Interactions between shape-persistent macromolecules as probed by AFM

• Johanna Blass,
• Jessica Brunke,
• Franziska Emmerich,
• Cédric Przybylski,
• Vasil M. Garamus,
• Artem Feoktystov,
• Roland Bennewitz,
• Gerhard Wenz and
• Marcel Albrecht

Beilstein J. Org. Chem. 2017, 13, 938–951, doi:10.3762/bjoc.13.95

• well as the silicon AFM tip, were first functionalized by a polysiloxane monolayer bearing isothiocyanate groups, which smoothly react with amines forming stable thiourea links [48]. Monolayers of β-CD or β-CD-polymer were obtained by attachment of monoamino β-CD or amino-modified CD polymer 12

• 5 nm corresponds to the combined height of the monolayers on tip and surface, each of about 2.5 nm. The typical rupture length for the CD–12 configuration is 10 nm, while it is 29 nm for the 12–CD configuration. The difference in maximum rupture length indicates a difference in the detachment

• interconnected by ditopic guest molecules require about five times higher separation energies than those functionalized with conventional CD monolayers. This significant enhancement of adhesion can be attributed to a strong cooperative effect favored by the rigidity of the polymer backbone and the regular

Sulfamide chemistry applied to the functionalization of self-assembled monolayers on gold surfaces

• Loïc Pantaine,
• Vincent Humblot,
• Vincent Coeffard and
• Anne Vallée

Beilstein J. Org. Chem. 2017, 13, 648–658, doi:10.3762/bjoc.13.64

• Surface, UMR CNRS 7197, 4 place Jussieu, 75005 Paris, France Université de Nantes, CNRS, CEISAM, UMR 6230, Faculté des Sciences et des Techniques, rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France 10.3762/bjoc.13.64 Abstract Aniline-terminated self-assembled monolayers (SAMs) on gold surfaces

• have successfully reacted with ArSO2NHOSO2Ar (Ar = 4-MeC6H4 or 4-FC6H4) resulting in monolayers with sulfamide moieties and different end groups. Moreover, the sulfamide groups on the SAMs can be hydrolyzed showing the partial regeneration of the aniline surface. SAMs were characterized by water

• contact angle (WCA) measurements, Fourier-transform infrared reflection absorption spectroscopy (IRRAS) and X-ray photoelectron spectroscopy (XPS). Keywords: gold surfaces; hydrolysis; IRRAS; reversibility; SAM; sulfamide; XPS; Introduction Self-assembled monolayers (SAMs) have raised considerable

Interactions between cyclodextrins and cellular components: Towards greener medical applications?

• Loïc Leclercq

Beilstein J. Org. Chem. 2016, 12, 2644–2662, doi:10.3762/bjoc.12.261

• monolayers [57] or liposome bilayers [60]. For instance, a typical paper has been published in 2001 by Leventis and Silvius [60]. In order to characterize the CDs capacity to bind cholesterol, the authors examined the catalytic transfer of cholesterol between liposomes composed of 1-stearoyl-2-oleoyl

Thiophene-forming one-pot synthesis of three thienyl-bridged oligophenothiazines and their electronic properties

• Dominik Urselmann,
• Konstantin Deilhof,
• Bernhard Mayer and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2016, 12, 2055–2064, doi:10.3762/bjoc.12.194

• to form self-assembled monolayers on gold [69][70][71] as well as on zinc and iron oxide surfaces [72]. Conceptually, thienyl-bridged oligophenothiazines can be considered as a novel type of structurally well-defined electron-rich oligophenothiazine–thiophene hybrids (Figure 1). Thereby, the strong

Organic chemistry meets polymers, nanoscience, therapeutics and diagnostics

• Vincent M. Rotello

Beilstein J. Org. Chem. 2016, 12, 1638–1646, doi:10.3762/bjoc.12.161

• adsorbed into the cationic monolayers of nanoparticles [39], and even photoactivatable drug [40] and DNA release [41]. When we started looking at how particles interact with proteins, however, very little was known about how these materials would play together. We found out pretty quickly that the answer

Optimized methods for preparation of 6^I-(ω-sulfanyl-alkylene-sulfanyl)-β-cyclodextrin derivatives

• Eva Bednářová,
• Simona Hybelbauerová and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2016, 12, 349–352, doi:10.3762/bjoc.12.38

