Self-assembly of organometallic Pd(II) complexes via CH3 center dot center dot center dot pi interactions: the first example of a cyclopalladated compound with herringbone stacking pattern

Two binuclear cyclometallated compounds [Pd(C-2,N-dmba)(mu-N-3)](2) (1) and [Pd-2(C-2,N-dmba)(2)(mu-N-3)(mu-Cl)] (2) (dmba = N,N-dimethylbenzylarnine) have been synthesized and characterized by elemental 3 analysis, IR and NMR spectroscopies and single crystal X-ray diffraction crystallography. The ability of CH3 groups to form C(sp(3))-H...pi hydrogen bonds with phenyl rings is responsible for the molecular self-assembly within the crystals of 1 and 2. Compound 1 crystallizes as one-dimensional supramolecular chains whereas the crystal packing of 2 consists of a herringbone of sandwiches composed by two inversely related [Pd-2(C-2,N-dmba)(2)(mu-N-3)(mu-Cl)] molecules. (c) 2007 Elsevier B.V. All rights reserved.

Self-assembly of Pd(II) pyrazolyl complexes to 1-D hydrogen-bonded coordination polymers

This work describes the synthesis and characterization of two novel Pd(II) pyrazolyl complexes of the type [PdX2(HdmPz)(2)](n) {X=SCN- (1), N-3(-) (2); HdmPz=3,5-dimethylpyrazole} that self-assemble through N-H...NCS or N-H...NNN hydrogen bonds to yield infinite one-dimensional chains, as confirmed by single crystal X-ray study on 1. The expected solid state polymeric structure for 2 is slowly broken up in CHCl3 Solution, leading to an equilibrium mixture of cis and trans-[Pd(N-3)(2)(HdmPz)(2)] monomers, as demonstrated by time-dependent IR and NMR studies. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Low-weight coordination polymers derived from the self-assembly reactions of Pd(II) pyrazolyl compounds and azide ion

The low-weight Pd(II) coordination polymers [(N(3))(HL)Pd {Pd(3)(mu-N(3))(mu-L)(5)}10(mu-L)(2)Pd(L)(HL)]{L = Pz(-) (1); mPz(-) (2), IPz(-)(3)} and [(N(3))(HPz)Pd{Pd(6)(mu-N(3))(2)(mu-PZ)(5)(mu-L)(5)}(10)(mu-L)(2)Pd(Pz)(HPz)] {L = mPz(-) (4), dmPz(-) (5); IPz(-) (6)} {L = pyrazolate (Pz(-)), 4-methylpyrazolate(mPz(-)), 4-iodopyrazo late (IPz(-)), 3,5-dimethylpyrazolate (dmPz(-))} have been prepared in this work. IR spectra clearly indicated the exobidentate nature of pyrazolato ligands as well the end-on coordination mode of the azido group. The molecular weight determinations by osmometry indicated that the species have a low degree of polymerization (n = 10). NMR experiments showed two pyrazolate environments in a 2:1 ratio, being assigned to the six-membered ring Pd(mu-L)(2)Pd and the Pd(mu-N(3))(mu-L)Pd metallocycle, respectively. UV-visible spectroscopy gave further evidences for the oligomeric structures of 1-6. Some alternative structures for the isostructural polymers have been suggested. (c) 2005 Elsevier Ltd. All rights reserved.

Effects of self-assembly process of latex spheres on the final topology of macroporous silica

This paper surveys the topology of macroporous silica prepared using latex templates covering the submicrometric range (0.1-0.7 mu m). The behavior of latex spheres in aqueous dispersion has been analyzed by dynamic light scattering (DLS) measurement indicating the most appropriate conditions to form well-defined cubic arrays. The optical behavior of latex spheres has been analyzed by transmittance and reflectance measurements in order to determine their diameter and filling factor when they were assembled in bidimensional arrays. Macroscopic templates have been obtained by a centrifugation process and their crystalline ordering has been confirmed by porosimetry and scanning electron microscopy. These self-assembled structures have been used to produce macroporous silica, whose final topology depends on the pore size distribution of the original template. It has been seen that latex spheres are ordered in a predominant fcc arrangement with slipping of tetragonal pores due to the action of attractive electrostatic interactions. The main effect is to change the spherical shape of voids in macroporous silica into a hexagonal configuration with possible applications to fabricate photonic devices with novel optical properties. (c) 2005 Elsevier B.V. All rights reserved.

