Molecular engineering of Surfaces Using Self-Assembled Monolayers

2005 ◽  
Vol 88 (1) ◽  
pp. 17-48 ◽  
Author(s):  
George M. Whitesides ◽  
Jennah K. Kriebel ◽  
J. Christopher Love

The self-assembly of molecules into structurally organized monolayers (SAMs) uses the flexibility of organic chemistry and coordination chemistry to generate well-defined, synthetic surfaces with known molecular and macroscopic properties. The process of designing monolayers with a specified structure gives a high level of control over the molecular-level composition in the direction perpendicular to a surface; soft lithographic technique gives useful (if lower) resolution in the plane of the surface. Alkanethiolates adsorbed on gold, silver, mercury, palladium and platinum are currently the best-defined systems of SAMs. They provide substrates for a number of applications-from studies of wetting and electron transport to patterns for growing mammalian cells. SAMs have made organic surfaces a central part of surface science. Understanding the principles by which they form, and connecting molecular-level structure with macroscopic properties, opens a wide range of areas to study and exploitation.

2012 ◽  
Vol 9 (1) ◽  
pp. 43 ◽  
Author(s):  
Hueyling Tan

Molecular self-assembly is ubiquitous in nature and has emerged as a new approach to produce new materials in chemistry, engineering, nanotechnology, polymer science and materials. Molecular self-assembly has been attracting increasing interest from the scientific community in recent years due to its importance in understanding biology and a variety of diseases at the molecular level. In the last few years, considerable advances have been made in the use ofpeptides as building blocks to produce biological materials for wide range of applications, including fabricating novel supra-molecular structures and scaffolding for tissue repair. The study ofbiological self-assembly systems represents a significant advancement in molecular engineering and is a rapidly growing scientific and engineering field that crosses the boundaries ofexisting disciplines. Many self-assembling systems are rangefrom bi- andtri-block copolymers to DNA structures as well as simple and complex proteins andpeptides. The ultimate goal is to harness molecular self-assembly such that design andcontrol ofbottom-up processes is achieved thereby enabling exploitation of structures developed at the meso- and macro-scopic scale for the purposes oflife and non-life science applications. Such aspirations can be achievedthrough understanding thefundamental principles behind the selforganisation and self-synthesis processes exhibited by biological systems.


Author(s):  
Len LeBlanc ◽  
Walter Kresic ◽  
Sean Keane ◽  
John Munro

This paper describes the integrity management framework utilized within the Enbridge Liquids Pipelines Integrity Management Program. The role of the framework is to provide the high-level structure used by the company to prepare and demonstrate integrity safety decisions relative to mainline pipelines, and facility piping segments where applicable. The scope is directed to corrosion, cracking, and deformation threats and all variants within those broad categories. The basis for the framework centers on the use of a safety case to provide evidence that the risks affecting the system have been effectively mitigated. A ‘safety case’, for the purposes of this methodology is defined as a structured argument demonstrating that the evidence is sufficient to show that the system is safe.[1] The decision model brings together the aspects of data integration and determination of maintenance timing; execution of prevention, monitoring, and mitigation; confirmation that the execution has met reliability targets; application of additional steps if targets are not met; and then the collation of the results into an engineering assessment of the program effectiveness (safety case). Once the program is complete, continuous improvement is built into the next program through the incorporation of research and development solutions, lessons learned, and improvements to processes. On the basis of a wide range of experiences, investigations and research, it was concluded that there are combinations of monitoring and mitigation methods required in an integrity program to effectively manage integrity threats. A safety case approach ultimately provides the structure for measuring the effectiveness of integrity monitoring and mitigation efforts, and the methodology to assess whether a pipeline is sufficiently safe with targets for continuous improvement. Hence, the need for the safety case is to provide transparent, quantitative integrity program performance results which are continually improved upon through ongoing revalidations and improvement to the methods utilized. This enables risk reduction, better stakeholder awareness, focused innovation, opportunities for industry information sharing along with other benefits.


