strengths was 2.01 showing a certain dimerization process. The Job mathematical method allowed the establishment of the stoichiometry and the formation constants for the heteroaggregates between the porphyrin and the phthalocy- anine (a diad between one phthalocyanine molecule and one porphyrin molecule and a triad between two phthalocyanine molecules and only one porphyrin molecule. The coulombic attraction resulting from the p-p interaction of the two highly conjugated macrocycles and from the interaction between the substituents, favors a face-to-face geometry.

  10. Supramolecular Assembly of Calcium Metal - Organic Frameworks with Structural Transformation

    Czech Academy of Sciences Publication Activity Database

    Liang, P.-Ch.; Liu, H.-K.; Yeh, Ch.-T.; Lin, Ch.-H.; Zima, Vítězslav

    2011-01-01

    Roč. 11, č. 3 (2011), 699-708 ISSN 1528-7483 R&D Projects: GA ČR GA203/08/0208 Institutional research plan: CEZ:AV0Z40500505 Keywords : metal - organic frameworks * calcium * structure Subject RIV: CA - Inorganic Chemistry Impact factor: 4.720, year: 2011

  11. 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.

  12. Self-assembly behaviours of peptide-drug conjugates: influence of multiple factors on aggregate morphology and potential self-assembly mechanism

    Science.gov (United States)

    Fan, Qin; Ji, Yujie; Wang, Jingjing; Wu, Li; Li, Weidong; Chen, Rui; Chen, Zhipeng

    2018-04-01

    Peptide-drug conjugates (PDCs) as self-assembly prodrugs have the unique and specific features to build one-component nanomedicines. Supramolecular structure based on PDCs could form various morphologies ranging from nanotube, nanofibre, nanobelt to hydrogel. However, the assembly process of PDCs is too complex to predict or control. Herein, we investigated the effects of extrinsic factors on assembly morphology and the possible formation of nanostructures based on PDCs. To this end, we designed a PDC consisting of hydrophobic drug (S)-ketoprofen (Ket) and valine-glutamic acid dimeric repeats peptide (L-VEVE) to study their assembly behaviour. Our results showed that the critical assembly concentration of Ket-L-VEVE was 0.32 mM in water to form various nanostructures which experienced from micelle, nanorod, nanofibre to nanoribbon. The morphology was influenced by multiple factors including molecular design, assembly time, pH and hydrogen bond inhibitor. On the basis of experimental results, we speculated the possible assembly mechanism of Ket-L-VEVE. The π-π stacking interaction between Ket molecules could serve as an anchor, and hydrogen bonded-induced β-sheets and hydrophilic/hydrophobic balance between L-VEVE peptide play structure-directing role in forming filament-like or nanoribbon morphology. This work provides a new sight to rationally design and precisely control the nanostructure of PDCs based on aromatic fragment.

  13. Bio-Inspired Supramolecular Chemistry Provides Highly Concentrated Dispersions of Carbon Nanotubes in Polythiophene

    Directory of Open Access Journals (Sweden)

    Yen-Ting Lin

    2016-06-01

    Full Text Available In this paper we report the first observation, through X-ray diffraction, of noncovalent uracil–uracil (U–U dimeric π-stacking interactions in carbon nanotube (CNT–based supramolecular assemblies. The directionally oriented morphology determined using atomic force microscopy revealed highly organized behavior through π-stacking of U moieties in a U-functionalized CNT derivative (CNT–U. We developed a dispersion system to investigate the bio-inspired interactions between an adenine (A-terminated poly(3-adeninehexyl thiophene (PAT and CNT–U. These hybrid CNT–U/PAT materials interacted through π-stacking and multiple hydrogen bonding between the U moieties of CNT–U and the A moieties of PAT. Most importantly, the U···A multiple hydrogen bonding interactions between CNT–U and PAT enhanced the dispersion of CNT–U in a high-polarity solvent (DMSO. The morphology of these hybrids, determined using transmission electron microscopy, featured grape-like PAT bundles wrapped around the CNT–U surface; this tight connection was responsible for the enhanced dispersion of CNT–U in DMSO.

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

    Science.gov (United States)

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

    2014-07-21

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

  15. Intelligent assembly time analysis, using a digital knowledge based approach

    NARCIS (Netherlands)

    Jin, Y.; Curran, R.; Butterfield, J.; Burke, R.; Welch, B.

    2009-01-01

    The implementation of effective time analysis methods fast and accurately in the era of digital manufacturing has become a significant challenge for aerospace manufacturers hoping to build and maintain a competitive advantage. This paper proposes a structure oriented, knowledge-based approach for

  16. 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

  17. Supramolecular Liquid Crystal Displays Construction and Applications

    OpenAIRE

    Hoogboom, J.T.V.

    2004-01-01

    This thesis describes chemical methodologies, which can be ued to construct alignment layers for liquid crystal display purposes in a non-clean room environment, by making use of supramolecular chemistry. These techniques are subsequently used to attain control over LCD-properties, both pre- and post-LCD construction. In addition, the thesis describes the application of LCD technology in biosensors.