• -cyclodextrins (β-CD-S-X-SH) – which can be attached to a gold surface [9][10] or a polydopamine-coated surface [11]. It has been already described that the surface coverage of self-assembled monolayers of CD derivatives on gold depends substantially on the linker between the sulfanyl group and the CD

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

• top layer (Figure 7C-1) and the bottom substrate (Figure 7C-2) is about 46 nm, suggesting that the original nanogel particles (30 to 50 nm in diameter) self-assemble at the oil–water interface to form interconnected monolayers. Hence, the Pickering emulsion should be fabricated from the monolayer

Thiazole-induced rigidification in substituted dithieno-tetrathiafulvalene: the effect of planarisation on charge transport properties

• Rupert G. D. Taylor,
• Joseph Cameron,
• Iain A. Wright,
• Neil Thomson,
• Olena Avramchenko,
• Alexander L. Kanibolotsky,
• Anto R. Inigo,
• Tell Tuttle and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1148–1154, doi:10.3762/bjoc.11.129

• transistors (OFETs) Compounds 1 and 2 were used in the fabrication of bottom-gate bottom-contact OFETs to give an indication on the applicability of these small molecules to organic semiconductor devices. The use of self-assembled monolayers (SAMs) was investigated with pentafluorobenzenethiol (PFBT) and

• solutions in dichloromethane. Optimised structures of 1 (left), 2 (centre) and 3 (right). Output characteristics of OFETs fabricated using compound 2 in CHCl3 with OTS (top) and PFBT/OTS (bottom) as self-assembled monolayers. AFM images of OFET devices fabricated using compound 2 in CHCl3 with OTS (left

Single-molecule conductance of a chemically modified, π-extended tetrathiafulvalene and its charge-transfer complex with F₄TCNQ

• Raúl García,
• M. Ángeles Herranz,
• Edmund Leary,
• M. Teresa González,
• Gabino Rubio Bollinger,
• Marius Bürkle,
• Linda A. Zotti,
• Yoshihiro Asai,
• Fabian Pauly,
• Juan Carlos Cuevas,
• Nicolás Agraït and
• Nazario Martín

Beilstein J. Org. Chem. 2015, 11, 1068–1078, doi:10.3762/bjoc.11.120

• ]. It is also rational to suppose that the, albeit charged, dithiole side groups of our CT complex would not strongly modify the conductance of the otherwise neutral anthracene-containing wire. Finally, we point out that recent conductive AFM measurements carried out on self-assembled monolayers of

Synthesis of tripodal catecholates and their immobilization on zinc oxide nanoparticles

• Franziska Klitsche,
• Julian Ramcke,
• Julia Migenda,
• Andreas Hensel,
• Tobias Vossmeyer,
• Horst Weller,
• Silvia Gross and
• Wolfgang Maison

Beilstein J. Org. Chem. 2015, 11, 678–686, doi:10.3762/bjoc.11.77

• formation of molecular monolayers by chemisorption of bifunctional anchor molecules. This approach depends critically on the choice of a suitable anchor group. Recently, bifunctional catecholates, inspired by mussel-adhesive proteins (MAPs) and bacterial siderophores, have received considerable interest as

• . Keywords: bifunctional anchors; catecholates; multivalency; poly(ethylene glycol); ZnO nanoparticles; Introduction An elegant approach to generate tailored materials and nanoparticles is the formation of molecular monolayers by chemisorption of bifunctional anchor molecules (Figure 1A) [1]. The

• metal surfaces in aqueous media [13]. We have recently reported non-peptidic trimeric catecholates and have demonstrated their potential to form stable molecular monolayers on bulk TiO2 and stainless steel surfaces in aqueous environment [14][15]. In the present work, we describe the synthesis of

Synthesis and surface grafting of a β-cyclodextrin dimer facilitating cooperative inclusion of 2,6-ANS

• Lars W. Städe,
• Thorbjørn T. Nielsen,
• Laurent Duroux,
• Reinhard Wimmer,
• Kyoko Shimizu and
• Kim L. Larsen

Beilstein J. Org. Chem. 2015, 11, 514–523, doi:10.3762/bjoc.11.58

• inclusion of 2,6-ANS into both cavities of the β-CD dimer. Surface grafting The β-CD dimer was grafted onto quartz slides activated for CuAAC using an in-house method for the preparation of azidosilane monolayers (unpublished results) involving vapor deposition of 3-glycidoxypropyltrimethoxysilane (GPTMS

