Improving the reactivity of phenylacetylene macrocycles toward topochemical polymerization by side chains modification

• Simon Rondeau-Gagné,
• Jules Roméo Néabo,
• Maxime Daigle,
• Katy Cantin and
• Jean-François Morin

Beilstein J. Org. Chem. 2014, 10, 1613–1619, doi:10.3762/bjoc.10.167

• provide control over the size, shape and electronic properties of the resulting nanoarchitectures [1][2][3]. It is therefore not surprising that supramolecular interactions are regularly used to afford long-range molecular organization for organic and molecular electronics applications in which high-level

• of organization is required to reach good charge transport properties [4][5][6]. However, supramolecular assemblies often suffer from poor stability, meaning that variation of the storage and device operation conditions can perturb the molecular organization, leading to a decline of the materials

• crystalline state to yield polydiacetylenes (PDAs) following a 1,4-addition mechanism, thus fixing the initial molecular organization through covalent bonds formation [12][13]. In order for this polymerization to proceed, the molecules within the assembly must be oriented relative to each other following

Biantennary oligoglycines and glyco-oligoglycines self-associating in aqueous medium

• Svetlana V. Tsygankova,
• Alexander A. Chinarev,
• Alexander B. Tuzikov,
• Nikolai Severin,
• Alexey A. Kalachev,
• Juergen P. Rabe,
• Alexandra S. Gambaryan and
• Nicolai V. Bovin

Beilstein J. Org. Chem. 2014, 10, 1372–1382, doi:10.3762/bjoc.10.140

• oligoglycines capable of association as well as the spectra of tri- and tetraantennary peptides described earlier display bands at 884, 1261, 1382, 1424 and 1654 cm−1, which are characteristic and specific for crystalline PG II. Based on the presence of these bands we conclude that the structure organization of

• biantennary oligoglycines is affected by several factors. 1) Mica but not graphite promotes the formation of tectomers. 2) The spatial organization of oligoglycine molecules in supramers corresponds to PG II conformation. 3) Not less than four glycine residues in each of two antennas are required for the

Synthesis, characterization and DNA interaction studies of new triptycene derivatives

• Sourav Chakraborty,
• Snehasish Mondal,
• Rina Kumari,
• Sourav Bhowmick,
• Prolay Das and
• Neeladri Das

Beilstein J. Org. Chem. 2014, 10, 1290–1298, doi:10.3762/bjoc.10.130

• functionalities) with DNA. According to a literature survey, many metal-free small molecules are known to modify structural organization of DNA through recognition, binding, cleavage or crosslinking and reportedly have widespread applications in biology [26]. Targeting of DNA by several DNA-damaging agents have

Amino acid motifs in natural products: synthesis of O-acylated derivatives of (2S,3S)-3-hydroxyleucine

• Oliver Ries,
• Martin Büschleb,
• Markus Granitzka,
• Dietmar Stalke and
• Christian Ducho

Beilstein J. Org. Chem. 2014, 10, 1135–1142, doi:10.3762/bjoc.10.113

• : Experimental procedures and NMR spectra of compounds 6–9, 11–13, 15–19, 21–24, 26–28, 30, 31, 33, 34, 36–41 and S1. Acknowledgements O. R., M. B. and C. D. thank the Deutsche Forschungsgemeinschaft (DFG, SFB 803 "Functionality controlled by organization in and between membranes") and the Fonds der Chemischen

Molecular architecture with carbohydrate functionalized β-peptides adopting 3₁₄-helical conformation

• Nitin J. Pawar,
• Navdeep S. Sidhu,
• George M. Sheldrick,
• Dilip D. Dhavale and
• Ulf Diederichsen

Beilstein J. Org. Chem. 2014, 10, 948–955, doi:10.3762/bjoc.10.93

• , xylose) as sugar-β-amino acids in a 314-helix. Up to three sugar units were linearly aligned with 5 Å distance (Figure 1). This kind of sugar organization will be of later relevance, e.g., in lectin binding studies and with respect to the investigation of multivalency effects [21][22][23]. The use of

The influence of intraannular templates on the liquid crystallinity of shape-persistent macrocycles

• Joscha Vollmeyer,
• Ute Baumeister and
• Sigurd Höger

Beilstein J. Org. Chem. 2014, 10, 910–920, doi:10.3762/bjoc.10.89

• compound molecules and also the interaction between the macrocycles and appropriate partners. For example, the 2D organization of shape-persistent macrocycles at suitable surfaces leads to long-range ordered patterns with nanoscale lattice parameters and, moreover, even to the epitaxial absorption of

Unusual polymorphism in new bent-shaped liquid crystals based on biphenyl as a central molecular core