  18. Understanding the Elementary Steps in DNA Tile-Based Self-Assembly.

    Science.gov (United States)

    Jiang, Shuoxing; Hong, Fan; Hu, Huiyu; Yan, Hao; Liu, Yan

    2017-09-26

    Although many models have been developed to guide the design and implementation of DNA tile-based self-assembly systems with increasing complexity, the fundamental assumptions of the models have not been thoroughly tested. To expand the quantitative understanding of DNA tile-based self-assembly and to test the fundamental assumptions of self-assembly models, we investigated DNA tile attachment to preformed "multi-tile" arrays in real time and obtained the thermodynamic and kinetic parameters of single tile attachment in various sticky end association scenarios. With more sticky ends, tile attachment becomes more thermostable with an approximately linear decrease in the free energy change (more negative). The total binding free energy of sticky ends is partially compromised by a sequence-independent energy penalty when tile attachment forms a constrained configuration: "loop". The minimal loop is a 2 × 2 tetramer (Loop4). The energy penalty of loops of 4, 6, and 8 tiles was analyzed with the independent loop model assuming no interloop tension, which is generalizable to arbitrary tile configurations. More sticky ends also contribute to a faster on-rate under isothermal conditions when nucleation is the rate-limiting step. Incorrect sticky end contributes to neither the thermostability nor the kinetics. The thermodynamic and kinetic parameters of DNA tile attachment elucidated here will contribute to the future improvement and optimization of tile assembly modeling, precise control of experimental conditions, and structural design for error-free self-assembly.

  19. Imaging and Quantitation of a Succession of Transient Intermediates Reveal the Reversible Self-Assembly Pathway of a Simple Icosahedral Virus Capsid.

    Science.gov (United States)

    Medrano, María; Fuertes, Miguel Ángel; Valbuena, Alejandro; Carrillo, Pablo J P; Rodríguez-Huete, Alicia; Mateu, Mauricio G

    2016-11-30

    Understanding the fundamental principles underlying supramolecular self-assembly may facilitate many developments, from novel antivirals to self-organized nanodevices. Icosahedral virus particles constitute paradigms to study self-assembly using a combination of theory and experiment. Unfortunately, assembly pathways of the structurally simplest virus capsids, those more accessible to detailed theoretical studies, have been difficult to study experimentally. We have enabled the in vitro self-assembly under close to physiological conditions of one of the simplest virus particles known, the minute virus of mice (MVM) capsid, and experimentally analyzed its pathways of assembly and disassembly. A combination of electron microscopy and high-resolution atomic force microscopy was used to structurally characterize and quantify a succession of transient assembly and disassembly intermediates. The results provided an experiment-based model for the reversible self-assembly pathway of a most simple (T = 1) icosahedral protein shell. During assembly, trimeric capsid building blocks are sequentially added to the growing capsid, with pentamers of building blocks and incomplete capsids missing one building block as conspicuous intermediates. This study provided experimental verification of many features of self-assembly of a simple T = 1 capsid predicted by molecular dynamics simulations. It also demonstrated atomic force microscopy imaging and automated analysis, in combination with electron microscopy, as a powerful single-particle approach to characterize at high resolution and quantify transient intermediates during supramolecular self-assembly/disassembly reactions. Finally, the efficient in vitro self-assembly achieved for the oncotropic, cell nucleus-targeted MVM capsid may facilitate its development as a drug-encapsidating nanoparticle for anticancer targeted drug delivery.

  20. Rational design of fiber forming supramolecular structures

    Science.gov (United States)

    Wang, Benjamin K; Kanahara, Satoko M

    2016-01-01

    Recent strides in the development of multifunctional synthetic biomimetic materials through the self-assembly of multi-domain peptides and proteins over the past decade have been realized. Such engineered systems have wide-ranging application in bioengineering and medicine. This review focuses on fundamental fiber forming α-helical coiled-coil peptides, peptide amphiphiles, and amyloid-based self-assembling peptides; followed by higher order collagen- and elastin-mimetic peptides with an emphasis on chemical / biological characterization and biomimicry. PMID:27022140

  1. 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.

  2. Ultrasensitive colorimetric detection of heparin based on self-assembly of gold nanoparticles on graphene oxide.

    Science.gov (United States)

    Fu, Xiuli; Chen, Lingxin; Li, Jinhua

    2012-08-21

    A novel colorimetric method was developed for ultrasensitive detection of heparin based on self-assembly of gold nanoparticles (AuNPs) onto the surface of graphene oxide (GO). Polycationic protamine was used as a medium for inducing the self-assembly of citrate-capped AuNPs on GO through electrostatic interaction, resulting in a shift in the surface plasmon resonance (SPR) absorption of AuNPs and exhibiting a blue color. Addition of polyanionic heparin disturbed the self-assemble of AuNPs due to its strong affinity to protamine. With the increase of heparin concentration, the amounts of self-assembly AuNPs decreased and the color changed from blue to red in solution. Therefore, a "blue-to-red" colorimetric sensing strategy based on self-assembly of AuNPs could be established for heparin detection. Compared with the commonly reported aggregation-based methods ("red-to-blue"), the color change from blue to red was more eye-sensitive, especially in low concentration of target. Moreover, stronger interaction between protamine and heparin led to distinguish heparin from its analogues as well as various potentially coexistent physiological species. The strategy was simply achieved by the self-assembly nature of AuNPs and the application of two types of polyionic media, showing it to be label-free, simple, rapid and visual. This method could selectively detect heparin with a detection limit of 3.0 ng mL(-1) in standard aqueous solution and good linearity was obtained over the range 0.06-0.36 μg mL(-1) (R = 0.9936). It was successfully applied to determination of heparin in fetal bovine serum samples as low as 1.7 ng mL(-1) with a linear range of 0-0.8 μg mL(-1).