Self-assembly in aqueous solution of amphiphilic graft copolymers from oxidized carboxymethylcellulose

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Self-Assembly of Poly(4-vynil-N-alkylpyridinium) Bromide onto Silica: Effect of Side-Chain Length on Structural Aspects at a Molecular Level

Self-assembly of poly(4-vynil-N-alkyl)pyridinium bromide with alkyl side chains of 2, 5, 7, 10, or 16 carbons from ethanolic solutions onto flat silica surfaces was studied by means of ellipsometry, atomic force microscopy (AFM), contact angle measurements, and sum-frequency generation (SFG) vibrational spectroscopy in the CH3 and CH2 stretch region. Ab initio quantum-chemical calculations on the N-alkylpyridinium side-group with restricted Hartree-Fock (RHF) method and 6-311G (d,p) basis set were C one to estimate the charge distribution along the pyridinium ring and the alkyl side-chain. SFG results showed that longer side chains promote the disorientation of the alkyl groups at the surface, corroborating with the contact angle values. AFM images revealed film homogeneity, regardless the alkyl side group. However, after 24 h contact with water, ringlike structures appeared on the film surfaces, when the polycation alkyl side chain had 7 or less carbons, and as the alkyl chain increased to 10 or 16 carbons, the films dewetted because the hydrophobic interactions prevailed over the electrostatic interactions between the pyridinium charged groups and the negatively charged SiO2 surface. Under acid conditions (HCl 0.1 mol.L-1), the film mean thickness values decreased up to 50% of original values when the alkyl side chains were ethyl or pentyl groups due to ion-pair disruption, but for longer groups they remained unchanged. Quantum-chemical optimization and Mulliken electron population showed that (i) from C2 to C15 the positive charge at the headgroup (HG) decreased 0.025, while the charge at combined HG + alpha-CH2 increased 0.037; and (ii) for C6 or longer, the alkyl side group presents a tilt in the geometry, moving away from the plane. Such effects summed up over the whole polymer chain give support to suggest that when the side chains are longer than 7 carbons, the hydrophobic interaction decreases film stability and increases acid resistance.

Self assembly of human septin 2 into amyloid filaments

Septins are a conserved group of GTP-binding proteins that form hetero-oligomeric complexes which assemble into filaments. These are essential for septin function, including their role in cytokinesis, cell division, exocytosis and membrane trafficking. Septin 2 (SEPT2) is a member of the septin family and has been associated with neurofibrillary tangles and other pathological features of senile plaques in Alzheimer's disease. An in silico analysis of the amino acid sequence of SEPT2 identified regions with a significant tendency to aggregate and/or form amyloid. These were all observed within the GTP-binding domain. This was consistent with the experimental identification of a structure rich in beta-sheet during temperature induced unfolding transitions observed for both the full length protein and the GTP-binding domain alone. This intermediate state is characterized by irreversible aggregation and has the ability to bind Thioflavin-T, suggesting its amyloid nature. Under electron microscopy, fibers extending for several micrometers in length could be visualized. The results shown in this study support the hypothesis that single septins, when present in excess or with unbalanced stoichiometries, may be unstable and assemble into amyloid-like structures. (C) 2011 Elsevier Masson SAS. All rights reserved.

Synthesis and characterisation of photoreactive silanes for the self-assembly on functionalised silica surfaces

