Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid

• Anna Wrona-Piotrowicz,
• Janusz Zakrzewski,
• Anna Gajda,
• Tadeusz Gajda,
• Anna Makal,
• Arnaud Brosseau and
• Rémi Métivier

Beilstein J. Org. Chem. 2015, 11, 2451–2458, doi:10.3762/bjoc.11.266

• , apart from the H1 atom which was involved in intermolecular hydrogen bond formation. (a) Dimers of π-stacked and hydrogen-bonded molecules of 3a represented in single figures; (b) network of weak C–H…O and C–H…π interactions stabilizing H-bonded dimer strings and (c) crystal packing along the

Preparation of Pickering emulsions through interfacial adsorption by soft cyclodextrin nanogels

• Shintaro Kawano,
• Toshiyuki Kida,
• Mitsuru Akashi,
• Hirofumi Sato,
• Motohiro Shizuma and
• Daisuke Ono

Beilstein J. Org. Chem. 2015, 11, 2355–2364, doi:10.3762/bjoc.11.257

• concentration (0.1 wt %), forming stable oil-in-water emulsions through interfacial adsorption by the CD nanogels. Conclusion: Soft CD nanogel particles adsorb at the oil–water interface with an effective coverage by forming a strong interconnected network and form a stable Pickering emulsion. The adsorption

• a good colloidal stability in water. Figure 2 shows the 1H NMR spectra of the DM-β-CD/PDI polymer and DM-β-CD. The peaks of the DM-β-CD and 1,4-phenylene dicarbamyl (PDC) segments are broadened due to the restricted movement of the network linkage of the polymer. The integral ratio of the peaks for

• is observed in the magnified image due to the fusion of CD nanogel particles (Figure 8B). The spherical CD nanogel particles are easily inter-penetrable [21] and may form a dense interconnected network (Figure 8B). The strong connectivity results in an interfacial layer, which effectively protects

Life lessons

• Jonathan R. Nitschke

Beilstein J. Org. Chem. 2015, 11, 2350–2354, doi:10.3762/bjoc.11.256

• group and I hope to address over the next few years include: How can we design a system of chemical assemblies to work together in a network, to accomplish a function collectively? Given that increasingly fine-grained control over self-assembled structure is being achieved, how can we design a self

Synthesis, structure, and mechanical properties of silica nanocomposite polyrotaxane gels

• Kazuaki Kato,
• Daisuke Matsui,
• Koichi Mayumi and
• Kohzo Ito

Beilstein J. Org. Chem. 2015, 11, 2194–2201, doi:10.3762/bjoc.11.238

• by a novel network formed using cyclodextrin-based polyrotaxanes. Covalent bond formation between the cyclic components of polyrotaxanes and the surface of silica nanoparticles (15 nm diameter) resulted in an infinite network structure without direct bonds between the main chain polymer and the

• not occur without silica. This suggests that the silica nanoparticles behave as cross-linkers. Viscoelastic measurements of the nanocomposite gels showed no stress relaxation regardless of the silica content for <20% compression strain, indicating an infinite stable network without physical cross

• -links that have finite lifetime. On the other hand, the infinite network exhibited an abnormally low Young’s modulus, ~1 kPa, which is not explainable by traditional rubber theory. In addition, the composite gels were tough enough to completely maintain the network structure under 80% compression strain

Polythiophene and oligothiophene systems modified by TTF electroactive units for organic electronics

• Alexander L. Kanibolotsky,
• Neil J. Findlay and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1749–1766, doi:10.3762/bjoc.11.191

• units into a conjugated network is a standard way to narrow the HOMO/LUMO band gap and examples of such units include dioxopyrrolopyrrole (DPP) [17][18][19], benzodifuranone [20] and boron-dipyrromethene (BODIPY) [21][22]. As a different class of electroactive materials, TTF derivatives are well-known

Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions

• Paul P. Kelly,
• Anja Eichler,
• Susanne Herter,
• David C. Kranz,
• Nicholas J. Turner and
• Sabine L. Flitsch