  3. Analysis of the equalizing holes resistance in fuel assembly spike for lead-based reactor

    International Nuclear Information System (INIS)

    Zhang, Guangyu; Jin, Ming; Wang, Jianye; Song, Yong

    2017-01-01

    Highlights: • A RELAP5 model for a 10 MWth lead-based reactor was built to study the hydrodynamic characteristics between the equalizing holes in the fuel assembly spike. • Different fuel assembly total blockage scenarios and different resistances for different fuel assemblies were examined. • The inherent safety characteristics of the lead-based reactor was improved by optimizing the configuration of equalizing holes in the fuel assembly spike. - Abstract: To avoid the damage of the fuel rod cladding when a fuel assembly (FA) is totally blocked, a special configuration of the fuel assembly spike was designed with some equalizing holes in the center region which can let the coolant to flow during the totally blockage scenarios of FA. To study the hydrodynamic characteristics between the equalizing holes and an appropriate resistance, a RELAP5 model was developed for a 10 MWth lead-based reactor which used lead-bismuth as coolant. Several FA total blockage and partial core blockage scenarios were selected. The simulation results indicated that when all the FA spike equalizing holes had the same hydraulic resistance, only a narrow range of suitable equalizing holes resistances could be chosen when a FA was blocked. However, in the two or more FA blockage scenarios, there were no appropriate resistances to meet the requirement. In addition, with different FA spike equalizing holes with different resistances, a large range of suitable equalizing hole resistances could be chosen. Especially a series of suitable resistances were selected when the small power FA resistance was 1/2, 1/4, 1/8 of the large one. Under these circumstances, one, two or three FA blockages would not damage the core. These demonstrated that selecting a series of suitable hydraulic resistances for the equalizing holes could improve the safety characteristics of the reactor effectively.

  4. 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

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

    DEFF Research Database (Denmark)

    Elizondo, Elisa; Larsen, Jannik; Hatzakis, Nikos

    2012-01-01

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

  6. Octanol-assisted liposome assembly on chip

    Science.gov (United States)

    Deshpande, Siddharth; Caspi, Yaron; Meijering, Anna E. C.; Dekker, Cees

    2016-01-01

    Liposomes are versatile supramolecular assemblies widely used in basic and applied sciences. Here we present a novel microfluidics-based method, octanol-assisted liposome assembly (OLA), to form monodisperse, cell-sized (5-20 μm), unilamellar liposomes with excellent encapsulation efficiency. Akin to bubble blowing, an inner aqueous phase and a surrounding lipid-carrying 1-octanol phase is pinched off by outer fluid streams. Such hydrodynamic flow focusing results in double-emulsion droplets that spontaneously develop a side-connected 1-octanol pocket. Owing to interfacial energy minimization, the pocket splits off to yield fully assembled solvent-free liposomes within minutes. This solves the long-standing fundamental problem of prolonged presence of residual oil in the liposome bilayer. We demonstrate the unilamellarity of liposomes with functional α-haemolysin protein pores in the membrane and validate the biocompatibility by inner leaflet localization of bacterial divisome proteins (FtsZ and ZipA). OLA offers a versatile platform for future analytical tools, delivery systems, nanoreactors and synthetic cells.

  7. 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

  8. Muscle assembly: a titanic achievement?

    Science.gov (United States)

    Gregorio, C C; Granzier, H; Sorimachi, H; Labeit, S

    1999-02-01

    The formation of perfectly aligned myofibrils in striated muscle represents a dramatic example of supramolecular assembly in eukaryotic cells. Recently, considerable progress has been made in deciphering the roles that titin, the third most abundant protein in muscle, has in this process. An increasing number of sarcomeric proteins (ligands) are being identified that bind to specific titin domains. Titin may serve as a molecular blueprint for sarcomere assembly and turnover by specifying the precise position of its ligands within each half-sarcomere in addition to functioning as a molecular spring that maintains the structural integrity of the contracting myofibrils.

  9. Formation of high-quality self-assembled monolayers of conjugated dithiols on gold : Base matters

    NARCIS (Netherlands)

    Valkenier, Hennie; Huisman, Everardus H.; Hal, Paul A. van; de Leeuw, Dagobert; Chiechi, Ryan C.; Hummelen, Jan C.