The aim of this thesis was to investigate novel techniques to create complex hierarchical chemical patterns on silica surfaces with micro to nanometer sized features. These surfaces were used for a site-selective assembly of colloidal particles and oligonucleotides. To do so, functionalised alkoxysilanes (commercial and synthesised ones) were deposited onto planar silica surfaces. The functional groups can form reversible attractive interactions with the complementary surface layers of the opposing objects that need to be assembled. These interactions determine the final location and density of the objects onto the surface. Photolithographically patterned silica surfaces were modified with commercial silanes, in order to create hydrophilic and hydrophobic regions on the surface. Assembly of hydrophobic silica particles onto these surfaces was investigated and finally, pH and charge effects on the colloidal assembly were analysed. In the second part of this thesis the concept of novel, "smart" alkoxysilanes is introduced that allows parallel surface activation and patterning in a one-step irradiation process. These novel species bear a photoreactive head-group in a protected form. Surface layers made from these molecules can be irradiated through a mask to remove the protecting group from selected regions and thus generate lateral chemical patterns of active and inert regions on the substrate. The synthesis of an azide-reactive alkoxysilane was successfully accomplished. Silanisation conditions were carefully optimised as to guarantee a smooth surface layer, without formation of micellar clusters. NMR and DLS experiments corroborated the absence of clusters when using neither water nor NaOH as catalysts during hydrolysis, but only the organic solvent itself. Upon irradiation of the azide layer, the resulting nitrene may undergo a variety of reactions depending on the irradiation conditions. Contact angle measurements demonstrated that the irradiated surfaces were more hydrophilic than the non-irradiated azide layer and therefore the formation of an amine upon irradiation was postulated. Successful photoactivation could be demonstrated using condensation patterns, which showed a change in wettability on the wafer surface upon irradiation. Colloidal deposition with COOH functionalised particles further underlined the formation of more hydrophilic species. Orthogonal photoreactive silanes are described in the third part of this thesis. The advantage of orthogonal photosensitive silanes is the possibility of having a coexistence of chemical functionalities homogeneously distributed in the same layer, by using appropriate protecting groups. For this purpose, a 3',5'-dimethoxybenzoin protected carboxylic acid silane was successfully synthesised and the kinetics of its hydrolysis and condensation in solution were analysed in order to optimise the silanisation conditions. This compound was used together with a nitroveratryl protected amino silane to obtain bicomponent surface layers. The optimum conditions for an orthogonal deprotection of surfaces modified with this two groups were determined. A 2-step deprotection process through a mask generated a complex pattern on the substrate by activating two different chemistries at different sites. This was demonstrated by colloidal adsorption and fluorescence labelling of the resulting substrates. Moreover, two different single stranded oligodeoxynucleotides were immobilised onto the two different activated areas and then hybrid captured with their respective complementary, fluorescent labelled strand. Selective hybridisation could be shown, although non-selective adsorption issues need to be resolved, making this technique attractive for possible DNA microarrays.

Fluorescent ionene-dye nanoparticles by electrostatic self-assembly

It is investigated that the association of linear cationic model polyelectrolytes with oppositely charged pyrenetetrasulfonate (PY) in aqueous solution. For this purpose water soluble ionenes were prepared via Menschutkin reaction from 1-4-diazabicyclo [2.2.2] octane and e.g. 1,6-dibromohexane and 1,4 dibromotransbuten. The complex formation between dye molecules PY and oppositely charged ionenes (PD4, PD6, PD4-2 and PD4coPD6) of different chemical structures in aqueous solution was studied by light scattering (LS), small angle neutron scattering (SANS), UV-Vis, fluorescence spectroscopy and atomic force microscopy (AFM). Spectrophotometric titration results revealed that PY molecules were bind to ionenes cooperative process due to π-π interaction. Cooperative binding constant KD was determined as 6.4 x 10^6 M^-1 (+ or - 10^5 M^-1). It was found that binding mode and geometry of PY is predominantly depending on inter-charge distances of corresponding ionenes. Resultant complexes have exhibited size and structure variation as a function of charge ratio (L), ionic strength, inter-charge distances. Spherical dye-ionene complexes of which radius of gyration ranging between (RG) 50 and 190 nm have been observed in PD4-PY system while this was not possible with a different ionene (PD6) or either case ionene excess. It was found that most of the PD4-PY complexes had RG / RH ~ 0.78. Based on the AFM and LS results, spherical complexes have certain colloidal stability and their size can effectively controlled by changing the L.

Structure and properties of nanostructures from polyelectrolytes and porphyrins: Self-Assembly in aqueous solution

In this work self-assembling model systems in aqueous solution were studied. The systems contained charged polymers, polyelectrolytes, that were combined with oppositely charged counterions to build up supramolecular structures. With imaging, scattering and spectroscopic techniques it was investigated how the structure of building units influences the structure of their assemblies. Polyelectrolytes with different chemical structure, molecular weight and morphology were investigated. In addition to linear polyelectrolytes, semi-flexible cylindrical bottle-brush polymers that possess a defined cross-section and a relatively high persistence along the backbone were studied. The polyelectrolytes were combined with structural organic counterions having charge numbers one to four. Especially the self-assembly of polyelectrolytes with different tetravalent water-soluble porphyrins was studied. Porphyrins have a rigid aromatic structure that has a structural effect on their self-assembly behavior and through which porphyrins are capable of self-aggregation via π-π interaction. The main focus of the thesis is the self-assembly of cylindrical bottle-brush polyelectrolytes with tetravalent porphyrins. It was shown that the addition of porphyrins to oppositely charged brush molecules induces a hierarchical formation of stable nanoscale brush-porphyrin networks. The networks can be disconnected by addition of salt and single porphyrin-decoratedrncylindrical brush polymers are obtained. These two new morphologies, brush-porphyrin networks and porphyrin-decorated brush polymers, may have potential as functional materials with interesting mechanical and optical properties.

