Synthesis of three-dimensional porous hyper-crosslinked polymers via thiol–yne reaction

• Mathias Lang,
• Alexandra Schade and
• Stefan Bräse

Beilstein J. Org. Chem. 2016, 12, 2570–2576, doi:10.3762/bjoc.12.252

• . Furthermore, adsorption measurements of HCPs 3 and 5 were carried out with nitrogen gas at 77 K after pre-drying for 16 h at 80 °C in vacuum. Both HCPs showed BET-surface areas >400 m2/g and the values of the specific surface area and cumulative volumes of the HCPs are collected in Table 2. The corresponding

• adsorption isotherms are depicted in Figure 4. The strong slope of the isotherms at low relative pressures indicates a permanent porous character of the materials. Also the step around p/p0 = 0.5 at desorption isotherms (Supporting Information File 1, Figures S1 and S2) indicates the mesoporous character of

• -ray diffraction (PXRD) and adsorption measurements using nitrogen at 77 K. IR-spectra of tetrathiol 2 (blue), tetraalkyne 1 (red) and HCP 3 (black). IR-spectra of tetrathiol 2 (blue), hexaalkyne 4 (red) and HCP 3 (black). SEM images of HCP 3 (left) and HCP 5 (right). Adsorption isotherms of HCP 3

Robust C–C bonded porous networks with chemically designed functionalities for improved CO₂ capture from flue gas

• Damien Thirion,
• Joo S. Lee,
• Ercan Özdemir and
• Cafer T. Yavuz

Beilstein J. Org. Chem. 2016, 12, 2274–2279, doi:10.3762/bjoc.12.220

• important pore sizes (2.2, 3.0, 5.0, 7.0 nm). Larger pores are required for post-modification, as the reagents may not be able to penetrate to the small micropores. CO2 sorption isotherms reflect the physisorptive nature of COP-156 with almost no hysteresis and an isosteric heat of adsorption (Qst) of 28.1

• cm−1), which loses intensity by the post-modification reactions. Gas adsorption (filled dots)-desorption (empty dots) isotherms and pore size distribution of COP-156 (black), COP-156-amine (blue) and COP-156-amidoxime (red). CO2 uptake under moist conditions at 40 °C of COP-156 (black) and COP-156

• -amine (blue). Synthesis route for COP-156 and COP-157, and the post-modification of COP-156. BET surface area, CO2 sorption properties at 273 K, 298 K and heat of adsorption values of all networks. Supporting Information Supporting Information File 388: Materials and methods, synthesis, FTIR spectra

Hydroxy-functionalized hyper-cross-linked ultra-microporous organic polymers for selective CO₂ capture at room temperature

• Partha Samanta,
• Priyanshu Chandra and
• Sujit K. Ghosh

Beilstein J. Org. Chem. 2016, 12, 1981–1986, doi:10.3762/bjoc.12.185

• , H2 and O2 at room temperature. A high isosteric heat of adsorption (Qst) has been obtained for both materials because of strong interactions between polar –OH groups and CO2 molecules. Keywords: carbon dioxide capture; hyper-cross-linked polymer; metal-organic framework; microporous organic polymer

• temperatures (273 K and 298 K) gas (CO2, N2, H2 and O2) adsorption experiments were carried out for both compounds. HCP-91 and HCP-94 showed selective CO2 capture at both temperatures over other flue gases. Results and Discussion For the synthesis of HCP-91 and HCP-94, we used 4-phenylphenol and 9

• , a clear capsule-type of morphology was found in the FESEM (Figure 2d and Figure S6). After all characterizations and proper desolvation of both compounds, we investigated their porosity. First, we measured the N2 adsorption at 77 K. The N2 uptake for HCP-91 was found to be 595 mL/g, whereas that for

Cross-linked cyclodextrin-based material for treatment of metals and organic substances present in industrial discharge waters

• Élise Euvrard,
• Nadia Morin-Crini,
• Coline Druart,
• Justine Bugnet,
• Bernard Martel,
• Cesare Cosentino,
• Virginie Moutarlier and
• Grégorio Crini

Beilstein J. Org. Chem. 2016, 12, 1826–1838, doi:10.3762/bjoc.12.172

• hydrocarbons (PAH) and three alkylphenols (AP), the material exhibited high adsorption capacities: >99% of Co2+, Ni2+ and Zn2+ were removed, between 65 and 82% of the PAHs, as well as 69 to 90% of the APs. Due to the structure of the polymer and its specific characteristics, such as the presence of carboxylic