    2011-01-01

    This Article reports a systematic study on the formation of self-assembled monolayers (SAMs) of conjugated molecules for molecular electronic (ME) devices. We monitored the deprotection reaction of acetyl protected dithiols of oligophenylene ethynylenes (OPEs) in solution using two different bases

  10. Multidimensional Test Assembly Based on Lagrangian Relaxation Techniques. Research Report 98-08.

    Science.gov (United States)

    Veldkamp, Bernard P.

    In this paper, a mathematical programming approach is presented for the assembly of ability tests measuring multiple traits. The values of the variance functions of the estimators of the traits are minimized, while test specifications are met. The approach is based on Lagrangian relaxation techniques and provides good results for the two…

  11. Designing thiophene-based azomethine oligomers with tailored properties: Self-assembly and charge carrier mobility

    DEFF Research Database (Denmark)

    Kiriy, N.; Bocharova, V.; Kiriy, A.

    2004-01-01

    This paper describes synthesis and characterization of two thiophene-based azomethines designed to optimize solubility, self-assembly, and charge carrier mobility. We found that incorporation of azomethine and amide moieties in the alpha,omega-position, and hexyl chains in the beta-position of th...... with the mobilities of the best organic semiconductors. All these significant differences in properties of related compounds can be attributed to the hydrogen bonding between QT-amide molecules responsible for the observed self-assembly....

  12. Supramolecular coordination polymer formed from artificial light-harvesting dendrimer.

    Science.gov (United States)

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

    2015-09-30

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

  13. An assembly system based on industrial robot with binocular stereo vision

    Science.gov (United States)

    Tang, Hong; Xiao, Nanfeng

    2017-01-01

    This paper proposes an electronic part and component assembly system based on an industrial robot with binocular stereo vision. Firstly, binocular stereo vision with a visual attention mechanism model is used to get quickly the image regions which contain the electronic parts and components. Secondly, a deep neural network is adopted to recognize the features of the electronic parts and components. Thirdly, in order to control the end-effector of the industrial robot to grasp the electronic parts and components, a genetic algorithm (GA) is proposed to compute the transition matrix and the inverse kinematics of the industrial robot (end-effector), which plays a key role in bridging the binocular stereo vision and the industrial robot. Finally, the proposed assembly system is tested in LED component assembly experiments, and the results denote that it has high efficiency and good applicability.

  14. Optimization of PWR fuel assembly radial enrichment and burnable poison location based on adaptive simulated annealing

    International Nuclear Information System (INIS)

    Rogers, Timothy; Ragusa, Jean; Schultz, Stephen; St Clair, Robert

    2009-01-01

    The focus of this paper is to present a concurrent optimization scheme for the radial pin enrichment and burnable poison location in PWR fuel assemblies. The methodology is based on the Adaptive Simulated Annealing (ASA) technique, coupled with a neutron lattice physics code to update the cost function values. In this work, the variations in the pin U-235 enrichment are variables to be optimized radially, i.e., pin by pin. We consider the optimization of two categories of fuel assemblies, with and without Gadolinium burnable poison pins. When burnable poisons are present, both the radial distribution of enrichment and the poison locations are variables in the optimization process. Results for 15 x 15 PWR fuel assembly designs are provided.

  15. Assembling and Using an LED-Based Detector to Monitor Absorbance Changes during Acid-Base Titrations

    Science.gov (United States)

    Santos, Willy G.; Cavalheiro, E´der T. G.

    2015-01-01

    A simple photometric assembly based in an LED as a light source and a photodiode as a detector is proposed in order to follow the absorbance changes as a function of the titrant volume added during the course of acid-base titrations in the presence of a suitable visual indicator. The simplicity and low cost of the electronic device allow the…

  16. Extension of the charge separated-state lifetime by supramolecular association of a tetrathiafulvalene electron donor to a zinc/gold bisporphyrin.

    Science.gov (United States)

    Boixel, Julien; Fortage, Jérôme; Blart, Errol; Pellegrin, Yann; Hammarström, Leif; Becker, Hans-Christian; Odobel, Fabrice

    2010-02-14

    Supramolecular triads were prepared by self-assembly of 4'-pyridyl-2-tetrathiafulvalene axially bound on ZnP-spacer-AuP(+) dyads; the lifetime of the charge separated state ((+)TTF-ZnP-Spacer-AuP ) formed upon light excitation of the triad is greatly increased with respect to that found in the parent dyad.

  17. Supramolecular dendritic pi-conjugated systems: synthesis of glycinylurea functionalized pi-conjugated diphenylanthracene guests and their complexation with dendritic hosts. Part I.

    NARCIS (Netherlands)

    Precup, F.S.; Schenning, A.P.H.J.; Meijer, E.W.; Hubca, G.