Beilstein J. Org. Chem. 2015, 11, 1713–1720, doi:10.3762/bjoc.11.186

• . Threonines in libraries II and III were often substituted for Phe, Gly or aliphatic side chains. The OH group was also frequently preserved by substitution with Ser, which in library V was always the case. Thr252 (library V) is involved in a proton relay network that promotes O–O bond scission during

Thermal properties of ruthenium alkylidene-polymerized dicyclopentadiene

• Yuval Vidavsky,
• Yotam Navon,
• Yakov Ginzburg,
• Moshe Gottlieb and
• N. Gabriel Lemcoff

Beilstein J. Org. Chem. 2015, 11, 1469–1474, doi:10.3762/bjoc.11.159

• long periods of time is highly improbable. As mentioned before, we hypothesized that the exothermic signal reemerged due to secondary metathesis reactions which can occur after polymer relaxation and repositioning of the active ruthenium alkylidene within the cross-linked polymer network. To validate

Tetrathiafulvalene-based azine ligands for anion and metal cation coordination

• Awatef Ayadi,
• Aziz El Alamy,
• Olivier Alévêque,
• Magali Allain,
• Nabil Zouari,
• Mohammed Bouachrine and
• Abdelkrim El-Ghayoury

Beilstein J. Org. Chem. 2015, 11, 1379–1391, doi:10.3762/bjoc.11.149

• form a stack along a-axis through S···S contacts (d(S···S) being between 3.70(6) and 3.90(7) Å) resulting into a 3D supramolecular network. The UV–visible absorption spectrum of the rhenium complex 3 recorded in a mixture of dichloromethane/acetonitrile (9:1, v/v) at room temperature (c 1.1 × 10−4 M

Are D-manno-configured Amadori products ligands of the bacterial lectin FimH?

• Tobias-Elias Gloe,
• Insa Stamer,
• Cornelia Hojnik,
• Tanja M. Wrodnigg and
• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2015, 11, 1096–1104, doi:10.3762/bjoc.11.123

• interactions between the FimH tyrosine gate and Amadori product 10. The effect of tilting of Amadori products 9 and 10 upon FimH complexation can also be analyzed by comparison of hydrogen bonding in the complex. Close inspection of the H-bond network reveals that the average length of H-bonds established with

• docked 2D-cartoons of MeMan (1, left) and the Amadori product 9 (right). The bottom cartoons are deduced from the docking result illustrating the predicted hydrogen bond network between amino acid side chains and the sugar hydroxy groups (not to scale). The Amadori rearrangement of aldoses with amines

Synthesis of photoresponsive cholesterol-based azobenzene organogels: dependence on different spacer lengths

• Yuchun Ren,
• Bin Wang and
• Xiuqing Zhang

Beilstein J. Org. Chem. 2015, 11, 1089–1095, doi:10.3762/bjoc.11.122

• the aggregates change from flower-like, network and rod with different sizes. By using IR and XRD characterization, it is found that intermolecular H-bonding, the solvents and van der Waals interaction are the main contributions to the specific superstructure. Keywords: azobenzene; cholesterol

• in different solvents were studied by SEM (Figure 4). With the reference to the images, it can be clearly seen that the structures of the three gelators are significantly different from each other. The morphologies of the aggregates change from flower-like to network and rod with different sizes

• . Obviously, the gel from ethanol mainly shows a similar flower-like morphology. When we focused on the isopropanol xerogel, we could see that there are many regularly three-dimensional network structures. In 1-butanol, the organogelator molecules in the gel phase were self-assembled into tightly staked rods

Donor–acceptor type co-crystals of arylthio-substituted tetrathiafulvalenes and fullerenes

• Xiaofeng Lu,
• Jibin Sun,
• Shangxi Zhang,
• Longfei Ma,
• Lei Liu,
• Hui Qi,
• Yongliang Shao and
• Xiangfeng Shao

