Ester formation at the liquid–solid interface

• Nguyen T. N. Ha,
• Thiruvancheril G. Gopakumar,
• Nguyen D. C. Yen,
• Carola Mende,
• Lars Smykalla,
• Maik Schlesinger,
• Roy Buschbeck,
• Tobias Rüffer,
• Heinrich Lang,
• Michael Mehring and
• Michael Hietschold

Beilstein J. Nanotechnol. 2017, 8, 2139–2150, doi:10.3762/bjnano.8.213

• perpendicular to surface according to Nath et al. [26][27]. The geometric parameters obtained from the simulations fit fairly well with the experiments, except for β (see Supporting Information File 1 for details). It has been shown that alkyl chains organize on HOPG in a zig-zag manner at well-defined sites

• the TMA head groups and blue lines indicate alkyl chains of synthesized monoester molecules. The orientation of the alkyl chain adopts an angle of ≈2° with respect to the A axis (indicated as β in other images). According to the calculation it is expected that the alkyl chain of synthesized monoester

Application of visible-light photosensitization to form alkyl-radical-derived thin films on gold

• Rashanique D. Quarels,
• Xianglin Zhai,
• Neepa Kuruppu,
• Jenny K. Hedlund,
• Ashley A. Ellsworth,
• Amy V. Walker,
• Jayne C. Garno and
• Justin R. Ragains

Beilstein J. Nanotechnol. 2017, 8, 1863–1877, doi:10.3762/bjnano.8.187

• , alkyl radicals from solution (in addition to crosslinking) will result in the formation of branched alkyl chains and multilayer formation. Our ongoing studies will demonstrate, inter alia, the functional group tolerance of this method. Nanopores within a film of Au–Me on Au(111) produced using immersion

Synthesis, spectroscopic characterization and thermogravimetric analysis of two series of substituted (metallo)tetraphenylporphyrins

• Rasha K. Al-Shewiki,
• Carola Mende,
• Roy Buschbeck,
• Pablo F. Siles,
• Oliver G. Schmidt,
• Tobias Rüffer and
• Heinrich Lang

Beilstein J. Nanotechnol. 2017, 8, 1191–1204, doi:10.3762/bjnano.8.121

• [26]. Furthermore, a single δs(C–H) absorption verifies that the CH3 group belongs to an aliphatic chain that is not branched, or that the Me group is terminal as in the –NMe2 entities of 2/2a–d. For branched alkyl chains the δs(C–H) vibration splits into two [26]. Thus, the absorptions no. 30 and no

The role of 2D/3D spin-polarization interactions in hybrid copper hydroxide acetate: new insights from first-principles molecular dynamics

• Ziyad Chaker,
• Guido Ori,
• Mauro Boero and
• Carlo Massobrio

Beilstein J. Nanotechnol. 2017, 8, 857–860, doi:10.3762/bjnano.8.86

• ; pressure; spin polarization; Introduction Copper hydroxide acetate Cu2(OH)3CH3COO·H2O (CuOHAc) is the precursor of a whole class of hybrid organic–inorganic materials that are made of inorganic sheets separated by alkyl chains (such as alkyl sulfates and carboxylates) or conjugated molecules (such as

Formation and shape-control of hierarchical cobalt nanostructures using quaternary ammonium salts in aqueous media

• Ruchi Deshmukh,
• Anurag Mehra and
• Rochish Thaokar

Beilstein J. Nanotechnol. 2017, 8, 494–505, doi:10.3762/bjnano.8.53

• proposed based on the fact that the radius of gyration of NH4+ is 0.90 Å [41], whereas the radius of gyration and the ionic radius of TMA+ are larger, namely, 1.93 Å and 2.9 Å, respectively [41][42]. The shape of the anisotropic cobalt nanostructures was next controlled by using additives with longer alkyl

• chains, TEAH and TBAH. As the length of the alkyl chain increases, the dissociation of OH− ions decreases and affects the morphology thus achieved. The use of TEAH and TBAH generates particles with distinct surface topology and crystalline properties. Using TEAH, small nanoplates of approximately 50–70

Methods for preparing polymer-decorated single exchange-biased magnetic nanoparticles for application in flexible polymer-based films