• (d, 2H), 2.94 (d, 2H), 2.79 (t, 1H). Surface grafting: Optically transparent silica slides were preactivated with azidosilane monolayers for the CuAAC grafting by vapor deposition of GPTMS (−800 mbar, 48 h, 105 °C) in 400 mM sodium azide in PEG400 [27] for 4 h at 40 °C. Following azidolysis, the

Electrochemical oxidation of cholesterol

• Jacek W. Morzycki and
• Andrzej Sobkowiak

Beilstein J. Org. Chem. 2015, 11, 392–402, doi:10.3762/bjoc.11.45

• ]. An interesting technique for non-enzymatic sensors represents molecularly imprinted self-assembled monolayers. In this approach, the layer containing organic compounds together with cholesterol is deposited on an electrode surface. Then, the cholesterol is removed from the layer, and the oxidation

C-5’-Triazolyl-2’-oxa-3’-aza-4’a-carbanucleosides: Synthesis and biological evaluation

• Roberto Romeo,
• Caterina Carnovale,
• Salvatore V. Giofrè,
• Maria A. Chiacchio,
• Adriana Garozzo,
• Emanuele Amata,
• Giovanni Romeo and
• Ugo Chiacchio

Beilstein J. Org. Chem. 2015, 11, 328–334, doi:10.3762/bjoc.11.38

• maintenance medium (DMEM with 2% heat inactivated FCS) was used to culture the viruses. Cell viability. The cytotoxicity of the tested compounds was evaluated by measuring the effect created on cell morphology and/or cell growth (cytostatic activity). Cell monolayers were prepared in 24-well tissue culture

Properties of cationic monosubstituted tetraalkylammonium cyclodextrin derivatives – their stability, complexation ability in solution or when deposited on solid anionic surface

• Martin Popr,
• Sergey K. Filippov,
• Nikolai Matushkin,
• Juraj Dian and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2015, 11, 192–199, doi:10.3762/bjoc.11.20

• ][17][18]. This approach offers self-assembled monolayers (SAMs) which can be utilized for derivatization of gold electrodes for the construction of electrochemical sensors [19][20] or even for the development of molecular printboards [21]. These results imply that the structure of CD derivatives

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

• Malgorzata Adamkiewicz David O'Hagan Georg Hahner EaStCHEM School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST, UK 10.3762/bjoc.10.307 Abstract C11-Vinyl-terminated self-assembled monolayers (SAMs) on silica surfaces are successfully modified in C–C bond forming reactions

• with dihalocarbenes to generate SAMs, terminated with dihalo- (fluoro, chloro, bromo) cyclopropane motifs with about 30% surface coverage. Keywords: difluoro-; dichloro-; dibromomethylenecyclopropanes; dihalocarbenes; self-assembled monolayers; surface coating; Introduction Self-assembled monolayers

• incorporating functional groups (FGs) on the surface of self-assembled monolayers (SAMs), illustrated for alkylsilanes onto silica. XPS scans after reactions with a) :CBr2; b) :CCl2 and c) :CF2. In each case the upper traces are scans of C11-vinyl SAMs, and the lower traces are C18-Me-terminated SAMs each

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

• Stefan-S. Jester A. Vikas Aggarwal Daniel Kalle Sigurd Hoger Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany 10.3762/bjoc.10.295 Abstract Self-assembled monolayers of a molecular spoked wheel (a shape

• the second layer. Keywords: molecular spoked wheels; scanning tunneling microscopy; self-assembled monolayers; solid/liquid interface; template; Introduction Molecular spoked wheels (MSWs) have gained increasing interest as two-dimensional (2D) carbon-based objects of adjustable sizes [1][2][3][4][5

• differences in the molecular structures that result in different adsorption behavior. While only 2D-crystalline monolayers were observed for the more flexible precursor 1, MSW 2 forms less ordered patterns and tends to form multilayers. A characteristic stacking of the macrocycles in the second layer on top

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

• macrocycle distances are mainly determined by their size and symmetry. This is an excellent example that the graphite acts as a template for the macrocycle organization independent from their specific interior. Keywords: conformational polymorphism; self-assembled monolayers; shape-persistent macrocycles

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

• hydrolytically stable structure and support the formation of monolayers on metal oxide surfaces. [34][35][36] Especially in the case of titanium mono-, bi- or even tridentate phosphate coordination leads to exceptional strong binding that could not be achieved by mere electrostatic interaction or hydrogen