    2007-01-01

    Glycinylurea functionalized p-conjugated diphenylanthracene guests (DPA guests) that bind to adamantyl urea modified dendritic hosts were synthesized and fully characterized by NMR spectroscopy (1H-NMR, 13C-NMR) and MALDI-TOF-MS. The resulting supramolecular assemblies have been investigated with

  18. Template-based self-assembly for silicon chips and 01005 surface-mount components

    International Nuclear Information System (INIS)

    Hoo, J H; Park, Kwang Soon; Baskaran, Rajashree; Böhringer, Karl F

    2014-01-01

    We present template-based microscale self-assembly as a technique that promotes the electronics industry's initiative towards functional diversification and function densification, demonstrating that our process can improve existing assembly and packaging techniques, and also enable possibilities restricted by current industry methodologies. We first present foundational work that performs part (370 × 370 × 150 µm 3 ) delivery to receptor sites (20 × 10 array) with a stochastic batch delivery process that completes within tens of seconds. The delivery mechanism is statistically characterized and a chemical kinetics inspired model is developed. Based on this understanding, repeatable and programmable 100% yield assembly is achieved in open-loop and feedback-based configurations. The established methodology is adapted to deliver and assemble standard 01 005 format (0.016″ × 0.008″, 0.4 mm × 0.2 mm) monolithic ceramic capacitors and thin-film resistors onto silicon substrates. This process is CMOS compatible and is competitive with capacitors and resistors fabricated through standard foundry processes. (paper)

  19. Cellular self-assembly and biomaterials-based organoid models of development and diseases.

    Science.gov (United States)

    Shah, Shivem B; Singh, Ankur

    2017-04-15

    Organogenesis and morphogenesis have informed our understanding of physiology, pathophysiology, and avenues to create new curative and regenerative therapies. Thus far, this understanding has been hindered by the lack of a physiologically relevant yet accessible model that affords biological control. Recently, three-dimensional ex vivo cellular cultures created through cellular self-assembly under natural extracellular matrix cues or through biomaterial-based directed assembly have been shown to physically resemble and recapture some functionality of target organs. These "organoids" have garnered momentum for their applications in modeling human development and disease, drug screening, and future therapy design or even organ replacement. This review first discusses the self-organizing organoids as materials with emergent properties and their advantages and limitations. We subsequently describe biomaterials-based strategies used to afford more control of the organoid's microenvironment and ensuing cellular composition and organization. In this review, we also offer our perspective on how multifunctional biomaterials with precise spatial and temporal control could ultimately bridge the gap between in vitro organoid platforms and their in vivo counterparts. Several notable reviews have highlighted PSC-derived organoids and 3D aggregates, including embryoid bodies, from a development and cellular assembly perspective. The focus of this review is to highlight the materials-based approaches that cells, including PSCs and others, adopt for self-assembly and the controlled development of complex tissues, such as that of the brain, gut, and immune system. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  20. Modeling Textural Processes during Self-Assembly of Plant-Based Chiral-Nematic Liquid Crystals

    Directory of Open Access Journals (Sweden)

    Yogesh K. Murugesan

    2010-12-01

    Full Text Available Biological liquid crystalline polymers are found in cellulosic, chitin, and DNA based natural materials. Chiral nematic liquid crystalline orientational order is observed frozen-in in the solid state in plant cell walls and is known as a liquid crystal analogue characterized by a helicoidal plywood architecture. The emergence of the plywood architecture by directed chiral nematic liquid crystalline self assembly has been postulated as the mechanism that leads to optimal cellulose fibril organization. In natural systems, tissue growth and development takes place in the presence of inclusions and secondary phases leaving behind characteristic defects and textures, which provide a unique testing ground for the validity of the liquid crystal self-assembly postulate. In this work, a mathematical model, based on the Landau-de Gennes theory of liquid crystals, is used to simulate defect textures arising in the domain of self assembly, due to presence of secondary phases representing plant cells, lumens and pit canals. It is shown that the obtained defect patterns observed in some plant cell walls are those expected from a truly liquid crystalline phase. The analysis reveals the nature and magnitude of the viscoelastic material parameters that lead to observed patterns in plant-based helicoids through directed self-assembly. In addition, the results provide new guidance to develop biomimetic plywoods for structural and functional applications.

  1. Rational design of single-molecule magnets: a supramolecular approach.

    Science.gov (United States)

    Glaser, Thorsten

    2011-01-07

    Since the discovery that Mn(12)OAc acts as a single-molecule magnet (SMM), an increasing number of transition metal complexes have been demonstrated to behave as SMMs. The signature of a SMM is a slow relaxation of the magnetization at low temperatures accompanied by a magnetic hysteresis. The origin of SMM behaviour is the existence of an appreciable thermal barrier U for spin-reversal called magnetic anisotropy barrier which is related to the combination of a large total spin ground state (S(t)) and an easy-axis magnetic anisotropy. The extensive research on Mn(12)OAc and other SMMs has established more prerequisites for a rational development of new SMMs besides the high-spin ground state and the magnetic anisotropy: the symmetry should be at least C(3) to minimize the quantum tunneling of the magnetization through the anisotropy barrier but lower than cubic to avoid the cancellation of the local anisotropies upon projection onto the spin ground state. Based on these prerequisites, we have designed the ligand triplesalen which combines the phloroglucinol bridging unit for high spin ground states by the spin-polarization mechanism with a salen-like ligand environment for single-site magnetic anisotropies by a strong tetragonal ligand field. The C(3) symmetric, trinuclear complexes of the triplesalen ligand (talen(t-Bu(2)))(6-) exhibit a strong ligand folding resulting in an overall bowl-shaped molecular structure. This ligand folding preorganizes the axial coordination sites of the metal salen subunits for the complementary binding of three facial nitrogen atoms of a hexacyanometallate unit. This leads to a high driving force for the formation of heptanuclear complexes [M(t)(6)M(c)](n+) by the assembly of three molecular building blocks. Attractive van der Waals interactions of the tert-butyl phenyl units of two triplesalen trinuclear building blocks increase the driving force. In this respect, we have been able to synthesize the isostructural series [Mn(III)(6

  2. Precise Steric Control over 2D versus 3D Self-Assembly of Antimony(III) Alkoxide Cages through Strong Secondary Bonding Interactions.