The calcite(10-14) surface: a versatile substrate for molecular self-assembly

This thesis presents a detailed and successful study of molecular self-assembly on the calcite CaCO3(10-14) surface. One reason for the superior applicability of this particular surface is given by reflecting the well-known growth modes. Layer-by-layer growth, which is a necessity for the formation of templated two-dimensional (2D) molecular structures, is particularly favoured on substrates with a high surface energy. The CaCO3(10-14) surface is among those substrates and, thus, most promising. rnrnAll experiments in this thesis were performed using the non-contact atomic force microscope (NC-AFM) under ultra-high vacuum conditions. The acquisition of drift-free data became in this thesis possible owing to the herein newly developed atom-tracking system. This system features a lateral tip-positioning precision of at least 50pm. Furthermore, a newly developed scan protocol was implemented in this system, which allows for the acquisition of dense three-dimensional (3D) data under room-temperature conditions. An entire 3D data set from a CaCO3(10-14) surface consisting of 85x85x500 pixel is discussed. rnrnThe row-pairing and (2x1) reconstructions of the CaCO3(10-14) surface constitute most interesting research subjects. For both reconstructions, the NC-AFM imaging was classified to a total of 12 contrast modes. Eight of these modes were observed within this thesis, some of them for the first time. Together with literature findings, a total of 10 modes has been observed experimentally to this day. Some contrast modes presented themselves as highly distance-dependent and at least for one contrast mode, a severe tip-termination influence was found. rnrnMost interestingly, the row-pairing reconstruction was found to break a symmetry element of the CaCO3(10-14) surface. With the presence of this reconstruction, the calcite (10-14) surface becomes chiral. From high-resolution NC-AFM data, the identification of the enantiomers is here possible and is presented for one enantiomer in this thesis. rnrnFive studies of self-assembled molecular structures on calcite (10-14) surfaces are presented. Only for one system, namely HBC/CaCO3(10-14), the formation of a molecular bulk structure was observed. This well-known occurence of weak molecule-insulator interaction hinders the investigation of two-dimensional molecular self-assembly. It was, however, possible to force the formation of an island phase for this system upon following a variable-temperature preparation. rnFor the C60/CaCO3(10-14) system it is most notably that no branched island morphologies were found. Instead, the first C60 layer appeared to wet the calcite surface. rnrnIn all studies, the molecules arranged themselves in ordered superstructures. A templating effect due to the underlying calcite substrate was evident for all systems. This templating strikingly led either to the formation of large commensurate superstructures, such as (2x15) with a 14 molecule basis for the C60/CaCO3(10-14) system, or prevented the vast growth of incommensurate molecular motifs, such as the chicken-wire structure in the trimesic acid (TMA)/CaCO3(10-14) system. rnrnThe molecule-molecule and the molecule-substrate interaction was increased upon choosing molecules with carboxylic acid moieties in the third, fourth and fifth study, using terephthalic acid, TMA and helicene molecules. In all these experiments, hydrogen-bonded assemblies were created. rnrnDirected hydrogen bond formation combined with intermolecular pi-pi interaction is employed in the fifth study, where the formation of uni-directional molecular "wires" from single helicene molecules succeeded. Each "wire" is composed of heterochiral helicene pairs, well-aligned along the [01-10] substrate direction and stabilised by pi-pi interaction.

