by Keyword: Assembly

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Duro-Castano, A., Moreira Leite, D., Forth, J., Deng, Y., Matias, D., Noble Jesus, C., Battaglia, G., (2020). Designing peptide nanoparticles for efficient brain delivery Advanced Drug Delivery Reviews 160, 52-77

The targeted delivery of therapeutic compounds to the brain is arguably the most significant open problem in drug delivery today. Nanoparticles (NPs) based on peptides and designed using the emerging principles of molecular engineering show enormous promise in overcoming many of the barriers to brain delivery faced by NPs made of more traditional materials. However, shortcomings in our understanding of peptide self-assembly and blood–brain barrier (BBB) transport mechanisms pose significant obstacles to progress in this area. In this review, we discuss recent work in engineering peptide nanocarriers for the delivery of therapeutic compounds to the brain: from synthesis, to self-assembly, to in vivo studies, as well as discussing in detail the biological hurdles that a nanoparticle must overcome to reach the brain.

Keywords: Alzheimer's disease, Blood-brain barrier, Drug delivery, Glioma, Parkinson's disease, Peptides, Self-assembly, Transcytosis

Park, D., Wershof, E., Boeing, S., Labernadie, A., Jenkins, R. P., George, S., Trepat, X., Bates, P. A., Sahai, E., (2020). Extracellular matrix anisotropy is determined by TFAP2C-dependent regulation of cell collisions Nature Materials 19, 227-238

The isotropic or anisotropic organization of biological extracellular matrices has important consequences for tissue function. We study emergent anisotropy using fibroblasts that generate varying degrees of matrix alignment from uniform starting conditions. This reveals that the early migratory paths of fibroblasts are correlated with subsequent matrix organization. Combined experimentation and adaptation of Vicsek modelling demonstrates that the reorientation of cells relative to each other following collision plays a role in generating matrix anisotropy. We term this behaviour ‘cell collision guidance’. The transcription factor TFAP2C regulates cell collision guidance in part by controlling the expression of RND3. RND3 localizes to cell–cell collision zones where it downregulates actomyosin activity. Cell collision guidance fails without this mechanism in place, leading to isotropic matrix generation. The cross-referencing of alignment and TFAP2C gene expression signatures against existing datasets enables the identification and validation of several classes of pharmacological agents that disrupt matrix anisotropy.

Keywords: Biomaterials – cells, Cell migration, Self-assembly, Tissues

Hamouda, I., Labay, C., Ginebra, M. P., Nicol, E., Canal, C., (2020). Investigating the atmospheric pressure plasma jet modification of a photo-crosslinkable hydrogel Polymer 192, 122308

Atmospheric pressure plasma jets (APPJ) have great potential in wound healing, bacterial disinfection and in cancer therapy. Recent studies pointed out that hydrogels can be used as screens during APPJ treatment, or even be used as reservoirs for reactive oxygen and nitrogen species generated by APPJ in liquids. Thus, novel applications are emerging for hydrogels which deserve fundamental exploration of the possible modifications undergone by the polymers in solution due to the reactivity with plasmas. Here we investigate the possible modifications occurred by APPJ treatment of an amphiphilic poly(ethylene oxide)-based triblock copolymer (tPEO) photo-crosslinkable hydrogel. While APPJ treatments lead to a certain degradation of the self-assembly of the polymeric chains at low concentrations (<2 g/L), at the higher concentrations required to form a hydrogel (>2 g/L), the polymeric chains are unaffected by APPJ and the hydrogel forming ability is kept. APPJ treatments induced a pre-crosslinking of the network with an increase of the mechanical properties of the hydrogel. Overall, the small modifications induced allow thinking of polymer solutions with hydrogel forming ability a new platform for several applications related to plasma medicine, and thus, with potential in different therapies.