Beilstein J. Org. Chem. 2015, 11, 1043–1051, doi:10.3762/bjoc.11.117

• form the 3D network of the present co-crystals. As shown in Figure S30 Supporting Information File 1, one A molecule is surrounded by five B molecules, and one B molecule is surrounded by five A molecules. There are multiple C–C close contacts (3.20–3.38 Å) between the neighboring C70 molecules along

• least one of the fullerene molecules. Moreover, the dimensionality of the packing motifs of fullerene molecules increases, resulting in a 2D network through multiple van der Waals forces. Upon further increase of the ratio of fullerene molecules in the co-crystal (e.g., 2·(C70)4·(PhCl)2), the packing

• structure becomes dominated by the C70 molecule, which forms the 3D network. The Ar-S-TTF and solvent molecules serve as the guests to occupy the void formed by the C70 molecules. The present results demonstrate that Ar-S-TTF molecules have three key features that enable formation of donor–acceptor type co

Synthesis and characterization of the cyanobenzene-ethylenedithio-TTF donor

• Sandrina Oliveira,
• Dulce Belo,
• Isabel C. Santos,
• Sandra Rabaça and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 951–956, doi:10.3762/bjoc.11.106

• spectra, ESI-QIT/MS is part of RNEM – Portuguese Mass Spectrometry Network, supported by Fundação para a Ciência e a Tecnologia (FCT). Work partially supported by FCT (Portugal) through contract PTDC/QEQ-SUP/1413/2012, contract RECI/QEQQIN/0189/2012 and contract UID/Multi/04349/2013 project.

Regulation of integrin and growth factor signaling in biomaterials for osteodifferentiation

• Qiang Wei,
• Theresa L. M. Pohl,
• Anja Seckinger,
• Joachim P. Spatz and
• Elisabetta A. Cavalcanti-Adam

Beilstein J. Org. Chem. 2015, 11, 773–783, doi:10.3762/bjoc.11.87

• virtually all cells in the body are exposed to and stem cells reside in, is an essential component in the stem cell niche [3]. The ECM is not an inert scaffold; instead, it is a dynamic network of molecules secreted by cells. Moreover, its biochemical, biophysical, and mechanical properties have emerged as

• , which can stimulate cell growth and differentiation, have also been employed for bone treatment [8][9]. Growth factors are water soluble proteins embedded in the ECM network mainly via non-covalent interactions with glycosaminoglycanes (GAG) [10]. Therefore, the ECM serves as a reservoir by establishing

Probing multivalency in ligand–receptor-mediated adhesion of soft, biomimetic interfaces

• Stephan Schmidt,
• Hanqing Wang,
• Daniel Pussak,
• Simone Mosca and
• Laura Hartmann

Beilstein J. Org. Chem. 2015, 11, 720–729, doi:10.3762/bjoc.11.82

• synthetic strategy allows for straightforward variation in grafting density and grafting length enabling the controlled presentation of mannose units on the PEG network. Finally we determined the specific adhesion of PEG-network-conjugated mannose units on ConA surfaces as a function of density and grafting

• and Discussion PEG-microgel synthesis and carboxylic acid grafting We started out synthesizing carboxylic acid-functionalized PEG particles with varying functionalization degree by grafting three types of carboxylic acid monomers to the PEG network: methacrylic acid (MA), acrylic acid (AA) and

• the radicals formed on the PEG network. The amount of radicals formed on the PEG chain is not affected by the presence of CA, but rather by the benzophenone concentration which was kept constant so far. Therefore, we varied the benzophenone concentration from 60 mmol/L to 420 mmol/L. From the results

Design, synthesis and photochemical properties of the first examples of iminosugar clusters based on fluorescent cores

• Mathieu L. Lepage,
• Antoine Mirloup,
• Manon Ripoll,
• Fabien Stauffert,
• Anne Bodlenner,
• Raymond Ziessel and
• Philippe Compain

