N-heterocyclic carbenes : the design concept for densely packed and thermally ultra-stable aromatic self-assembled monolayers

Self-assembled monolayers (SAMs) of N-heterocyclic carbenes (NHCs) on metal substrates are currently one of the most promising systems in context of molecular-scale engineering of surfaces and interfaces, crucial for numerous applications. Interest in NHC SAMs is mainly driven by their assumingly higher thermal stability compared to thiolate SAMs most broadly used at the moment. Most of the NHC SAMs utilize imidazolium as an anchoring group for linking molecules to the metal substrate via carbene C atom. It is well established in the literature that standing up and stable NHC SAMs are built only when using bulky side groups attached to nitrogen heteroatoms in imidazolium moiety, which, however, leads to monolayers exhibiting much lower packing density compared to thiolate SAMs. Here, by combined X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and temperature-programmed secondary ion mass spectrometry analysis, we demonstrate that using NHCs with small methyl side groups in combination with simple, solution-based preparation leads to the formation of aromatic monolayers exhibiting at least doubled surface density, upright molecular orientation, and ultra-high thermal stability compared to the NHC SAMs reported before. These parameters are crucial for most applications, including, in particular, molecular and organic electronics, where aromatic SAMs serve either as a passive element for electrode engineering or as an active part of organic field effect transistors and novel molecular electronics devices

Formation of Highly Ordered Self-Assembled Monolayers of Alkynes on Au(111) Substrate

Self-assembled monolayers (SAMs), prepared by reaction of terminal n-alkynes (HC≡C(CH2)nCH3, n = 5, 7, 9, and 11) with Au(111) at 60 °C were characterized using scanning tunneling microscopy (STM), infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS), and contact angles of water. In contrast to previous spectroscopic studies of this type of SAMs, these combined microscopic and spectroscopic experiments confirm formation of highly ordered SAMs having packing densities and molecular chain orientations very similar to those of alkanethiolates on Au(111). Physical properties, hydrophobicity, high surface order, and packing density, also suggest that SAMs of alkynes are similar to SAMs of alkanethiols. The formation of high-quality SAMs from alkynes requires careful preparation and manipulation of reactants in an oxygen-free environment; trace quantities of O2 lead to oxidized contaminants and disordered surface films. The oxidation process occurs during formation of the SAM by oxidation of the −C≡C– group (most likely catalyzed by the gold substrate in the presence of O2).Chemistry and Chemical Biolog

Security theory and practice: Stablisation and reconstrution of post-conlict areas in the 21st century

Wprowadzenie: Cieszymy się, że możemy skierować do Państwa rąk kolejny numer periodyku „Bezpieczeństwo.Teoria i Praktyka”, tym razem poświęcony problematyce stabilizacji i odbudowy obszarów pokonfliktowych w XXI w. Podjęty temat jest niezwykle ważny, ponieważ żyjemy w czasach nieuporządkowanego świata, w którym liczba konfliktów zbrojnych o różnej skali i charakterze oraz wynikające z nich konsekwencje wpływają destrukcyjnie na ład międzynarodowy.Umiędzynarodowienie konfliktów wewnętrznych pełni często funkcję instrumentalną w grze, której stawką jest zajęcie przez dane państwo właściwego – z punktu widzenia jego decydentów – miejsca w nowym systemie ról międzynarodowych. Przykładem tego jest wojna domowa w Syrii, którą Jerzy Zdanowski w artykule rozpoczynającym tom traktuje jako „wojnę zastępczą”. Krótko przedstawia także istotę rekonstrukcji obszarów pokonfliktowych, czym jako badacz rozwija myśli pułkownika Piotra Gąstała, wieloletniego żołnierza i dowódcy Jednostki Wojskowej GROM, który podczas swojej służby przebywał w niejednym państwie dotkniętym konfliktem zbrojnym i wojną oraz ich skutkami. W udzielonym wywiadzie odnosi się on do zagadnienia stabilizacji ze swojej perspektywy – praktyka, któremu nie raz, na terenie prowadzenia działań wojskowych, przyszło mierzyć się z tym wszystkim, co kryje się pod tym pojęciem. Należy przy tym uwzględnić, że jako żołnierz jednostki specjalnej wykonywał tam specyficzne działania. O tym, jak podchodzą do nich nie tylko praktycy, ale i badacze, pisze Piotr Orłowski, analizując znaczenie sił specjalnych jako narzędzia stabilizacji na obszarach pokonfliktowych

Characterizing the Metal–SAM Interface in Tunneling Junctions

his paper investigates the influence of the interface between a gold or silver metal electrode and an n-alkyl SAM (supported on that electrode) on the rate of charge transport across junctions with structure Met(Au or Ag)TS/A(CH2)nH//Ga2O3/EGaIn by comparing measurements of current density, J(V), for Met/AR = Au/thiolate (Au/SR), Ag/thiolate (Ag/SR), Ag/carboxylate (Ag/O2CR), and Au/acetylene (Au/C≡CR), where R is an n-alkyl group. Values of J0 and β (from the Simmons equation) were indistinguishable for these four interfaces. Since the anchoring groups, A, have large differences in their physical and electronic properties, the observation that they are indistinguishable in their influence on the injection current, J0 (V = 0.5) indicates that these four Met/A interfaces do not contribute to the shape of the tunneling barrier in a way that influences J(V).Chemistry and Chemical Biolog

Odd-even effect in peptide SAMs-competition of secondary structure and molecule–substrate interaction

Peptide-based self-assembled monolayers (SAMs) are well known to be crucial for biocompatible surface formation on inorganic substrates applied for implants, biosensors, or tissue engineering. Moreover, recently these bioinspired nanostructures are also considered particularly interesting for molecular electronics applications due to their surprisingly high conductance and thickness-independent capacitance, which make them a very promising element of organic field-effect transistors (OFETs). Our structural analysis conducted for a series of prototypic homooligopeptides based on glycine (Gly) with cysteine (Cys) as a substrate bonding group chemisorbed on Au and Ag metal substrates (GlynCys/Au(Ag), n = 1−9) exhibits the formation by these monolayers secondary structure close to β-sheet conformation with pronounced odd−even structural effect strongly affecting packing density and conformation of molecules in the monolayer, which depend on the length of molecules and the type of metal substrate. Our experiments indicate that the origin of these structural effects is related to the either cooperative or competitive relationship between the type of secondary structure formed by these molecules and the directional character of their chemical bonding to the metal substrate. The current analysis opens up the opportunity for the rational design of these biologically inspired nanostructures, which is crucial both for mentioned biological and electronic applications