Keywords: Atmospheric pressure plasma jet, Hydrogel, Photo-crosslinking, Polymer solution, Self-assembly

Duro-Castano, Aroa, Nebot, Vicent J., Niño-Pariente, Amaya, Armiñán, Ana, Arroyo-Crespo, Juan J., Paul, Alison, Feiner-Gracia, Natalia, Albertazzi, Lorenzo, Vicent, María J., (2017). Capturing “extraordinary” soft-assembled charge-like polypeptides as a strategy for nanocarrier design Advanced Materials 29, (39), 1702888

The rational design of nanomedicines is a challenging task given the complex architectures required for the construction of nanosized carriers with embedded therapeutic properties and the complex interface of these materials with the biological environment. Herein, an unexpected charge-like attraction mechanism of self-assembly for star-shaped polyglutamates in nonsalty aqueous solutions is identified, which matches the ubiquitous “ordinary–extraordinary” phenomenon previously described by physicists. For the first time, a bottom-up methodology for the stabilization of these nanosized soft-assembled star-shaped polyglutamates is also described, enabling the translation of theoretical research into nanomaterials with applicability within the drug-delivery field. Covalent capture of these labile assemblies provides access to unprecedented architectures to be used as nanocarriers. The enhanced in vitro and in vivo properties of these novel nanoconstructs as drug-delivery systems highlight the potential of this approach for tumor-localized as well as lymphotropic delivery.

Keywords: Charge-like, Drug delivery, Polymer therapeutics, Polypeptides, Self-assembly

Santander-Nelli, M., Silva, C. P., Espinoza-Vergara, J., Silva, J. F., Olguín, C. F., Cortés-Arriagada, D., Zagal, J. H., Mendizabal, F., Díez-Pérez, I., Pavez, J., (2017). Tailoring electroactive surfaces by non-template molecular assembly. Towards electrooxidation of L-cysteine Electrochimica Acta 254, 201-213

We have prepared a nanoelectrode ensemble containing vertically aligned single walled carbon nanotubes (SWCNTs) using a non-template molecular self-assembling strategy. We used a bottom-up construction approach to assemble amino functionalized SWCNTs (af-SWCNTs) in a well-defined architecture. These af-SWCNTs were linked and vertically aligned to pre-formed self-assembled monolayers of 4-MBA. A Cobalt(II) tetracarboxyphthalocyanine (Co(COOH)4Pc) complex was covalently bonded to external portion of af-SWCNTs to complete the final nanoelectrode ensemble. X-ray photoelectron spectroscopy (XPS) and Atomic Force Microcopy (AFM) confirmed the effectiveness of the assembling steps on the gold surface starting from the Au/MBA SAMs. The system Au/4-MBA/af-SWCNTs shows an interface with large ordered array, which exhibits a high activity for the electrooxidation of L-cysteine (L-cys). Theoretical calculations suggest that the incorporation of the af-SWCNTs increased the activity of the assembly to electronic transfer and it was observed that the electrooxidation reaction is energetically favorable.

Keywords: Bottom-up construction, DFT, Modified electrode, Molecular assembly, SAMs, Single walled carbon nanotube

Beun, L. H., Albertazzi, L., Van Der Zwaag, D., De Vries, R., Cohen Stuart, M. A., (2016). Unidirectional living growth of self-assembled protein nanofibrils revealed by super-resolution microscopy ACS Nano 10, (5), 4973-4980

Protein-based nanofibrils are emerging as a promising class of materials that provide unique properties for applications such as biomedical and food engineering. Here, we use atomic force microscopy and stochastic optical reconstruction microscopy imaging to elucidate the growth dynamics, exchange kinetics, and polymerization mechanism for fibrils composed of a de novo designed recombinant triblock protein polymer. This macromolecule features a silk-inspired self-assembling central block composed of GAGAGAGH repeats, which are known to fold into a β roll with turns at each histidine and, once folded, to stack, forming a long, ribbon-like structure. We find several properties that allow the growth of patterned protein nanofibrils: the self-assembly takes place on only one side of the growing fibrils by the essentially irreversible addition of protein polymer subunits, and these fibril ends remain reactive indefinitely in the absence of monomer ("living ends"). Exploiting these characteristics, we can grow stable diblock protein nanofibrils by the sequential addition of differently labeled proteins. We establish control over the block length ratio by simply varying monomer feed conditions. Our results demonstrate the use of engineered protein polymers in creating precisely patterned protein nanofibrils and open perspectives for the hierarchical self-assembly of functional biomaterials.