• with the surface of the titanium alloy. The stable interaction observed is also achieved by coordinative binding of the oxygen in the phosphate group, which support the formation of monolayers on the titanium [42][43]. Conclusion Covalent functionalization of DND was carried out by different paths

Lateral ordering of PTCDA on the clean and the oxygen pre-covered Cu(100) surface investigated by scanning tunneling microscopy and low energy electron diffraction

• Stefan Gärtner,
• Benjamin Fiedler,
• Oliver Bauer,
• Antonela Marele and
• Moritz M. Sokolowski

Beilstein J. Org. Chem. 2014, 10, 2055–2064, doi:10.3762/bjoc.10.213

• + ions at an energy of 1000 eV and at a sample temperature of 620 K for 30 min and subsequent annealing at 770 K for 60 min. PTCDA was purchased from Sigma-Aldrich and purified by gradient sublimation. The deposition was performed at sample temperatures of 300–450 K, using a rate of 0.2 monolayers min−1

Theoretical study of the adsorption of benzene on coinage metals

• Werner Reckien,
• Melanie Eggers and
• Thomas Bredow

Beilstein J. Org. Chem. 2014, 10, 1775–1784, doi:10.3762/bjoc.10.185

• ; dispersion correction; template; Introduction The adsorption of organic molecules on metals is of great interest since the formation of thin films and self-assembled monolayers opens the way toward a functionalization of surfaces [1][2][3][4][5][6][7][8]. The adsorbed molecules often contain an aromatic

Postsynthetic functionalization of glycodendrons at the focal point

• Thisbe K. Lindhorst and
• Katharina Elsner

Beilstein J. Org. Chem. 2014, 10, 1482–1487, doi:10.3762/bjoc.10.152

• mimetics that are amenable to a variety of applications, employing Langmuir films [16], self-assembled monolayers (SAMs) [17][18][19] or lipid bilayers [20], for example. We will eventually optimize some of the described reactions where necessary and validate the described procedures for modification of

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

• associates formed in solution corresponds to PG II. The sensitivity of routine Raman scattering method is insufficient for the work with oligoglycine monolayers, so indirect methods were used in order to attribute formed material to a PG II structure. More specifically, geometrical parameters of the layers

Molecular recognition of surface-immobilized carbohydrates by a synthetic lectin

• Melanie Rauschenberg,
• Eva-Corrina Fritz,
• Christian Schulz,
• Tobias Kaufmann and
• Bart Jan Ravoo

Beilstein J. Org. Chem. 2014, 10, 1354–1364, doi:10.3762/bjoc.10.138

• microcontact printed on epoxide-terminated self-assembled monolayers. Successive prints resulted in simple microarrays of two carbohydrates. The selectivity of the synthetic lectin was investigated by incubation on the immobilized carbohydrates. Selective binding of the synthetic lectin to immobilized NANA and

• morphology [47][48][49][50]. Therefore, the epoxide SAMs were prepared by the method of Julthongpiput et al. because well-defined monolayers of epoxides on glass and silicon substrates can be obtained by using (3-glycidoxypropyl)trimethoxysilane in toluene [42]. The successful surface modification was

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

• , in this case one of the azobenzene rings has a p-mercaptophenyl group through which it is associated with an Au(111) layer [130]. All the azobenzenes are oriented and form self-assembled monolayers (SAMs). The trans–cis isomerization process of the azobenzene unit placed in the metal layer takes

Multistep organic synthesis of modular photosystems

• Naomi Sakai and
• Stefan Matile

Beilstein J. Org. Chem. 2012, 8, 897–904, doi:10.3762/bjoc.8.102

• , that is, a boiling 5:1:1 mixture of water, 24% NH4OH and 30% H2O2, and then rinsed with bidistilled water and EtOH, and dried. Then the ITO was immersed in a 3 mM solution of initiator 2 in DMSO for 2 days. The formation of monolayers of 48 on ITO electrodes was followed by the inhibition of potassium

• ferricyanide reduction in solution, and by absorption spectroscopy (Scheme 4). The obtained monolayers of 48 were annealed for 1 h in the oven at 120 °C. These conditions are known to improve the covalent bonding between phosphonic acids and the ITO substrate [26]. The disulfide protecting groups on the