    Science.gov (United States)

    Moaven, Shiva; Yu, Jingze; Yasin, Jason; Unruh, Daniel K; Cozzolino, Anthony F

    2017-07-17

    Antimony(III) alkoxide cages were designed as building blocks for predictable supramolecular self-assembly. Supramolecular synthons featuring two Sb···O secondary bonding interactions (SBIs), each SBI stronger than 30 kJ/mol, were used to drive the formation of the supramolecular architectures. Judicious choice of pendant groups provided predictable control over the formation of self-assembled 3D columnar helices, which crystallized with hollow morphologies, or a self-assembled 2D bilayer. The Sb-O stretching frequency provides a spectroscopic signature of Sb···O SBI formation.

  3. Data base of reactor physics experimental results in Kyoto University critical assembly experimental facilities

    International Nuclear Information System (INIS)

    Ichihara, Chihiro; Fujine, Shigenori; Hayashi, Masatoshi

    1986-01-01

    The Kyoto University critical assembly experimental facilities belong to the Kyoto University Research Reactor Institute, and are the versatile critical assembly constructed for experimentally studying reactor physics and reactor engineering. The facilities are those for common utilization by universities in whole Japan. During more than ten years since the initial criticality in 1974, various experiments on reactor physics and reactor engineering have been carried out using many experimental facilities such as two solidmoderated cores, a light water-moderated core and a neutron generator. The kinds of the experiment carried out were diverse, and to find out the required data from them is very troublesome, accordingly it has become necessary to make a data base which can be processed by a computer with the data accumulated during the past more than ten years. The outline of the data base, the data base CAEX using personal computers, the data base supported by a large computer and so on are reported. (Kako, I.)

  4. Supracolloidal Architectures Self-Assembled in Microdroplets.

    Science.gov (United States)

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

    2015-10-26

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

  5. Self-assembly of protein-based biomaterials initiated by titania nanotubes.

    Science.gov (United States)

    Forstater, Jacob H; Kleinhammes, Alfred; Wu, Yue

    2013-12-03

    Protein-based biomaterials are a promising strategy for creating robust highly selective biocatalysts. The assembled biomaterials must sufficiently retain the near-native structure of proteins and provide molecular access to catalytically active sites. These requirements often exclude the use of conventional assembly techniques, which rely on covalent cross-linking of proteins or entrapment within a scaffold. Here we demonstrate that titania nanotubes can initiate and template the self-assembly of enzymes, such as ribonuclease A, while maintaining their catalytic activity. Initially, the enzymes form multilayer thick ellipsoidal aggregates centered on the nanotube surface; subsequently, these nanosized entities assemble into a micrometer-sized enzyme material that has enhanced enzymatic activity and contains as little as 0.1 wt % TiO2 nanotubes. This phenomenon is uniquely associated with the active anatase (001)-like surface of titania nanotubes and does not occur on other anatase nanomaterials, which contain significantly fewer undercoordinated Ti surface sites. These findings present a nanotechnology-enabled mechanism of biomaterial growth and open a new route for creating stable protein-based biomaterials and biocatalysts without the need for chemical modification.

  6. 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

  7. 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.

  8. Photon Upconversion and Molecular Solar Energy Storage by Maximizing the Potential of Molecular Self-Assembly.

    Science.gov (United States)

    Kimizuka, Nobuo; Yanai, Nobuhiro; Morikawa, Masa-Aki

    2016-11-29

    The self-assembly of functional molecules into ordered molecular assemblies and the fulfillment of potentials unique to their nanotomesoscopic structures have been one of the central challenges in chemistry. This Feature Article provides an overview of recent progress in the field of molecular self-assembly with the focus on the triplet-triplet annihilation-based photon upconversion (TTA-UC) and supramolecular storage of photon energy. On the basis of the integration of molecular self-assembly and photon energy harvesting, triplet energy migration-based TTA-UC has been achieved in varied molecular systems. Interestingly, some molecular self-assemblies dispersed in solution or organogels revealed oxygen barrier properties, which allowed TTA-UC even under aerated conditions. The elements of molecular self-assembly were also introduced to the field of molecular solar thermal fuel, where reversible photoliquefaction of ionic crystals to ionic liquids was found to double the molecular storage capacity with the simultaneous pursuit of switching ionic conductivity. A future prospect in terms of innovating molecular self-assembly toward molecular systems chemistry is also discussed.