Keywords: Nanofibrils, Protein polymers, Self-assembly, STORM microscopy

Maggi, Claudio, Simmchen, Juliane, Saglimbeni, Filippo, Katuri, Jaideep, Dipalo, Michele, De Angelis, Francesco, Sánchez, Samuel, Di Leonardo, Roberto, (2016). Self-assembly of micromachining systems powered by Janus micromotors Small 12, (4), 446-451

Janus particles can self-assemble around microfabricated gears in reproducible configurations with a high degree of spatial and orientational order. The final configuration maximizes the torque applied on the rotor leading to a unidirectional and steady rotating motion. The interplay between geometry and dynamical behavior leads to the self-assembly of Janus micromotors starting from randomly distributed particles.

Keywords: Active catalytic particles, Microgears, Micromachines, Janus particles, Self-assembly, Self-propulsion

Coelho, N. M., Llopis-Hernández, V., Salmerón-Sánchez, M., Altankov, G., (2016). Dynamic reorganization and enzymatic remodeling of type IV collagen at cell–biomaterial interface Advances in Protein Chemistry and Structural Biology (ed. Christo, Z. Christov), Academic Press (San Diego, USA) 105, 81-104

Abstract Vascular basement membrane remodeling involves assembly and degradation of its main constituents, type IV collagen (Col IV) and laminin, which is critical during development, angiogenesis, and tissue repair. Remodeling can also occur at cell–biomaterials interface altering significantly the biocompatibility of implants. Here we describe the fate of adsorbed Col IV in contact with endothelial cells adhering on positively charged NH2 or hydrophobic CH3 substrata, both based on self-assembly monolayers (SAMs) and studied alone or mixed in different proportions. AFM studies revealed distinct pattern of adsorbed Col IV, varying from single molecular deposition on pure NH2 to network-like assembly on mixed SAMs, turning to big globular aggregates on bare CH3. Human umbilical endothelial cells (HUVECs) interact better with Col IV adsorbed as single molecules on NH2 surface and readily rearrange it in fibril-like pattern that coincide with secreted fibronectin fibrils. The cells show flattened morphology and well-developed focal adhesion complexes that are rich on phosphorylated FAK while expressing markedly low pericellular proteolytic activity. Conversely, on hydrophobic CH3 substrata HUVECs showed abrogated spreading and FAK phosphorylation, combined with less reorganization of the aggregated Col IV and significantly increased proteolytic activity. The later involves both MMP-2 and MMP-9, as measured by zymography and FITC-Col IV release. The mixed SAMs support intermediate remodeling activity. Taken together these results show that chemical functionalization combined with Col IV preadsorption provides a tool for guiding the endothelial cells behavior and pericellular proteolytic activity, events that strongly affect the fate of cardiovascular implants.

Keywords: Type IV collagen, Adsorption, Remodeling, Pericellular proteolysis, Reorganization, Substratum chemistry, CH3 and NH2 groups, Self-assembly monolayers

Aragonès, Albert C., Darwish, Nadim, Im, JongOne, Lim, Boram, Choi, Jeongae, Koo, Sangho, Díez-Pérez, Ismael, (2015). Fine-tuning of single-molecule conductance by tweaking both electronic structure and conformation of side substituents Chemistry – A European Journal , 21, (21), 7716-7720

Herein, we describe a method to fine-tune the conductivity of single-molecule wires by employing a combination of chemical composition and geometrical modifications of multiple phenyl side groups as conductance modulators embedded along the main axis of the electronic pathway. We have measured the single-molecule conductivity of a novel series of phenyl-substituted carotenoid wires whose conductivity can be tuned with high precision over an order of magnitude range by modulating both the electron-donating character of the phenyl substituent and its dihedral angle. It is demonstrated that the electronic communication between the phenyl side groups and the molecular wire is maximized when the phenyl groups are twisted closer to the plane of the conjugated molecular wire. These findings can be refined to a general technique for precisely tuning the conductivity of molecular wires.