• Anna Kovářová,
• Svatopluk Světlík,
• Václav Kozmík,
• Jiří Svoboda,
• Vladimíra Novotná,
• Damian Pociecha,
• Ewa Gorecka and
• Natalia Podoliak

Beilstein J. Org. Chem. 2014, 10, 794–807, doi:10.3762/bjoc.10.75

• strengthening of the upper polar mode, then both parameters Δε and fr decrease on cooling. A schematic organization of bent-shaped molecules in layers can be proposed (Figure 12). In the first column in Figure 12, the arrangement of molecules in subsequent layers of the SmCAPA phase is shown. In the middle part

• -Dimensional plot of the imaginary part of permittivity, ε’’, versus temperature and frequency for IIb. Temperature dependence of the dielectric strength, Δε, and relaxation frequency, fr, for IIb. Schematic organization of bent-shaped molecules in layers for the SmCAPA–SmCG–SmCSPA sequence of mesophases. In

Asymmetric total synthesis of a putative sex pheromone component from the parasitoid wasp Trichogramma turkestanica

• Danny Geerdink,
• Jeffrey Buter,
• Teris A. van Beek and
• Adriaan J. Minnaard

Beilstein J. Org. Chem. 2014, 10, 761–766, doi:10.3762/bjoc.10.71

• putative sex pheromone 2. Supporting Information Supporting Information File 272: Detailed experimental procedures and spectral data of all new compounds. Acknowledgements This work was financially supported by The Netherlands Organization for Scientific Research (NWO-CW). Mr. K. Ward of Ward

End-group-functionalized poly(N,N-diethylacrylamide) via free-radical chain transfer polymerization: Influence of sulfur oxidation and cyclodextrin on self-organization and cloud points in water

• Sebastian Reinelt,
• Daniel Steinke and
• Helmut Ritter

Beilstein J. Org. Chem. 2014, 10, 680–691, doi:10.3762/bjoc.10.61

• increase of the cloud points again. Dynamic light scattering measurements: Influence of RAMEB-CD on self-organization behavior. Dynamic light scattering (DLS) measurements were conducted in order to understand the surprising phenomena that the cloud point of 4-tert-octylphenol end-group bearing polymers

Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products

• Alexander O. Terent'ev,
• Dmitry A. Borisov,
• Vera A. Vil’ and
• Valery M. Dembitsky

Beilstein J. Org. Chem. 2014, 10, 34–114, doi:10.3762/bjoc.10.6

• biological activity. In medicinal chemistry of peroxides, particular emphasis is given to the design of compounds having activity against causative agents of malaria and helminth infections. The World Health Organization (WHO) considers malaria as one of the most dangerous social diseases. Worldwide, 300–500

The myxocoumarins A and B from Stigmatella aurantiaca strain MYX-030

• Tobias A. M. Gulder,
• Snežana Neff,
• Traugott Schüz,
• Tammo Winkler,
• René Gees and
• Bettina Böhlendorf

Beilstein J. Org. Chem. 2013, 9, 2579–2585, doi:10.3762/bjoc.9.293

• structural organization of the aromatic system was further investigated by HMBC spectroscopy. The proton at 7.43 ppm showed strong correlations with two of the heteroatom-substituted carbons at 157.8 and 148.3 ppm, the putatively alkyl substituted position at 118.6 ppm, as well as the C atom at 103.2 ppm

Investigating the continuous synthesis of a nicotinonitrile precursor to nevirapine

• Ashley R. Longstreet,
• Suzanne M. Opalka,
• Brian S. Campbell,
• B. Frank Gupton and
• D. Tyler McQuade

Beilstein J. Org. Chem. 2013, 9, 2570–2578, doi:10.3762/bjoc.9.292

• tenofovir (TDF) is one of the preferred first-line combination drug therapies recommended by the World Health Organization (WHO) [3][4][5]. WHO initiatives are expected to increase the demand for nevirapine over the next 10 years (Figure 1) [6]. Although several viable NNRT substitutes for nevirapine are

Microflow photochemistry: UVC-induced [2 + 2]-photoadditions to furanone in a microcapillary reactor

• Sylvestre Bachollet,
• Kimitada Terao,
• Shin Aida,
• Yasuhiro Nishiyama,
• Kiyomi Kakiuchi and
• Michael Oelgemöller

Beilstein J. Org. Chem. 2013, 9, 2015–2021, doi:10.3762/bjoc.9.237

• (Ministry of Education, Culture, Sports, Science and Technology of the Japanese Government) and the Student Exchange Support Program from the Japan Student Service Organization (JASSO). The authors thank Dr. Norbert Hoffmann (University of Reims) for providing the UV-spectrum of 1.