• Laurence Ourry,
• Delphine Toulemon,
• Souad Ammar and
• Fayna Mammeri

Beilstein J. Nanotechnol. 2017, 8, 408–417, doi:10.3762/bjnano.8.43

• the catalyst. The length of the carbon backbone of the initiator (between phosphate and α-bromo-ester functions) is very important to the ATRP polymerization rate when initiators are directly anchored to the particle surface. Sunday et al. [36] reported that long alkyl chains (16 carbon atoms) or

Optical absorption signature of a self-assembled dye monolayer on graphene

• Tessnim Sghaier,
• Sylvain Le Liepvre,
• Céline Fiorini,
• Ludovic Douillard and
• Fabrice Charra

Beilstein J. Nanotechnol. 2016, 7, 862–868, doi:10.3762/bjnano.7.78

• , we chose an alkylated form of this dye, N,N′-ditridecylperylene-3,4,9,10-tetracarboxylic diimide (PTCDI-C13), in order to take advantage of the interactions between n-alkyl chains and graphitic substrates for forming a spontaneously self-assembled monolayer at the interface between the solution and

• a finite number of lattice orientations, indicating an epitaxial relationship with the graphitic lattice. These results are fully consistent with the expected formation of a self-assembled monolayer in which the molecules are lying flat on the substrate, with adsorbed n-alkyl chains aligned on the C

• changes of the optical bandgap. However, alkyl chains present here should reduce such interactions by maintaining the conjugated moiety at a larger distance from graphene. This is substantiated by the preservation of the absorption line-shape and the balance between vibronic contributions. This also means

Rigid multipodal platforms for metal surfaces

• Michal Valášek,
• Marcin Lindner and
• Marcel Mayor

Beilstein J. Nanotechnol. 2016, 7, 374–405, doi:10.3762/bjnano.7.34

• formed by the adsorption of normal n-alkylthiols 5 and bidentate analogues 3, 4 having similar chain lengths, to provide systematic control in packing density (Figure 2). The comparison showed that the SAMs of tridentate adsorbate 2 have lower packing densities of alkyl chains than the SAMs of bidentate

• observed for the ferrocene-terminated adamantane 19. This is in contrast to the fact that n-alkanethiols form closely packed SAMs, in which flexible alkyl chains are fixed at a linear conformation to maximize the intermolecular affinity. Recently Weidner and co-workers presented a study of adamantane-based

• according to the XPS, NEXAFS spectroscopy, and sum frequency generation (SFG) spectroscopy measurements. Also, the calculated thickness based on the XPS data is in agreement with monolayer coverage. The perpendicular orientation and scope of spatial alignment for different alkyl chains exhibit that lateral

Characterisation of thin films of graphene–surfactant composites produced through a novel semi-automated method

• Nik J. Walch,
• Alexei Nabok,
• Frank Davis and
• Séamus P. J. Higson

Beilstein J. Nanotechnol. 2016, 7, 209–219, doi:10.3762/bjnano.7.19

• films of graphene-surfactant composites Langmuir–Blodgett and Langmuir–Schaefer deposition Both composite materials obtained, e.g., graphene(+)CTAB and graphene(−)SDS, appeared to be soluble in water due to the presence of ionic groups, NMe3+ and SO3−, respectively. Yet, the presence of alkyl chains and

• adding surface tension sensors to control the amount of surfactant being added to the reactor, thus maintaining a constant and optimum surface tension. The formation of individual graphene flakes and the interaction of alkyl chains of the surfactants with graphene were, respectively, confirmed with Raman

Orthogonal chemical functionalization of patterned gold on silica surfaces

• Francisco Palazon,
• Didier Léonard,
• Thierry Le Mogne,
• Francesca Zuttion,
• Céline Chevalier,
• Magali Phaner-Goutorbe,
• Éliane Souteyrand,
• Yann Chevolot and
• Jean-Pierre Cloarec

Beilstein J. Nanotechnol. 2015, 6, 2272–2277, doi:10.3762/bjnano.6.233

• ] or other [27][28] self-assembled monolayers may provide a higher diversity of potential biomolecules to immobilize. Shorter spacer chains (e.g., short alkyl chains) may also be useful to immobilize the target as close to the metal surface (i.e., the maximum intensity of the evanescent field) as