Keywords: Carotenoids, Conductance, Self-assembly, Single-molecule studies, STM break junction

Mendes, A. C., Smith, K. H., Tejeda-Montes, E., Engel, E., Reis, R. L., Azevedo, H. S., Mata, Alvaro, (2013). Co-assembled and microfabricated bioactive membranes Advanced Functional Materials 23, (4), 430-438

The fabrication of hierarchical and bioactive self-supporting membranes, which integrate physical and biomolecular elements, using a single-step process that combines molecular self-assembly with soft lithography is reported. A positively charged multidomain peptide (with or without the cell-adhesive sequence arginine-glycine-aspartic acid-serine (RGDS)) self-assembles with hyaluronic acid (HA), an anionic biopolymer. Optimization of the assembling conditions enables the realization of membranes with well-controlled and easily tunable features at multiple size scales including peptide sequence, building-block co-assembly, membrane thickness, bioactive epitope availability, and topographical pattern morphology. Membrane structure, morphology, and bioactivity are investigated according to temperature, assembly time, and variations in the experimental setup. Furthermore, to evaluate the physical and biomolecular signaling of the self-assembled microfabricated membranes, rat mesenchymal stem cells are cultured on membranes exhibiting various densities of RGDS and different topographical patterns. Cell adhesion, spreading, and morphology are significantly affected by the surface topographical patterns and the different concentrations of RGDS. The versatility of the combined bottom-up and top-down fabrication processes described may permit the development of hierarchical macrostructures with precise biomolecular and physical properties and the opportunity to fine tune them with spatiotemporal control.

Keywords: Membrane scaffolds, Mesenchymal stem cells, Microfabrication, Self-assembly, Topography

Valle-Delgado, J. J., Liepina, I., Lapidus, D., Sabaté, R., Ventura, S., Samitier, J., Fernàndez-Busquets, X., (2012). Self-assembly of human amylin-derived peptides studied by atomic force microscopy and single molecule force spectroscopy Soft Matter 8, (4), 1234-1242

The self-assembly of peptides and proteins into amyloid fibrils of nanometric thickness and up to several micrometres in length, a phenomenon widely observed in biological systems, has recently aroused a growing interest in nanotechnology and nanomedicine. Here we have applied atomic force microscopy and single molecule force spectroscopy to study the amyloidogenesis of a peptide derived from human amylin and of its reverse sequence. The spontaneous formation of protofibrils and their orientation along well-defined directions on graphite and DMSO-coated graphite substrates make the studied peptides interesting candidates for nanotechnological applications. The measured binding forces between peptides correlate with the number of hydrogen bonds between individual peptides inside the fibril structure according to molecular dynamics simulations.

Keywords: Amyloid fibril, Amyloidogenesis, Binding forces, Fibril structure, Graphite substrate, Molecular dynamics simulations, Nanometrics, Protofibrils, Single molecule force spectroscopy, Spontaneous formation, Atomic force microscopy, Atomic spectroscopy, Graphite, Hydrogen bonds, Medical nanotechnology, Molecular dynamics, Molecular physics, Self assembly, Thickness measurement, Peptides

Baccar, Z.M., Caballero, D., Eritja, R., Errachid, A., (2012). Development of an impedimetric DNA-biosensor based on layered double hydroxide for the detection of long ssDNA sequences Electrochimica Acta 74, 123-129

DNA testing requires the development of sensitive and fast devices to measure the presence of nucleic acid sequences by DNA hybridization. In this paper, a simple and label-free DNA-biosensor has been investigated based on the detection of DNA hybridization on layered double hydroxide (LDH) nanomaterials with special emphasis on targeting long single stranded DNA sequences. First, the immobilization of a 20 bases long DNA probe on a thin layer of Mg2AlCO3 and Mg3AlCO3 LDH was studied. Then, DNA hybridization reaction was detected by means of Electrochemical Impedance Spectroscopy. The resulting biosensor showed a high sensitivity for the detection of 80 bases long DNA complementary sequences. The dynamic range was 18–270 ng/ml with a detection limit lower than 1.8 ng/ml.