Beilstein J. Org. Chem. 2015, 11, 659–667, doi:10.3762/bjoc.11.74

• International Centre for Frontier Research in Chemistry (icFRC) and doctoral fellowships from the French Department of Research to Mathieu L. Lepage and Fabien Stauffert. Antoine Mirloup thanks the Rhin-Solar EC Network supported by the European Fund for Regional Development (FEDER) in the framework of the

Natural phenolic metabolites with anti-angiogenic properties – a review from the chemical point of view

• Qiu Sun,
• Jörg Heilmann and
• Burkhard König

Beilstein J. Org. Chem. 2015, 11, 249–264, doi:10.3762/bjoc.11.28

• either anti- or pro-angiogenic activity, which are embedded together with enzymes and signaling molecules (Table 1) into a very complex network of signaling pathways [3][4]. For example, in the case of cancer development, the growing tumor disturbs the angiogenic balance in tissue and induces the

Inclusion of trans-resveratrol in methylated cyclodextrins: synthesis and solid-state structures

• Lee Trollope,
• Dyanne L. Cruickshank,
• Terence Noonan,
• Susan A. Bourne,
• Milena Sorrenti,
• Laura Catenacci and
• Mino R. Caira

Beilstein J. Org. Chem. 2014, 10, 3136–3151, doi:10.3762/bjoc.10.331

• (primary methoxy), with respective O···O distances of 2.731(6) and 2.829(7) Å. A complex network of hydrogen bonds stabilises the crystal structure; these include host–guest O–H···O and C–H···O hydrogen bonds, host–host C–H···O hydrogen bonds, guest–water and water–water O–H···O hydrogen bonds. Crystal

• hydrogen atoms of the water molecules in difference Fourier syntheses. Both disorder components of the RSV molecule engage in equivalent hydrogen bonds with the host molecule. Stabilisation of the crystal structure of TMB·RSV·5.6H2O is effected by a complex network of attractive interactions, including

Release of β-galactosidase from poloxamine/α-cyclodextrin hydrogels

• César A. Estévez,
• José Ramón Isasi,
• Eneko Larrañeta and
• Itziar Vélaz

Beilstein J. Org. Chem. 2014, 10, 3127–3135, doi:10.3762/bjoc.10.330

• network structure (Figure 2). In a previous work, the rheological behavior of poloxamine/α-CD mixtures was investigated [16]. A 10% (w/w) solution of α-CD was selected as an intermediate value between the solubility limit of this cyclodextrin (14%) and a lower limit which yields mostly solutions instead

Synthesis and characterization of pH responsive D-glucosamine based molecular gelators

• Navneet Goyal,
• Hari P. R. Mangunuru,
• Bargav Parikh,
• Sonu Shrestha and
• Guijun Wang

Beilstein J. Org. Chem. 2014, 10, 3111–3121, doi:10.3762/bjoc.10.328

• microscopy. As shown in Figure 4, the gels from the various amide derivatives typically formed a fibrous network, compound 8 formed shorter fibers (~20 μm in lengths), compound 13 formed longer fibrous assemblies (40–100 μm), and compound 11 formed long and uniform fibers with average lengths over 100 μm

First chemoenzymatic stereodivergent synthesis of both enantiomers of promethazine and ethopropazine

• Paweł Borowiecki,
• Daniel Paprocki and
• Maciej Dranka

Beilstein J. Org. Chem. 2014, 10, 3038–3055, doi:10.3762/bjoc.10.322

• its secondary structure mainly by stabilization of the internal hydrogen-bonding network in the molecule, thus improving the reactivity and selectivity of organic substrate transformations. Therefore, an appropriate medium selection in which a relatively high solubility of the phenothiazinic substrate

Synthetic strategies for the fluorescent labeling of epichlorohydrin-branched cyclodextrin polymers

• Milo Malanga,
• Mihály Bálint,
• István Puskás,
• Kata Tuza,
• Tamás Sohajda,
• László Jicsinszky,
• Lajos Szente and
• Éva Fenyvesi