• groups and CD cavities, the adsorption mechanism involves four main interactions: ion exchange, electrostatic interactions and precipitation for metal removal, and inclusion complexes for organics removal. In industrial discharge waters, competition effects appeared, especially because of the presence of

• calcium at high concentrations, which competed with other pollutants for the adsorption sites of the adsorbent. Keywords: alkylphenols; adsorption; cyclodextrin; metals; polycyclic aromatic hydrocarbons; Introduction Although considerable efforts have been made by the industrial sector over the last 30

Towards potential nanoparticle contrast agents: Synthesis of new functionalized PEG bisphosphonates

• Souad Kachbi-Khelfallah,
• Maelle Monteil,
• Margery Cortes-Clerget,
• Evelyne Migianu-Griffoni,
• Jean-Luc Pirat,
• Olivier Gager,
• Julia Deschamp and
• Marc Lecouvey

Beilstein J. Org. Chem. 2016, 12, 1366–1371, doi:10.3762/bjoc.12.130

• for biomedical imaging applications, the adsorption of plasmatic proteins on the surface of nanoparticles must be prevented to reduce the hepatic capture and increase the plasmatic time life. In biologic media, metal oxide nanoparticles are not stable and must be coated by biocompatible organic

Highly stable and reusable immobilized formate dehydrogenases: Promising biocatalysts for in situ regeneration of NADH

• Barış Binay,
• Dilek Alagöz,
• Deniz Yildirim,
• Ayhan Çelik and
• S. Seyhan Tükel

Beilstein J. Org. Chem. 2016, 12, 271–277, doi:10.3762/bjoc.12.29

• using multi-point attachment strategies [18][19][20]. The immobilization mechanism of enzymes is based on the hydrophobic adsorption of enzymes onto the supports and then the covalent immobilization of enzymes. Besides, these supports are easily modified to generate new groups for the immobilization of

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

• property of CD nanogels on the droplet surface has great potential to become new microcapsule building blocks with porous surfaces. These microcapsules may act as stimuli-responsive nanocarriers and nanocontainers. Keywords: crosslinked cyclodextrin polymer; interfacial adsorption; nanogel; Pickering

• emulsion; Introduction Pickering emulsions, which are emulsions stabilized by colloidal particles instead of conventional low-molecular-weight surfactants [1], are formed through the adsorption of colloidal particles at an oil–water interface to give stable emulsion droplets. Particle adsorption, which

Ru complexes of Hoveyda–Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions

• Hynek Balcar,
• Naděžda Žilková,
• Martin Kubů,
• Michal Mazur,
• Zdeněk Bastl and
• Jiří Čejka

Beilstein J. Org. Chem. 2015, 11, 2087–2096, doi:10.3762/bjoc.11.225

• organic ligands to induce adsorption or catalytic functionalities [29][30]. The detailed structures of zeolites MCM-22, MCM-36 and MCM-56 used as supports in this work are depicted in [31][32]. Results and Discussion Hybrid catalyst preparation and characterization Immobilization of HGIIN+X complexes

• decomposition of the PF6− anion and ligand exchange at the Ru atom most likely accompanied the immobilization. The XRD and nitrogen adsorption measurements confirmed that the layered structure of the supports was preserved in the prepared hybrid catalysts. The activity of hybrid catalysts was studied (i) in RCM

• passed through a column filled with activated alumina. Nitrogen adsorption/desorption isotherms were measured on a Micromeritics GEMINI II 2370 volumetric Surface Area Analyzer at liquid nitrogen temperature (−196 °C) to determine the surface area and pore volume. Prior to the sorption measurements, all

New palladium–oxazoline complexes: Synthesis and evaluation of the optical properties and the catalytic power during the oxidation of textile dyes

• Rym Hassani,
• Mahjoub Jabli,
• Yakdhane Kacem,
• Jérôme Marrot,
• Damien Prim and
• Béchir Ben Hassine

Beilstein J. Org. Chem. 2015, 11, 1175–1186, doi:10.3762/bjoc.11.132

• PdII ions, leading to the adsorption of dyes. Moreover, the decolorization of the solution by Pd and Pd complexes has also been applied [23]. In this paper, we report the synthesis and characterization of some new palladacycles. Optical properties were determined and the catalytic activity of these

