Molecular modelling of self-assembled alkynyl monolayer structures — Unnatural symmetry units, surface bonding, and topochemical polymerization1

2003 ◽  
Vol 81 (11) ◽  
pp. 1228-1240 ◽  
Author(s):  
Adam J Dickie ◽  
Ashok K Kakkar ◽  
Michael A Whitehead
Keyword(s):  
Molecular Modelling ◽  
Self Assembled Monolayers ◽  
Head Group ◽  
Topochemical Polymerization ◽  
Assembled Monolayers ◽  
Molecular Modelling Studies ◽  
Modelling Studies ◽  
Modelling Techniques ◽  
Self Assembled ◽  
Group Structures

Geometric modelling techniques are used to map the potential energies of packing for self-assembled alkyl- and phenyl-backboned monolayers across a range of intermolecular separations. Natural packing distances of 4.2–4.4 Å produce less stable, more isotropic monolayers because of repulsive interchain contacts. Optimizations at unnatural surface densities found thin films of lower energy and higher symmetry existed at increased chain–chain separations. Head-group bonding is therefore identified as a force for controlling monolayer order. Analysis of the natural monolayer structures on a silicon dioxide surface determined the favourable head-group structures, and allowed the topochemical polymerization of p-bis(butadiynyl)benzene monolayers to be rationalized.Key words: self-assembled monolayers, molecular modelling studies, repeating symmetry units, thin-film order, topochemical polymerization.

Realizing high aspect ratio silver micro and nanostructures by microcontact printing of alkyl thiol self-assembled monolayers

MRS Advances ◽  
2019 ◽  
Vol 4 (44-45) ◽  
pp. 2441-2451
Author(s):  
Amare Benor ◽  
Asman Tamang ◽  
Veit Wagner ◽  
Alberto Salleo ◽  
Dietmar Knipp
Keyword(s):  
Aspect Ratio ◽  
Noble Metal ◽  
Microcontact Printing ◽  
Self Assembled Monolayers ◽  
Head Group ◽  
Material System ◽  
Printing Process ◽  
Aspect Ratios ◽  
Assembled Monolayers ◽  
Self Assembled

ABSTRACTThe patterning of gold and silver micro and nanostructures on rigid and flexible substrates is investigated by microcontact printed thiol based self-assembled monolayers. The aspect ratio of the noble metal micro and nanostructures is determined by interaction of the -SH head group of the CH3(CH2)19SH molecules and the surface of the noble metal. Silver micro and nanostructures with >10 times higher aspect ratios can be realized in comparison to commonly realized gold micro and nanostructures. The printing process is described, and the etching process is characterized in terms of etching window and etching selectivity. Potential electronic and photonic applications of the micro and nanostructures are discussed taking the boundary conditions of the printing process and the selected material system into consideration.

scholarly journals N.m.r. and molecular-modelling studies of the solution conformation of heparin

1993 ◽  
Vol 293 (3) ◽  
pp. 849-858 ◽  
Author(s):  
B Mulloy ◽  
M J Forster ◽  
C Jones ◽  
D B Davies
Keyword(s):  
Molecular Modelling ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Spin Lattice ◽  
Conformational Energy Calculations ◽  
Molecular Modelling Studies ◽  
Modelling Studies ◽  
Modelling Techniques ◽  
Nuclear Overhauser

The solution conformations of heparin and de-N-sulphated, re-N-acetylated heparin have been determined by a combination of n.m.r. spectroscopic and molecular-modelling techniques. The 1H- and 13C-n.m.r. spectra of these polysaccharides have been assigned. Observed 1H-1H nuclear Overhauser enhancements (n.O.e.s) have been simulated using the program NOEMOL [Forster, Jones and Mulloy (1989) J. Mol. Graph. 7, 196-201] for molecular models derived from conformational-energy calculations; correlation times for the simulations were chosen to fit experimentally determined 13C spin-lattice relaxation times. In order to achieve good agreement between calculated and observed 1H-1H n.O.e.s it was necessary to assume that the reorientational motion of the polysaccharide molecules was not isotropic, but was that of a symmetric top. The resulting model of heparin in solution is similar to that determined in the fibrous state by X-ray-diffraction techniques [Nieduszynski, Gardner and Atkins (1977) Am. Chem. Soc. Symp. Ser. 48, 73-80].

scholarly journals Unraveling the dynamics and structure of functionalized self-assembled monolayers on gold using 2D IR spectroscopy and MD simulations

2016 ◽  
Vol 113 (18) ◽  
pp. 4929-4934 ◽  
Author(s):  
Chang Yan ◽  
Rongfeng Yuan ◽  
William C. Pfalzgraff ◽  
Jun Nishida ◽  
Lu Wang ◽  
...  
Keyword(s):  
Alkyl Chain ◽  
Md Simulations ◽  
Self Assembled Monolayers ◽  
Head Group ◽  
Molecular Motions ◽  
2D Ir ◽  
Assembled Monolayers ◽  
Self Assembled ◽  
Group Density ◽  
Dynamics Simulations

Functionalized self-assembled monolayers (SAMs) are the focus of ongoing investigations because they can be chemically tuned to control their structure and dynamics for a wide variety of applications, including electrochemistry, catalysis, and as models of biological interfaces. Here we combine reflection 2D infrared vibrational echo spectroscopy (R-2D IR) and molecular dynamics simulations to determine the relationship between the structures of functionalized alkanethiol SAMs on gold surfaces and their underlying molecular motions on timescales of tens to hundreds of picoseconds. We find that at higher head group density, the monolayers have more disorder in the alkyl chain packing and faster dynamics. The dynamics of alkanethiol SAMs on gold are much slower than the dynamics of alkylsiloxane SAMs on silica. Using the simulations, we assess how the different molecular motions of the alkyl chain monolayers give rise to the dynamics observed in the experiments.

Synthesis of Disulfides Containing a Corrinoid Head Group for Preparation of Self-Assembled Monolayers

Synlett ◽  
2005 ◽  
Vol 2005 (12) ◽  
pp. 1901-1904
Author(s):  
Reinhart Keese ◽  
Joana Mendonça ◽  
Reto Luginbühl ◽  
Hans Siegenthaler
Keyword(s):  
Self Assembled Monolayers ◽  
Head Group ◽  
Assembled Monolayers ◽  
Self Assembled

Electrochemical behavior of self-assembled monolayers based on functionalized oligothiophenes

1998 ◽  
Vol 95 (6) ◽  
pp. 1339-1342 ◽  
Author(s):  
R. Michalitsch ◽  
A. El Kassmi ◽  
P. Lang ◽  
A. Yassar ◽  
F. Garnier
Keyword(s):  
Electrochemical Behavior ◽  
Self Assembled Monolayers ◽  
Assembled Monolayers ◽  
Self Assembled

Imaging of patterned self-assembled monolayers by scanning photoelectron microscopy

2003 ◽  
Vol 104 ◽  
pp. 459-462 ◽  
Author(s):  
R. Klauser ◽  
M. Zharnikov ◽  
I.-H. Hong ◽  
S.-C. Wang ◽  
A. Gölzhäuser ◽  
...  
Keyword(s):  
Self Assembled Monolayers ◽  
Assembled Monolayers ◽  
Scanning Photoelectron Microscopy ◽  
Self Assembled
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