  9. Estratégia supramolecular para a nanotecnologia Supramolecular approach to nanotechnology

    Directory of Open Access Journals (Sweden)

    Koiti Araki

    2007-12-01

    Full Text Available Brazilian science is evolving rapidly and steadly in the last 10 years, reaching the 15º place in the international ranking. Research in nanotechnology is following a similar way generating new scientific and technological knowledge in several frontiers but specially in the interfaces of two or more areas, where Chemistry is consolidating itself as a central science. In this context, the supramolecular approach is a very promissing one because it allows the build-up of a chemical inteligence using all the sistematized knowledge for the design and development of new nanomaterials and products. The great challenge of Chemistry is not decrease the dimensionality of the materials but instead find ways to increase the dimensionality and structural complexity keeping strict control on the interactions between the components, in order to generate materials with new properties and functionalities. Unfortunately, the current vigorous advancement of scientific research has not been followed by the transformation of such know-how into patents and produts. Therefore much efforts should be devoted to build a national science and technology program, joining all the segments of the society involved in the technological development (university, institutes of technological research, industry and government in order to promote the furtherance of the Brazilian technological base. Only in this way it is possible to evolve to a technological society capable to transform the scientific knowledge into wealthy, thus sustaining the socioeconomic development of the country.

  10. Research on the Optimization Method of Arm Movement in the Assembly Workshop Based on Ergonomics

    Science.gov (United States)

    Hu, X. M.; Qu, H. W.; Xu, H. J.; Yang, L.; Yu, C. C.

    2017-12-01

    In order to improve the work efficiency and comfortability, Ergonomics is used to research the work of the operator in the assembly workshop. An optimization algorithm of arm movement in the assembly workshop is proposed. In the algorithm, a mathematical model of arm movement is established based on multi rigid body movement model and D-H method. The solution of inverse kinematics equation on arm movement is solved through kinematics theory. The evaluation functions of each joint movement and the whole arm movement are given based on the comfortability of human body joint. The solution method of the optimal arm movement posture based on the evaluation functions is described. The software CATIA is used to verify that the optimal arm movement posture is valid in an example and the experimental result show the effectiveness of the algorithm.

  11. Virus-Assembled Flexible Electrode-Electrolyte Interfaces for Enhanced Polymer-Based Battery Applications

    Directory of Open Access Journals (Sweden)

    Ayan Ghosh

    2012-01-01

    Full Text Available High-aspect-ratio cobalt-oxide-coated Tobacco mosaic virus (TMV- assembled polytetrafluoroethylene (PTFE nonstick surfaces were integrated with a solvent-free polymer electrolyte to create an anode-electrolyte interface for use in lithium-ion batteries. The virus-assembled PTFE surfaces consisted primarily of cobalt oxide and were readily intercalated with a low-molecular-weight poly (ethylene oxide (PEO based diblock copolymer electrolyte to produce a solid anode-electrolyte system. The resulting polymer-coated virus-based system was then peeled from the PTFE backing to produce a flexible electrode-electrolyte component. Electrochemical studies indicated the virus-structured metal-oxide PEO-based interface was stable and displayed robust charge transfer kinetics. Combined, these studies demonstrate the development of a novel solid-state electrode architecture with a unique peelable and flexible processing attribute.

  12. 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.

  13. 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

  14. Hydrazine-mediated construction of nanocrystal self-assembly materials.

    Science.gov (United States)

    Zhou, Ding; Liu, Min; Lin, Min; Bu, Xinyuan; Luo, Xintao; Zhang, Hao; Yang, Bai

    2014-10-28

    Self-assembly is the basic feature of supramolecular chemistry, which permits to integrate and enhance the functionalities of nano-objects. However, the conversion of self-assembled structures to practical materials is still laborious. In this work, on the basis of studying one-pot synthesis, spontaneous assembly, and in situ polymerization of aqueous semiconductor nanocrystals (NCs), NC self-assembly materials are produced and applied to design high performance white light-emitting diode (WLED). In producing self-assembly materials, the additive hydrazine (N2H4) is curial, which acts as the promoter to achieve room-temperature synthesis of aqueous NCs by favoring a reaction-controlled growth, as the polyelectrolyte to weaken inter-NC electrostatic repulsion and therewith facilitate the one-dimensional self-assembly, and in particular as the bifunctional monomers to polymerize with mercapto carboxylic acid-modified NCs via in situ amidation reaction. This strategy is versatile for mercapto carboxylic acid-modified aqueous NCs, for example CdS, CdSe, CdTe, CdSe(x)Te(1-x), and Cd(y)Hg(1-y)Te. Because of the multisite modification with carboxyl, the NCs act as macromonomers, thus producing cross-linked self-assembly materials with excellent thermal, solvent, and photostability. The assembled NCs preserve strong luminescence and avoid unpredictable fluorescent resonance energy transfer, the main problem in design WLED from multiple NC components. These advantages allow the fabrication of NC-based WLED with high color rendering index (86), high luminous efficacy (41 lm/W), and controllable color temperature.