Properties of PTFE tape as a semipermeable membrane in fluorous reactions

• Brendon A. Parsons,
• Olivia Lin Smith,
• Myeong Chae and
• Veljko Dragojlovic

Beilstein J. Org. Chem. 2015, 11, 980–993, doi:10.3762/bjoc.11.110

• to some compounds, such as dimethyl phthalate, solvent adsorption to the tape altered its permeability and allowed diffusion through channels of solvent within the PTFE tape. In this case, the solvent-filled pores of the PTFE tape are chemically more akin to the adsorbed solvent rather than to the

• through PTFE tape, even if though they do not wet the tape by adsorption [32]. Finally, when peroxide in tert-butanol/water (2:1) was the oxidant and 9,10-bis(phenylethynyl)anthracene the acceptor, solvent-assisted diffusion of dimethyl phthalate was visualized (Figure 14). One can observe bright green

• solid. As mentioned earlier, the pores are estimated from scanning electron micrographs to be about 0.5 μm in size and they may change in size and number if the tape is stretched [29][31]. The non-porous nature of bulk PTFE precludes the adsorption of other materials. This may be the reason why solvents

Carboxylated dithiafulvenes and tetrathiafulvalene vinylogues: synthesis, electronic properties, and complexation with zinc ions

• Yunfei Wang and
• Yuming Zhao

Beilstein J. Org. Chem. 2015, 11, 957–965, doi:10.3762/bjoc.11.107

• properties of the coordination polymer were investigated by infrared spectroscopy, cyclic voltammetry, powder X-ray diffraction, and differential scanning calorimetric analyses. Furthermore, the microscopic porosity and surface area of the Zn-TTFV coordination polymer were measured by nitrogen gas adsorption

• structures in the solid state with certain microscopic porosity. To assess the porous properties of Zn-TTFV 8, nitrogen gas adsorption analysis was conducted at 77 K. The adsorption isotherm shown in Figure 5A indicates a Type-II adsorption behaviour. Application of the Brunauer–Emmett–Teller (BET) model

• gave a BET surface area of 148.2 m2 g−1 and an adsorption average pore diameter of 10.2 nm. The pore size distribution analysis data revealed that Zn-TTFV coordination polymer 8 carried microporosity primarily in the range of tens of nanometers. Scanning electron microscopic (SEM) imaging was performed

Terminal lipophilization of a unique DNA dodecamer by various nucleolipid headgroups: Their incorporation into artificial lipid bilayers and hydrodynamic properties

• Emma Werz and
• Helmut Rosemeyer

Beilstein J. Org. Chem. 2015, 11, 913–929, doi:10.3762/bjoc.11.103

• aforementioned experiment, the oligomer 12 is highly resistant against perfusions. After 3 perfusions, interrupted by incubation periods of 10 min each, a constant normalized bilayer brightness of about 60–65% is reached, which stays constant for more than 1 h and 6 perfusions. Figure 8 displays the adsorption

• decreasing mobility of the oligomer from position 1 < position 2 < position 3 clearly indicates a loose adsorption at the bilayer (position 2) followed by incorporation within the bilayer (position 3). Obviously, at position 2 (which is only ≈5–10 µm away from the bilayer), an attractive interaction exists

Adsorption mechanism and valency of catechol-functionalized hyperbranched polyglycerols

• Stefanie Krysiak,
• Qiang Wei,
• Klaus Rischka,
• Andreas Hartwig,
• Rainer Haag and
• Thorsten Hugel

Beilstein J. Org. Chem. 2015, 11, 828–836, doi:10.3762/bjoc.11.92

Impact of multivalent charge presentation on peptide–nanoparticle aggregation

• Daniel Schöne,
• Boris Schade,
• Christoph Böttcher and
• Beate Koksch

Beilstein J. Org. Chem. 2015, 11, 792–803, doi:10.3762/bjoc.11.89

• µM, unbound peptide could not be detected anymore whereas single and unbound nanoparticles are observed (Figure 7c). The obtained assemblies show a highly ordered adsorption of nanoparticles on the surface of the fiber in a three dimensional manner, which was supported by stereo Cryo TEM

Highly selective generation of vanillin by anodic degradation of lignin: a combined approach of electrochemistry and product isolation by adsorption