Beilstein J. Org. Chem. 2014, 10, 3007–3018, doi:10.3762/bjoc.10.319

• polymeric network before the introduction of the anchoring group for the fluorescent labeling (Scheme 3). Methylated cyclodextrins have peculiar properties concerning both solubility and complex formation thus targeting a water-soluble methylated β-CD polymer with a low degree of substitution can be

• the product as shown in Supporting Information File 1, Figure S16. The tosyl-related impurities (tosic acid/tosylate) were determined by CE and the level of the impurities resulted below 0.02% w/w. The introduction of tosyl groups into the methylated polymeric network only slightly modifies the

• eventual modification of the 6-monoazido-6-monodeoxy-β-CD monomer with pendant group that do not interfere with any of the steps for the fluorescent tagging can add interesting properties to the polymeric network. The branching of 6-monoazido-6-monodeoxy-β-CD (Scheme 4) with epichlorohydrin leads to an

Mono- and multilayers of molecular spoked carbazole wheels on graphite

• Stefan-S. Jester,
• A. Vikas Aggarwal,
• Daniel Kalle and
• Sigurd Höger

Beilstein J. Org. Chem. 2014, 10, 2783–2788, doi:10.3762/bjoc.10.295

• (nominal) unit cell of a = b = 6.9 ± 0.2 nm, γ(a,b) = 60 ± 2° (red lines) is approximated. (b) A copy of the STM image shown in (a), where the centers of all MSWs are marked by red dots, and dashed lines are drawn to connect all adjacent dots, so that a network structure results, which is shown without the

Self-assembled monolayers of shape-persistent macrocycles on graphite: interior design and conformational polymorphism

• Joscha Vollmeyer,
• Friederike Eberhagen,
• Sigurd Höger and
• Stefan-S. Jester

Beilstein J. Org. Chem. 2014, 10, 2774–2782, doi:10.3762/bjoc.10.294

• . Thereby the coordination numbers of the molecules – defined as the directions along which the side chains stabilize the network [15] – are reduced from six in polymorph A (Figure 4a–c, Figure 5a–d) to two in polymorph B (Figure 4d–f, Figure 5e). Both supramolecular patterns are closely related to their

Anomalous diffusion of Ibuprofen in cyclodextrin nanosponge hydrogels: an HRMAS NMR study

• Monica Ferro,
• Franca Castiglione,
• Carlo Punta,
• Lucio Melone,
• Walter Panzeri,
• Barbara Rossi,
• Francesco Trotta and
• Andrea Mele

Beilstein J. Org. Chem. 2014, 10, 2715–2723, doi:10.3762/bjoc.10.286

• growth of the polycondensation products leads to a statistic three-dimensional network characterized by different types of cavities, namely the apolar cavity of the CD units and the pores of the growing polymer. As previously stressed, CDNS are, in the majority of cases, completely – or almost completely

• spectroscopies [14][15][16]. CDNS are per se not soluble, due to the extended three-dimensional covalent network. However, in many cases they showed interesting swelling properties when contacted with water or water solution only, affording hydrogels. The swelling ability of CDNS depends on different factors

• confined drug inside the polymeric network, especially in the gel state. To this end, the use of high resolution magic angle spinning (HRMAS) NMR spectroscopy [20] opened the possibility of using the whole repertoire of NMR experiments to spot on the structural and dynamic properties of the drug entrapped

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

• Diego Cortizo-Lacalle,
• Calvyn T. Howells,
• Upendra K. Pandey,
• Joseph Cameron,
• Neil J. Findlay,
• Anto Regis Inigo,
• Tell Tuttle,
• Peter J. Skabara and
• Ifor D. W. Samuel

Beilstein J. Org. Chem. 2014, 10, 2683–2695, doi:10.3762/bjoc.10.283

• interpenetrating network they form within a bulk heterojunction (BHJ), has led to intense research directed towards the synthesis of conjugated polymers for bulk heterojunction organic photovoltaics (OPVs) [1][2][3]. In these devices, the conjugated polymer acts as an electron donor and a soluble fullerene, most