Atomic-scale characterization of diamond surfaces and fullerene self-assembly

In this thesis, elemental research towards the implantation of a diamond-based molecular quantum computer is presented. The approach followed requires linear alignment of endohedral fullerenes on the diamond C(100) surface in the vicinity of subsurface NV-centers. From this, four fundamental experimental challenges arise: 1) The well-controlled deposition of endohedral fullerenes on a diamond surface. 2) The creation of NV-centers in diamond close to the surface. 3) Preparation and characterization of atomically-flat diamondsurfaces. 4) Assembly of linear chains of endohedral fullerenes. First steps to overcome all these challenges were taken in the framework of this thesis. Therefore, a so-called “pulse injection” technique was implemented and tested in a UHV chamber that was custom-designed for this and further tasks. Pulse injection in principle allows for the deposition of molecules from solution onto a substrate and can therefore be used to deposit molecular species that are not stable to sublimation under UHV conditions, such as the endohedral fullerenes needed for a quantum register. Regarding the targeted creation of NV-centers, FIB experiments were carried out in cooperation with the group of Prof. Schmidt-Kaler (AG Quantum, Physics Department, Johannes Gutenberg-Universität Mainz). As an entry into this challenging task, argon cations were implanted into (111) surface-oriented CaF2 crystals. The resulting implantation spots on the surface were imaged and characterized using AFM. In this context, general relations between the impact of the ions on the surface and their valency or kinetic energy, respectively, could be established. The main part of this thesis, however, is constituted by NCAFM studies on both, bare and hydrogen-terminated diamond C(100) surfaces. In cooperation with the group of Prof. Dujardin (Molecular Nanoscience Group, ISMO, Université de Paris XI), clean and atomically-flat diamond surfaces were prepared by exposure of the substrate to a microwave hydrogen plasma. Subsequently, both surface modifications were imaged in high resolution with NC-AFM. In the process, both hydrogen atoms in the unit cell of the hydrogenated surface were resolved individually, which was not achieved in previous STM studies of this surface. The NC-AFM images also reveal, for the first time, atomic-resolution contrast on the clean, insulating diamond surface and provide real-space experimental evidence for a (2×1) surface reconstruction. With regard to the quantum computing concept, high-resolution NC-AFM imaging was also used to study the adsorption and self-assembly potential of two different kinds of fullerenes (C60 and C60F48) on aforementioned diamond surfaces. In case of the hydrogenated surface, particular attention was paid to the influence of charge transfer doping on the fullerene-substrate interaction and the morphology emerging from self-assembly. Finally, self-assembled C60 islands on the hydrogen-terminated diamond surface were subject to active manipulation by an NC-AFM tip. Two different kinds of tip-induced island growth modes have been induced and were presented. In conclusion, the results obtained provide fundamental informations mandatory for the realization of a molecular quantum computer. In the process it was shown that NC-AFM is, under proper circumstances, a very capable tool for imaging diamond surfaces with highest resolution, surpassing even what has been achieved with STM up to now. Particular attention was paid to the influence of transfer doping on the morphology of fullerenes on the hydrogenated diamond surface, revealing new possibilities for tailoring the self-assembly of molecules that have a high electron affinity.

Atomistic simulations of 2D bicomponent self-assembly: from molecular recognition to self-healing

Supramolecular two-dimensional engineering epitomizes the design of complex molecular architectures through recognition events in multicomponent self-assembly. Despite being the subject of in-depth experimental studies, such articulated phenomena have not been yet elucidated in time and space with atomic precision. Here we use atomistic molecular dynamics to simulate the recognition of complementary hydrogen-bonding modules forming 2D porous networks on graphite. We describe the transition path from the melt to the crystalline hexagonal phase and show that self-assembly proceeds through a series of intermediate states featuring a plethora of polygonal types. Finally, we design a novel bicomponent system possessing kinetically improved self-healing ability in silico, thus demonstrating that a priori engineering of 2D self-assembly is possible.

Self-assembly of focal point oligo-catechol ethylene glycol dendrons on titanium oxide surfaces: adsorption kinetics, surface characterization, and nonfouling properties

This work covers the synthesis of second-generation, ethylene glycol dendrons covalently linked to a surface anchor that contains two, three, or four catechol groups, the molecular assembly in aqueous buffer on titanium oxide surfaces, and the evaluation of the resistance of the monomolecular adlayers against nonspecific protein adsorption in contact with full blood serum. The results were compared to those of a linear poly(ethylene glycol) (PEG) analogue with the same molecular weight. The adsorption kinetics as well as resulting surface coverages were monitored by ex situ spectroscopic ellipsometry (VASE), in situ optical waveguide lightmode spectroscopy (OWLS), and quartz crystal microbalance with dissipation (QCM-D) investigations. The expected compositions of the macromolecular films were verified by X-ray photoelectron spectroscopy (XPS). The results of the adsorption study, performed in a high ionic strength ("cloud-point") buffer at room temperature, demonstrate that the adsorption kinetics increase with increasing number of catechol binding moieties and exceed the values found for the linear PEG analogue. This is attributed to the comparatively smaller and more confined molecular volume of the dendritic macromolecules in solution, the improved presentation of the catechol anchor, and/or their much lower cloud-point in the chosen buffer (close to room temperature). Interestingly, in terms of mechanistic aspects of "nonfouling" surface properties, the dendron films were found to be much stiffer and considerably less hydrated in comparison to the linear PEG brush surface, closer in their physicochemical properties to oligo(ethylene glycol) alkanethiol self-assembled monolayers than to conventional brush surfaces. Despite these differences, both types of polymer architectures at saturation coverage proved to be highly resistant toward protein adsorption. Although associated with higher synthesis costs, dendritic macromolecules are considered to be an attractive alternative to linear polymers for surface (bio)functionalization in view of their spontaneous formation of ultrathin, confluent, and nonfouling monolayers at room temperature and their outstanding ability to present functional ligands (coupled to the termini of the dendritic structure) at high surface densities.