• Dominik Schmitt,
• Carolin Regenbrecht,
• Marius Hartmer,
• Florian Stecker and
• Siegfried R. Waldvogel

Beilstein J. Org. Chem. 2015, 11, 473–480, doi:10.3762/bjoc.11.53

• lignin research. So far most of the developed methods fail in technical application since no viable concept for work-up is included. This work represents a combined approach of electrochemical conversion of Kraft lignin and product recovery by adsorption on a strongly basic anion exchange resin

• acidification and precipitation of remaining lignin. The latter represents a significant advantage compared with conventional work-up protocols of lignin solutions. Keywords: adsorption; electrochemistry; lignin; nickel; renewable resources; Introduction The biopolymer lignin is one of the most abundant and

• phenolate stronger, ionic interactions usually dominate at basic pH [39]. But even under acidic conditions strong interactions between the polymer backbone and the adsorptive phase remain [40]. For this reason several commercially available resins were tested concerning their adsorption and desorption

IR and electrochemical synthesis and characterization of thin films of PEDOT grown on platinum single crystal electrodes in [EMMIM]Tf₂N ionic liquid

• Andrea P. Sandoval,
• Marco F. Suárez-Herrera and
• Juan M. Feliu

Beilstein J. Org. Chem. 2015, 11, 348–357, doi:10.3762/bjoc.11.40

• adsorption at the surface in which this vibrational mode is active. These features could mean that the consumption of anions (from the IL to inside the polymer) is directly related to the generation of positive charge, which occurs in two regions that correlate well with the peaks A1/C1 and A2/C2 observed in

Formulation development, stability and anticancer efficacy of core-shell cyclodextrin nanocapsules for oral chemotherapy with camptothecin

• Hale Ünal,
• Naile Öztürk and
• Erem Bilensoy

Beilstein J. Org. Chem. 2015, 11, 204–212, doi:10.3762/bjoc.11.22

• based on its amino groups. Coating with CS resulted in an increment in particle size due to the adsorption of CS molecules on the nanocapsule surface [34]. This coating is believed to be of importance due to the penetration enhancing properties of chitosan through the intestinal mucosa by opening of

3α,5α-Cyclocholestan-6β-yl ethers as donors of the cholesterol moiety for the electrochemical synthesis of cholesterol glycoconjugates

• Aneta M. Tomkiel,
• Adam Biedrzycki,
• Jolanta Płoszyńska,
• Dorota Naróg,
• Andrzej Sobkowiak and
• Jacek W. Morzycki

Beilstein J. Org. Chem. 2015, 11, 162–168, doi:10.3762/bjoc.11.16

• oxidation currents are approximately equal to the half of oxidation current of 6d and also other investigated compounds. This is probably caused by the electrode blocking due to an adsorption of the oxidation products. The fact that the electrochemical oxidation of 6f and 6g starts at more negative

Organic chemistry on surfaces: Direct cyclopropanation by dihalocarbene addition to vinyl terminated self-assembled monolayers (SAMs)

• Malgorzata Adamkiewicz,
• David O’Hagan and
• Georg Hähner

Beilstein J. Org. Chem. 2014, 10, 2897–2902, doi:10.3762/bjoc.10.307

• reported the formation of high quality vinyl-terminated SAMs generated from the vapour phase by adsorption of octadecyltrichlorosilanes onto silicon wafers [16]. With access to these SAMs it became an objective to explore functional group modification of the vinyl double bond. Carbon–carbon bond formation

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

• behave as more or less rigid objects of certain sizes and shapes – depending on their chemical structures. In addition, the images provide insight into the multilayer growth of the molecular spoked wheels (MSWs), where the first adlayer acts as a template for the commensurate adsorption of molecules in

• -intraannular alkoxy side chains fit (after adsorption) into the triangular cavity regions between each two spokes and the rim. Based on the observed intermolecular distances and an alignment of the alkoxy side chains along the HOPG main axis directions [10][11], an intermolecular side chain interdigitation

• octyloxy side chains are (most probably) adsorbed on the HOPG substrate in the intermolecular pores of the first layer. The results clearly indicate that not only the HOPG acts as a template for the organization of the first molecular adlayer, but the adsorption pattern is transferred to the second layer

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

• . (c) Hexagonal pattern of molecular hexagons where all alkoxy side chains are adsorbed on the substrate along the six HOPG main axis directions, d1, d2, and d3, that are defined by the arrows in (a). Backbones are shown as bold black and grey lines, and the alkoxy side chains that after adsorption