Topochemical control of the photodimerization of aromatic compounds by γ-cyclodextrin thioethers in aqueous solution

• Hai Ming Wang and
• Gerhard Wenz

Beilstein J. Org. Chem. 2013, 9, 1858–1866, doi:10.3762/bjoc.9.217

• transformations in homogeneous media, and various mixtures of products are obtained. Pre-organization of the reactants in the solid state [3] or by various templates in solution has been the best solution to this problem [4][5]. Cyclic host molecules large enough to accommodate two reacting molecules are the

• the dominant factor, but rather the pre-organization of the guest molecules in the CD cavity prior to excitation has the greatest effect. The distribution of the stereoisomers appears to be mainly topochemically [5] controlled because of the short lifetime of the excited state of COU. Quantum

• photoproduct from aqueous solution by liquid/liquid extraction simplifies the scale up. Yields of photodimer based on the complex were nearly quantitative. The observed supramolecular catalysis was explained by the high pre-organization resulting from the tight packing of the two guests in the cavity, which

Molecular assembly of amino acid interlinked, topologically symmetric, π-complementary donor–acceptor–donor triads

• M. B. Avinash,
• K. V. Sandeepa and
• T. Govindaraju

Beilstein J. Org. Chem. 2013, 9, 1565–1571, doi:10.3762/bjoc.9.178

• organization of D-A stacks could bring about significant improvement in the conductivity through directional charge transfer. Herein, we have chosen three D-A-D triads (1–3) of pyrene and NDI interlinked by different amino acids, namely alanine, phenylalanine and isoleucine (Figure 1). The choice of amino

Enhancement of efficiency in organic photovoltaic devices containing self-complementary hydrogen-bonding domains

• Rohan J. Kumar,
• Jegadesan Subbiah and
• Andrew B. Holmes

Beilstein J. Org. Chem. 2013, 9, 1102–1110, doi:10.3762/bjoc.9.122

• possible modes of self-organization. In order to further investigate the plausibility of each scenario, GIAO shielding calculations were used to predict the 1H NMR chemical shifts of (i) the optimized structure of 1 (Figure 2), (ii) an anti-symmetric dimer of 2 (Figure 5a) and (iii) the same dimer

• organic photovoltaic devices fabricated with 1:1 blends of 2 with PCBM it was observed that the fill factor increased in comparison with the data reported for a similar molecule (1) that did not show evidence of self-organization. The use of designed hydrogen-bonding interactions to produce hierarchical

• materials may be a suitable approach to improve OPV device efficiencies through the enhanced self-organization of materials. N-ethylhexyl-substituted (1) [20] and target free N–H (2) cyanopyridone structures. (a) Chloroform (solid line) and thin-film (dashed line) UV–vis absorption and emission spectra and

Thermotropic and lyotropic behaviour of new liquid-crystalline materials with different hydrophilic groups: synthesis and mesomorphic properties

• Alexej Bubnov,
• Miroslav Kašpar,
• Věra Hamplová,
• Ute Dawin and
• Frank Giesselmann

Beilstein J. Org. Chem. 2013, 9, 425–436, doi:10.3762/bjoc.9.45

• behaviour. Such materials are of high potential interest for challenging issues such as the self-organization of carbon nanotubes or various nanoparticles. Thermotropic mesomorphic properties have been studied by using polarizing optical microscopy, differential scanning calorimetry and X-ray scattering

• such as the organization of carbon nanotubes [17] or various nanoparticles [18] in a liquid-crystalline matrix. To reach the goal, several new multifunctional liquid-crystalline materials possessing either ethylene glycol units (denoted as TL1 and TL2) or a different number of hydroxy groups (denoted

Thioester derivatives of the natural product psammaplin A as potent histone deacetylase inhibitors

• Matthias G. J. Baud,
• Thomas Leiser,
• Vanessa Petrucci,
• Mekala Gunaratnam,
• Stephen Neidle,
• Franz-Josef Meyer-Almes and
• Matthew J. Fuchter

Beilstein J. Org. Chem. 2013, 9, 81–88, doi:10.3762/bjoc.9.11

• . Keywords: epigenetics; histone deacetylase; natural product; prodrug; psammaplin A; thioester; Introduction Chromatin is a macromolecular complex consisting of DNA, histone and nonhistone proteins. The epigenetic control of chromatin organization plays a major role in the regulation of gene expression

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225

• chemistry. Today the situation has completely changed, as is, among other things, demonstrated by numerous review articles and a recent two volumes monograph on modern allene chemistry [12][13][14]. As far as the organization of the present review is concerned, we have tried to cover the literature up to

Self-assembled organic–inorganic magnetic hybrid adsorbent ferrite based on cyclodextrin nanoparticles

• Ângelo M. L. Denadai,
• Frederico B. De Sousa,
• Joel J. Passos,
• Fernando C. Guatimosim,
• Kirla D. Barbosa,
• Ana E. Burgos,
• Fernando Castro de Oliveira,
• Jeann C. da Silva,
• Bernardo R. A. Neves,
• Nelcy D. S. Mohallem and
• Rubén D. Sinisterra