  15. Photo-Crosslinking Induced Geometric Restriction Controls the Self-Assembly of Diphenylalanine Based Peptides

    International Nuclear Information System (INIS)

    Tie Zuo-Xiu; Qin Meng; Zou Da-Wei; Cao Yi; Wang Wei

    2011-01-01

    The diphenylalanine (FF) motif has been widely used in the design of peptides that are capable of forming various ordered structures, such as nanotubes, nanospheres and hydrogels. In these assemblies, FF based peptides adopt an antiparallel structure and are stabilized by π — π stacking among the phenyl groups. Here we show that assembly of FF-based peptides can be controlled by their geometric restrictions. Using tripeptide FFY (L-Phe-L-Phe-L-Tyr) as an example, we demonstrate that photo-crosslinking of C-terminal tyrosine can impose a geometric restriction to the formation of an antiparallel structure, leading to a structural change of the assemblies from nanosphere to amorphous. This finding is confirmed using far-UV circular dichroism, Fourier transform infrared spectroscopy and atomic force microscopy. Based on such a mechanism, we are able to control the gel-sol transition of Fmoc-FFY using the geometric restriction induced by photo-crosslinking of C-terminal tyrosine groups. We believe that geometric restriction should be considered as an important factor in the design of peptide-based materials. It can also be implemented as a useful strategy for the construction of environment-responsive 'smart' materials. (cross-disciplinary physics and related areas of science and technology)

  16. Photo-crosslinking induced geometric restriction controls the self-assembly of diphenylalanine based peptides

    International Nuclear Information System (INIS)

    Tie Zuoxiu; Qin Meng; Zou Dawei; Cao Yi; Wang Wei

    2011-01-01

    The diphenylalanine (FF) motif has been widely used in the design of peptides that are capable of forming various ordered structures, such as nanotubes, nanospheres and hydrogels. In these assemblies, FF based peptides adopt an antiparallel structure and are stabilized by π-π stacking among the phenyl groups. Here we show that assembly of FF-based peptides can be controlled by their geometric restrictions. Using tripeptide FFY (L-Phe-L-Phe-L-Tyr) as an example, we demonstrate that photo-crosslinking of C-terminal tyrosine can impose a geometric restriction to the formation of an antiparallel structure, leading to a structural change of the assemblies from nanosphere to amorphous. This finding is confirmed using far-UV circular dichroism, Fourier transform infrared spectroscopy and atomic force microscopy. Based on such a mechanism, we are able to control the gel-sol transition of Fmoc-FFY using the geometric restriction induced by photo-crosslinking of C-terminal tyrosine groups. We believe that geometric restriction should be considered as an important factor in the design of peptide-based materials. It can also be implemented as a useful strategy for the construction of environment-responsive 'smart' materials. (authors)

  17. 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.

  18. White-light-emitting supramolecular gels.

    Science.gov (United States)

    Praveen, Vakayil K; Ranjith, Choorikkat; Armaroli, Nicola

    2014-01-07

    Let there be light, let it be white: Recent developments in the use of chromophore-based gels as scaffolds for the assembly of white-light-emitting soft materials have been significant. The main advantage of this approach lies in the facile accommodation of selected luminescent components within the gel. Excitation-energy-transfer processes between these components ultimately generate the desired light output. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Supracolloidal Assemblies as Sacrificial Templates for Porous Silk-Based Biomaterials

    Directory of Open Access Journals (Sweden)

    John G. Hardy

    2015-08-01

    Full Text Available Tissues in the body are hierarchically structured composite materials with tissue-specific properties. Urea self-assembles via hydrogen bonding interactions into crystalline supracolloidal assemblies that can be used to impart macroscopic pores to polymer-based tissue scaffolds. In this communication, we explain the solvent interactions governing the solubility of urea and thereby the scope of compatible polymers. We also highlight the role of solvent interactions on the morphology of the resulting supracolloidal crystals. We elucidate the role of polymer-urea interactions on the morphology of the pores in the resulting biomaterials. Finally, we demonstrate that it is possible to use our urea templating methodology to prepare Bombyx mori silk protein-based biomaterials with pores that human dermal fibroblasts respond to by aligning with the long axis of the pores. This methodology has potential for application in a variety of different tissue engineering niches in which cell alignment is observed, including skin, bone, muscle and nerve.

  20. MR-1S Interacts with PET100 and PET117 in Module-Based Assembly of Human Cytochrome c Oxidase

    Directory of Open Access Journals (Sweden)

    Sara Vidoni

    2017-02-01

    Full Text Available The biogenesis of human cytochrome c oxidase (COX is an intricate process in which three mitochondrial DNA (mtDNA-encoded core subunits are assembled in a coordinated way with at least 11 nucleus-encoded subunits. Many chaperones shared between yeast and humans are involved in COX assembly. Here, we have used a MT-CO3 mutant cybrid cell line to define the composition of assembly intermediates and identify new human COX assembly factors. Quantitative mass spectrometry analysis led us to modify the assembly model from a sequential pathway to a module-based process. Each module contains one of the three core subunits, together with different ancillary components, including HIGD1A. By the same analysis, we identified the short isoform of the myofibrillogenesis regulator 1 (MR-1S as a new COX assembly factor, which works with the highly conserved PET100 and PET117 chaperones to assist COX biogenesis in higher eukaryotes.