Optimized design of a nanostructured SPCE-based multipurpose biosensing platform formed by ferrocene-tethered electrochemically-deposited cauliflower-shaped gold nanoparticles

• Wicem Argoubi,
• Maroua Saadaoui,
• Sami Ben Aoun and
• Noureddine Raouafi

Beilstein J. Nanotechnol. 2015, 6, 1840–1852, doi:10.3762/bjnano.6.187

• recent works support the fact the electron-transfer rates can be enhanced by the conformational changes especially of long alkyl chains and biomolecules used to tether ferrocene to a gold surface [31][32][33][34]. The current variation stopped at high concentration because of the saturation of all the

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

• Ping Du,
• David Bléger,
• Fabrice Charra,
• Vincent Bouchiat,
• David Kreher,
• Fabrice Mathevet and
• André-Jean Attias

Beilstein J. Nanotechnol. 2015, 6, 632–639, doi:10.3762/bjnano.6.64

• controlling supramolecular chemistry on surfaces, the interdigitation of alkyl chains was chosen because graphite surfaces such as HOPG exhibit a high affinity for n-alkane chains which form close-packed 2D lamellae described by the Groszek model [27]. This is due to the close match between the intra- and

• inter-chain distances and the graphite lattice parameters. More precisely, a new functional group, also called a “molecular clip”, was designed in order to mimic the adsorption of n-alkane chains on HOPG. This molecular unit presents two alkyl chains linked by a π-conjugated bridge. Since the distance

• between the two alkyl chains is twice the interchain distance in a well-organized n-alkane lamella, this unit acts as a supramolecular, functional linking group able to form strong, surface-assisted, intermolecular “clips” by interdigitation of the alkyl chains of two functional groups leading to the

Entropy effects in the collective dynamic behavior of alkyl monolayers tethered to Si(111)

• Christian Godet

Beilstein J. Nanotechnol. 2015, 6, 583–594, doi:10.3762/bjnano.6.60

• low energy excitations (here the n-alkyl bending vibrational mode) collected from the thermal bath. This collective dynamic behavior of alkyl chains tethered to Si is also confirmed by the asymmetric relaxation peak shape related to many-body interactions in complex systems. Keywords: admittance

• , lateral (in-plane) inhomogeneity and transverse gradient of disorder [3]. As far as disorder is concerned, in model systems made of linear alkyl chains tethered in a densely packed array, experiments and simulations indicate that a quasi-perfect order can be obtained (at least locally) at low temperature

• ] conformational changes on electron transport properties have rarely been explicitly described. In this context, this admittance spectroscopy study emphasizes a collective dynamic behavior of linear saturated (n-alkyl) chains tethered to Si(111). Dynamic properties are very sensitive to structure and conformation

Poly(styrene)/oligo(fluorene)-intercalated fluoromica hybrids: synthesis, characterization and self-assembly

• Giuseppe Leone,
• Francesco Galeotti,
• William Porzio,
• Guido Scavia,
• Luisa Barba,
• Gianmichele Arrighetti,
• Giovanni Ricci,
• Chiara Botta and
• Umberto Giovanella

Beilstein J. Nanotechnol. 2014, 5, 2450–2458, doi:10.3762/bjnano.5.254

• with the alkyl chains extending nearly parallel to the SME lamellae is in agreement with XRD data. In such a configuration the evaluated Ad value of the oligo(fluorene) can range from 0.4 to 0.5 nm2 according to the available space to extend the lateral chains, which is smaller than the SME equivalent

Spectroscopic mapping and selective electronic tuning of molecular orbitals in phosphorescent organometallic complexes – a new strategy for OLED materials

• Pascal R. Ewen,
• Jan Sanning,
• Tobias Koch,
• Nikos L. Doltsinis,
• Cristian A. Strassert and
• Daniel Wegner

Beilstein J. Nanotechnol. 2014, 5, 2248–2258, doi:10.3762/bjnano.5.234

• additional role of van der Waals forces between neighboring R3 alkyl chains for the self-assembly. (a) Energy and LDOS of calculated orbitals for C1 in the gas phase. Here, a work function of 5.1 eV was assumed. This value results from minimizing the energy differences between calculated and measured