Beilstein J. Org. Chem. 2012, 8, 1867–1876, doi:10.3762/bjoc.8.215

• . Ferrite morphology in the solid state was affected by βCD insertion, probably due to its size and key role as modulator during inorganic nucleation. Ferrites presented at least three different organization scales, from the micrometric to the nanometric level, and on the nanometric scale it was possible to

• verify the material organization and particle size distribution. Lower domains, and greater specific area and free volume were observed for the Fe-Ni/Zn/βCD material. On the micrometric level, both ferrites have comparable behavior, with quite similar size distribution and ZP values, although Fe-Ni/Zn

Polysiloxane ionic liquids as good solvents for β-cyclodextrin-polydimethylsiloxane polyrotaxane structures

• Narcisa Marangoci,
• Rodinel Ardeleanu,
• Laura Ursu,
• Constanta Ibanescu,
• Maricel Danu,
• Mariana Pinteala and
• Bogdan C. Simionescu

Beilstein J. Org. Chem. 2012, 8, 1610–1618, doi:10.3762/bjoc.8.184

• number of works that showed their use as solvents or as solvents for synthesis and catalysis [4][5][6]. In this context ILs, which have polar and nonpolar regions, could play an important role in the field of supramolecular organization of different supramolecular structures (such as polyrotaxanes or

Synthesis of trifunctional cyclo-β-tripeptide templates

• Frank Stein,
• Tahir Mehmood,
• Tilman Plass,
• Javid H. Zaidi and
• Ulf Diederichsen

Beilstein J. Org. Chem. 2012, 8, 1576–1583, doi:10.3762/bjoc.8.180

• N-terminal amino group at the activated carbonyl group provided cleavage of the cyclized β-tripeptide from the resin. Purification did not require any chromatography since organization by intermolecular hydrogen bonding resulted in decreased solubility and precipitation of the β-tripeptide template

• ]-cycloaddition under mild conditions. The template approach allows for the preparation of constructs that, e.g., combine biological activity, fluorescence labelling and cell-penetrating or cell-directing units in one molecule to be used for in vivo studies. The defined spatial organization of recognition units

Restructuring polymers via nanoconfinement and subsequent release

• Alan E. Tonelli

Beilstein J. Org. Chem. 2012, 8, 1318–1332, doi:10.3762/bjoc.8.151

• consequence of the structural organization of the polymer–host-ICs. Polymer chains in host-IC crystals are confined to occupy narrow channels (diameter ~0.5–1.0 nm) formed by the small-molecule hosts around the included guest polymers during IC crystallization. This results in the separation and high

• . In this review we summarize the behaviors and uses of coalesced polymers, and attempt to draw conclusions on the relationship between their behavior and the organization/structures/conformations of the constituent polymer chains achieved upon coalescence from their ICs. Keywords: cyclodextrins

• ; inclusion compounds; nanoconfinement; organization; polymers; properties; release; urea; Introduction The behaviors and properties of polymer materials are closely related to the organizations, structures, and morphologies of their constituent chains, which can be significantly altered during their

Design of a novel tryptophan-rich membrane-active antimicrobial peptide from the membrane-proximal region of the HIV glycoprotein, gp41

• Evan F. Haney,
• Leonard T. Nguyen,
• David J. Schibli and
• Hans J. Vogel

Beilstein J. Org. Chem. 2012, 8, 1172–1184, doi:10.3762/bjoc.8.130

• not disrupt bilayer organization in neutral liposomes to the same extent as gp41w or gp41w-4R (Figure 4C). Differential scanning calorimetry The gp41w derivatives were added to 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (DPPG) lipid

• added to the DPPC lipid suspensions, the resulting thermograms showed that these peptides had very drastic effects on the organization of DPPC bilayers (Figure 5). The final heating scan of gp41w-4R mixed with DPPC phospholipids shows a sharp transition at ~36 °C with a broad shoulder between 37–40 °C

• formation of peptide–lipid aggregates. The addition of gp41w-4R to DPPG yields peaks in the thermogram at 33 and 36 °C, suggesting that when gp41w-4R binds to negatively charged liposomes, it destabilizes the organization of the bilayer. Apparently, some unbound DPPG remains as well because there is still a

Control over molecular motion using the cis–trans photoisomerization of the azo group

• Estíbaliz Merino and
• María Ribagorda

Beilstein J. Org. Chem. 2012, 8, 1071–1090, doi:10.3762/bjoc.8.119

• conformational changes in polymers. There may also be variations in the organization of large assemblies of molecules in gels or liquid crystals. When polarized light is used, the photoisomerization often induces a reorganization of chromophores that can be reflected in the circular dichroism spectra. The basic