Keywords: DNA-biosensor, Nanomaterials, Layered double hydroxide, Self-assembly

Miranda Coelho, Nuno, Gonzalez-Garcia, Cristina, Salmeron-Sanchez, Manuel, Altankov, George, (2011). Arrangement of type IV collagen on NH(2) and COOH functionalized surfaces Biotechnology and Bioengineering , 108, (12), 3009-3018

Apart from the paradigm that cell-biomaterials interaction depends on the adsorption of soluble adhesive proteins we anticipate that upon distinct conditions also other, less soluble ECM proteins such as collagens, associate with the biomaterials interface with consequences for cellular response that might be of significant bioengineering interest. Using atomic force microscopy (AFM) we seek to follow the nanoscale behavior of adsorbed type IV collagen (Col IV)-a unique multifunctional matrix protein involved in the organization of basement membranes (BMs) including vascular ones. We have previously shown that substratum wettability significantly affects Col IV adsorption pattern, and in turn alters endothelial cells interaction. Here we introduce two new model surfaces based on self-assembled monolayers (SAMs), a positively charged - NH(2), and negatively charged -COOH surface, to learn more about their particular effect on Col IV behavior. AFM studies revealed distinct pattern of Col IV assembly onto the two SAMs resembling different aspects of network-like structure or aggregates (suggesting altered protein conformation). Moreover, the amount of adsorbed FITC-labeled Col IV was quantified and showed about twice more protein on NH(2) substrata. Human umbilical vein endothelial cells attached less efficiently to Col IV adsorbed on negatively charged COOH surface judged by altered cell spreading, focal adhesions formation, and actin cytoskeleton development. Immunofluorescence studies also revealed better Col IV recognition by both alpha(1) and alpha(2) integrins on positively charged NH(2) substrata resulting in higher phosphorylated focal adhesion kinase recruitment in the focal adhesion complexes. On COOH surface, no integrin clustering was observed. Taken altogether these results, point to the possibility that combined NH(2) and Col IV functionalization may support endothelization of cardiovascular implants.

Keywords: Collagen type IV, SAMs, AFM, Surface-induced protein assembly, Endothelial cells, Vascular grafts

Coelho, N. M., Gonzalez-Garcia, C., Planell, J. A., Salmeron-Sanchez, M., Altankov, G., (2010). Different assembly of type iv collagen on hydrophilic and hydrophobic substrata alters endothelial cells interaction European Cells & Materials , 19, 262-272

Considering the structural role of type IV collagen (Col IV) in the assembly of the basement membrane (BM) and the perspective of mimicking its organization for vascular tissue engineering purposes, we studied the adsorption pattern of this protein on model hydrophilic (clean glass) and hydrophobic trichloro(octadecyl) silane (ODS) surfaces known to strongly affect the behavior of other matrix proteins. The amount of fluorescently labeled Col IV was quantified showing saturation of the surface for concentration of the adsorbing solution of about 50 mu g/ml, but with approximately twice more adsorbed protein on ODS. AFM studies revealed a fine-nearly single molecular size-network arrangement of Col IV on hydrophilic glass, which turns into a prominent and growing polygonal network consisting of molecular aggregates on hydrophobic ODS. The protein layer forms within minutes in a concentration-dependent manner. We further found that human umbilical vein endothelial cells (HUVEC) attach less efficiently to the aggregated Col IV (on ODS), as judged by the significantly altered cell spreading, focal adhesions formation and the development of actin cytoskeleton. Conversely, the immunofluorescence studies for integrins revealed that the fine Col IV network formed on hydrophilic substrata is better recognized by the cells via both alpha 1 and alpha 2 heterodimers which support cellular interaction, apart from these on hydrophobic ODS where almost no clustering of integrins was observed.