Controlling the dispersion of supported polyoxometalate heterogeneous catalysts: impact of hybridization and the role of hydrophilicity–hydrophobicity balance and supramolecularity

• Gijo Raj,
• Colas Swalus,
• Eglantine Arendt,
• Pierre Eloy,
• Michel Devillers and
• Eric M. Gaigneaux

Beilstein J. Nanotechnol. 2014, 5, 1749–1759, doi:10.3762/bjnano.5.185

• they were deposited. Finally, we submitted the hybrid structures to an UV–ozone treatment to study the role of the alkyl chains in determining the well-defined supramolecular architectures of the organic–inorganic hybrids priorly observed. Experimental Reagents DODA (C38H80NBr, M = 630.95 g·mol−1) was

• -assembled chains of DODA (0.35 nm high), oriented at 120° were formed on HOPG (Figure 3a). The 120° angle coincides with the primitive hexagonal lattice structure of the underlying HOPG plane. Thus, the alkyl chains of the DODA are epitaxially arranged on HOPG surface. It is known that the close match of

• the C–C bond length (0.251 nm), and the crystallographic <1120> HOPG spacing (0.246 nm) favours an epitaxial growth of alkyl chains on HOPG, oriented along the <1120> lattice direction [29]. In contrast, DODA form small island structures of 1.5 nm height on mica (Figure 3b). On the hydrophilic mica

Non-covalent and reversible functionalization of carbon nanotubes

• Antonello Di Crescenzo,
• Valeria Ettorre and
• Antonella Fontana

Beilstein J. Nanotechnol. 2014, 5, 1675–1690, doi:10.3762/bjnano.5.178

• CNTs surface and dissolve both individual and bundled SWCNTs in organic solvents. The solid SWCNTs–Zn-protoporphyrin nanocomposite is readily separable from the solution and can be easily redissolved in DMF. Typical dispersants are polymers formed by repetitive units of alkyl chains and aromatic

• the assembling of SDS on the nanotube surface [63]. They discovered, through TEM analysis, that surfactants characterized by long alkyl chains, either SDS, cationic octadecyltrimethylammonium bromide (OTABr) and nitrilotriacetic acid substituted with a single lipidic saturated chain of 10, 12, 14, or

• surfactant on the individual SWCNTs (see Figure 3, arrangement C). Analogously, we have evidenced [66][67] that gemini surfactants, characterized by two alkyl chains and two polar head groups separated by a spacer in a single molecule, are relatively effective dispersants also below their CMC or at very low

Surface assembly and nanofabrication of 1,1,1-tris(mercaptomethyl)heptadecane on Au(111) studied with time-lapse atomic force microscopy

• Tian Tian,
• Burapol Singhana,
• Lauren E. Englade-Franklin,
• Xianglin Zhai,
• T. Randall Lee and
• Jayne C. Garno

Beilstein J. Nanotechnol. 2014, 5, 26–35, doi:10.3762/bjnano.5.3

• formed a monolayer in which the alkyl chains are highly disordered on the surface as compared to SAMs derived from monodentate n-alkanethiols reported from studies with sum frequency generation imaging microscopy [38]. The packing density followed the trend monodentate > bidentate > tridentate. There is

Selective surface modification of lithographic silicon oxide nanostructures by organofunctional silanes

• Thomas Baumgärtel,
• Christian von Borczyskowski and
• Harald Graaf

Beilstein J. Nanotechnol. 2013, 4, 218–226, doi:10.3762/bjnano.4.22

• ± 0.1) nm. Silane layer thicknesses that are smaller than the molecular length may be explained by a low surface coverage. If the monolayer is not densely packed, the molecules will not stand nearly upright (in all-trans conformation), but the alkyl chains will orient more parallel to the surface, which

Dimer/tetramer motifs determine amphiphilic hydrazine fibril structures on graphite

• Loji K. Thomas,
• Nadine Diek,
• Uwe Beginn and
• Michael Reichling

Beilstein J. Nanotechnol. 2012, 3, 658–666, doi:10.3762/bjnano.3.75

• alkyl chains. The nanoscale morphology is a consequence of the basic molecular geometry, where it follows that a closure to form a fibril is not always likely for the doubly substituted hydrazine. Therefore, we also observe crystallite formation. Keywords: fibrils; graphite; hydrazide; hydrazine