• representative of the series of 1–3 that form the same patterns), its alterable side chain interaction schemes, and the resulting pattern geometries. (a) Eight alkoxy side chains are attached to four corners of the backbone. After adsorption, four side chains align along the crystallographic main axis direction

• substrate, whereas two side chains of each molecule point towards the solution phase (black dots). The arrows in (b) define the HOPG crystallographic main axis directions d1, d2, and d3. The backbones are shown as bold black and grey lines with alkoxy side chains that after adsorption align along d1 (thin

Detonation nanodiamonds biofunctionalization and immobilization to titanium alloy surfaces as first steps towards medical application

• Juliana P. L. Gonçalves,
• Afnan Q. Shaikh,
• Manuela Reitzig,
• Daria A. Kovalenko,
• Jan Michael,
• René Beutner,
• Gianaurelio Cuniberti,
• Dieter Scharnweber and
• Jörg Opitz

Beilstein J. Org. Chem. 2014, 10, 2765–2773, doi:10.3762/bjoc.10.293

• modified titanium alloys surfaces by scanning and transmission electron microscopy. The process described shows an adsorption and immobilization of modified nanodiamonds on titanium; where aminosilanized nanodiamonds coupled with O-phosphorylethanolamine show a homogeneous interaction with the titanium

• alloy surface. Figure 4 shows the topological information of all nanodiamond entities immobilized onto Ti6Al7Nb surfaces either by adsorption to preformed anodic oxide layers (adDND), or by adsorption to air formed oxide layers followed by growth of the oxide layer by anodic polarization (anodDND

• functionalized with the phosphate group after the silanization process. These results indicate that the surface functionalization of DND is one important parameter for successful adsorption and immobilization on titanium alloy substrate. Another crucial parameter is to achieve a stable suspension of nanodiamonds

Removal of volatile organic compounds using amphiphilic cyclodextrin-coated polypropylene

• Ludmilla Lumholdt,
• Sophie Fourmentin,
• Thorbjørn T. Nielsen and
• Kim L. Larsen

Beilstein J. Org. Chem. 2014, 10, 2743–2750, doi:10.3762/bjoc.10.290

• other words, coated PP pieces were fully submerged in the water phase for the entire experiment as opposed to non-coated PP pieces which were not wettable and, therefore, only partly submerged. This made the comparison between the adsorption of the VOCs by coated and non-coated PP problematic, as the

• former was an expression of aqueous adsorption, while the latter was of gaseous adsorption. Furthermore, it has been shown that the ACD coating is equally distributed along the PP fibres [22]. Hence, it could be argued that no crude PP fibres are present in a coated PP sample and, therefore, no

• adsorption by the untreated PP itself. For these reasons, it was decided to view the adsorption of the coated PP samples as a combination of the adsorption caused by the coating together with the potential, possible adsorption of crude PP fibres (if present), and accordingly no direct comparisons were made

Synthesis of nanodiamond derivatives carrying amino functions and quantification by a modified Kaiser test

• Gerald Jarre,
• Steffen Heyer,
• Elisabeth Memmel,
• Thomas Meinhardt and
• Anke Krueger

Beilstein J. Org. Chem. 2014, 10, 2729–2737, doi:10.3762/bjoc.10.288

• samples carrying amino groups count among these) is prone to unspecific adsorption of organic molecules via hydrogen bonding and other interactions [29]. Therefore it seems reasonable to assume that the rather low amounts of hydrindantin formed upon the addition of KCN can be adsorbed on the diamond

• can be used for other nanoparticles with similar adsorption properties as well and represents a useful addition to the wet-chemical analysis of functional groups on nanomaterials. Experimental General chemicals and methods Detonation diamond has been purchased from Gansu Lingyun Corp. (Lanzhou, China

Encapsulation of biocides by cyclodextrins: toward synergistic effects against pathogens

• Véronique Nardello-Rataj and
• Loïc Leclercq

Beilstein J. Org. Chem. 2014, 10, 2603–2622, doi:10.3762/bjoc.10.273

• /polyacrylonitrile/copper nanorods composite fibers by adsorption and reduction. The composite fibers were fully characterized by FTIR, SEM, TEM, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The results indicated that the copper nanorods were not only successfully synthesized on the surface