Keywords: Collagen type IV, Adsorption, Assembly, Hydrophilic, Hydrophobic, Surfaces

Arteaga, O., Escudero, C., Oncins, G., El-Hachemic, Z., Llorens, J., Crusats, J., Canillas, A., Ribo, J. M., (2009). Reversible mechanical induction of optical activity in solutions of soft-matter nanophases Chemistry - An Asian Journal , 4, (11), 1687-1696

Nanophases of J-aggregates of several achiral amphiphilic porphyrins, which have thin long acicular shapes (nanoribbons), show the immediate and reversible formation of a stationary mechano-chiral state in the solution by vortex stirring, as detected by their circular dichroic signals measured by 2-modulator generallized ellipsometry. The results suggest that when a macroscopic chiral force creates supramolecular chirality, it also creates an enantiomeric excess of screw distortions, which may be detected by their excitonic absorption. An explanation on the effect of the shear flow gradients is proposed on the basis of the orientation of the rotating particles in the vortex and the size, shape, and mechanical properties of the nanoparticles.

Keywords: Chirality, Circular dichroism, Nanoparticles, Selfassembly, Supramolecular chemistry

Fonollosa, J., Carmona, M., Santander, J., Fonseca, L., Moreno, M., Marco, S., (2009). Limits to the integration of filters and lenses on thermoelectric IR detectors by flip-chip techniques Sensors and Actuators A: Physical , 149, (1), 65-73

In the trend towards miniaturization, a detector module containing multiple IR sensor channels is being built and characterized. In its final form it contains thermopiles, narrow band filters and Fresnel lenses. An important feature of such module is the assembly by flip-chip of the IR filters on top of the thermopiles. The performance of the filter-thermopile ensemble has been assessed by physical simulation and experiments and it has been optimized by the use of an empirically validated model. It has been found that integration of filters (or lenses) too close to the IR detector may lead to degraded performance due to thermal coupling. The impact and extent of this degradation has been thoroughly explored, being the main parameter the distance between the IR sensor and the filter. To avoid such detrimental effects a possibility is to set the device in vacuum conditions, obtaining an improved output response and avoiding the influence of the filters. Another way is to increase the solder joint height. Beyond a certain height, the filter is considered to be isolated from the thermopile.

Keywords: Assembly, Infrared sensor, Infrared filter, Fresnel lenses, FEM simulation, Optimization

Oncins, Gerard, Vericat, Carolina, Sanz, Fausto, (2008). Mechanical properties of alkanethiol monolayers studied by force spectroscopy Journal of Chemical Physics , 128, (4), 044701

The mechanical properties of alkanethiol monolayers on Au(111) in KOH solution have been studied by force spectroscopy. The analysis of the vertical force versus penetration curves showed that monolayer penetration is a stepped process that combines elastic regions with sudden penetration events. The structural meaning of these events can be explained both by the creation of gauche defects on the hydrocarbon chains and by a cooperative molecular tilting model proposed by Barrena et al. [J. Chem. Phys. 113, 2413 (2000)]. The validity of these models for alkanethiol monolayers of different compactness and chain length has been discussed. The Young's modulus (E) of the monolayers has been calculated by using a recently developed model which considers the thickness of the monolayer as a parameter, thus allowing a decoupling of the mechanical properties of the thiol layer from those of the Au(111) substrate. As a result, the calculated E values are in the range of 50-150 Pa, which are remarkably lower than those previously reported in the literature.

Keywords: Adsorbed layers, AFM, Gold, Monolayers, Organic compounds, Self-assemblyYoung's modulus