• Experimental section). As the alkyl chain length is known to influence column formation in the bulk, the length of alkyl chains for both molecules is kept identical such that the focus of the study is solely on the geometry/symmetry aspect [6]. In Figure 1, a wedge shape is shown superimposed on the molecular

• functionalities can efficiently stabilize structures through intermolecular hydrogen bonds. On the other hand, the alkyl chains are expected to promote self-assembly into extended structures through interchain van der Waals interactions as well as adsorption on HOPG due to their epitaxial match with the C–C bonds

Horizontal versus vertical charge and energy transfer in hybrid assemblies of semiconductor nanoparticles

• Gilad Gotesman,
• Rahamim Guliamov and
• Ron Naaman

Beilstein J. Nanotechnol. 2012, 3, 629–636, doi:10.3762/bjnano.3.72

• 0.42 [Å]−1. The value of the effective β is smaller than expected for alkyl chains (β ≈ 1 [Å]−1) and may indicate that the NPs are linked with several molecules in parallel. Since the PL signal is given in arbitrary units and since we are interested only in the ratio between signals, the absolute

Variations in the structure and reactivity of thioester functionalized self-assembled monolayers and their use for controlled surface modification

• Inbal Aped,
• Yacov Mazuz and
• Chaim N. Sukenik

Beilstein J. Nanotechnol. 2012, 3, 213–220, doi:10.3762/bjnano.3.24

• -carbon chain instead of the 11 carbons in 1a) [15][20], we reported the photoconversion of a thioacetate-decorated SAM to a sulfonated surface by UV irradiation in air. In that case, the initially deposited thioacetate-functionalized SAM had more closely packed alkyl chains (FTIR: methylene stretching

Self-assembly of octadecyltrichlorosilane: Surface structures formed using different protocols of particle lithography

• ChaMarra K. Saner,
• Kathie L. Lusker,
• Zorabel M. LeJeune,
• Wilson K. Serem and
• Jayne C. Garno

Beilstein J. Nanotechnol. 2012, 3, 114–122, doi:10.3762/bjnano.3.12

• , interactions between the end groups, interactions between the alkyl chains of the silane molecules, and the nature of the substrates [45][46]. These intramolecular interactions, along with parameters such as temperature, solvent type and trace amounts of water, present a challenge for reproducible fabrication

Surface functionalization of aluminosilicate nanotubes with organic molecules

• Wei Ma,
• Weng On Yah,
• Hideyuki Otsuka and
• Atsushi Takahara

Beilstein J. Nanotechnol. 2012, 3, 82–100, doi:10.3762/bjnano.3.10

• has been reported by our group [32]. More recently, we developed an approach for anchoring alkyl chains on an imogolite surface from aqueous solution [33]. The adsorption of molecules on the inorganic surface from aqueous solution is particularly necessary for imogolite, because imogolite nanotubes

• 0.67 nm for the freeze-dried imogolite can be assigned to the (100), (110), (001), and (211) planes of the quasi-monoclinic packing of the synthetic imogolite nanotubes [24]. For DDPO4-imogolite, the broad diffraction around q = 13.8 nm−1 is probably due to the disordered grafted alkyl chains. The

Self-assembled monolayers and titanium dioxide: From surface patterning to potential applications

• Yaron Paz

Beilstein J. Nanotechnol. 2011, 2, 845–861, doi:10.3762/bjnano.2.94

• situation may prevail also with SAMs having long alkyl chains, whose outer groups are located far from the substrate and in which multiple intermolecular van-der-Waals (VdW) interactions play a larger role. The high solubility of polysiloxanes in CO2 led researchers to study the silanization of titanium

• , yielding a tilt angle of the alkyl chains of 21° relative to the surface normal. It should be noted that the uniform growth mechanism is considered to be typical for molecules that do not cross link (such as Si(CH3)2-Cl for example) [15], hence it may imply that this was the case also with the

• compared with alkyl isocyanate SAMs on SiO2. Similar to other SAMs on many substrates, the longer the alkyl chains were, the more stable were the SAMs, by virtue of a larger number of VdW interactions. TiO2 grown on SAMs There are quite a large number of manuscripts describing the growth of titanium