2012 ◽  
Vol 9 (1) ◽  
pp. 43
Author(s):  
Huey Ling Tan

Molecular self-assembly is ubiquitous in nature and has emerged as a new approach to produce new materials in chemistry, engineering, nanotechnology, polymer science and materials. Molecular self-assembly has been attracting increasing interest from the scientific community in recent years due to its importance in understanding biology and a variety of diseases at the molecular level. In the last few years, considerable advances have been made in the use of peptides as building blocks to produce biological materials for wide range of applications, including fabricating novel supra-molecular structures and scaffolding for tissue repair. The study of biological self-assembly systems represents a significant advancement in molecular engineering and is a rapidly growing scientific and engineering field that crosses the boundaries of existing disciplines. Many self-assembling systems are range from bi- and tri-block copolymers to DNA structures as well as simple and complex proteins and peptides. The ultimate goal is to harness molecular self-assembly such that design and control of bottom-up processes is achieved thereby enabling exploitation of structures developed at the meso- and macro-scopic scale for the purposes of life and non-life science applications. Such aspirations can be achieved through understanding the fundamental principles behind the self­ organisation and self-synthesis processes exhibited by biological systems.


2001 ◽  
Vol 707 ◽  
Author(s):  
Kazuyuki Kuroda ◽  
Atsushi Shimojima

ABSTRACTVarious layered hybrid films prepared from organoalkoxysilanes with long organic chains, based on the self-assembly of the hydrolyzed species, are reviewed. Morphological control of transparent and oriented films was achieved by cohydrolysis and polycondensation with tetraalkoxysilanes, followed by dip- or spin-coating. In addition to alkyltrialkoxysilanes, alkyldimethylmonoalkoxy- and alkylmethyldialkoxy-silanes were also used as the structural units, implying that the inorganic–organic interface can be designed at a molecular level. In these cases, co-condensation in the precursor solution plays an essential role in the formation of homogeneous and ordered films. Alkenyltriethoxysilanes with terminal C=C bonds were also employed to prepare layered hybrid films. Interlayer chains were polymerized upon UV irradiation, and the resulting films exhibited a significant increase in the hardness if compared with the films before polymerization. Hybrid films thus obtained are a new class of materials and of great interest for a wide range of materials chemistry.


2015 ◽  
Vol 1113 ◽  
pp. 586-593 ◽  
Author(s):  
Hamizah Shamsudeen ◽  
Huey Ling Tan

Molecular self-assembly is ubiquitous in nature and has now emerged as a new approach in chemical synthesis, engineering, nanotechnology, polymer science, and materials. Molecular self-assembly has been attracting increasing interest from the scientific community in the recent years due to its importance in understanding biology and a variety of diseases at the molecular level. In the last few years, considerable advances have been made in the use of peptides as building blocks to produce biological materials for wide range of applications, including fabricating novel supra-molecular structures and scaffolding for tissue repair. Today, the study of biological self-assembly systems represent a significant advance in the molecular engineering and is a rapidly growing scientific and engineering field that crosses the boundaries of existing disciplines. Many self-assembling systems are range from bi-and tri-block copolymers to complex DNA structures as well as simple and complex proteins and peptides. The attractiveness of such bottom-up processes lies in their capability to build uniform, functional units or arrays and the possibility to exploit such structures at meso-and macroscopic scale for life and non-life science applications.


2020 ◽  
Author(s):  
Emmanuel Margolin ◽  
Matthew Verbeek ◽  
Ann Meyers ◽  
Ros Chapman ◽  
Anna-Lise Williamson ◽  
...  

AbstractAn effective prophylactic vaccine is urgently needed to protect against SARS-CoV-2 infection. The viral spike, which mediates entry into cells by interacting with the host angiotensin-converting enzyme 2, is the primary target of most vaccines in development. These vaccines aim to elicit protective immunity against the glycoprotein by use of inactivated virus, vector-mediated delivery of the antigen in vivo, or by direct immunization with the purified antigen following expression in a heterologous system. These approaches are mostly dependent on the growth of mammalian or insect cells, which requires a sophisticated infrastructure that is not generally available in developing countries due to the incumbent costs which are prohibitive. Plant-based subunit vaccine production has long been considered as a cheaper alternative, although low expression yields and differences along the secretory pathway to mammalian cells have posed a challenge to producing certain viral glycoproteins. Recent advances that have enabled many of these constraints to be addressed include expressing the requisite human proteins in plants to support the maturation of the protein of interest. In this study we investigated these approaches to support the production of a soluble and putatively trimeric SARS-CoV-2 spike mimetic in Nicotiana benthamiana via transient Agrobacterium-mediated expression. The co-expression of human calreticulin dramatically improved the accumulation of the viral spike, which was barely detectable in the absence of the co-expressed accessory protein. The viral antigen was efficiently processed even in the absence of co-expressed furin, suggesting that processing may have occurred at the secondary cleavage site and was mediated by an endogenous plant protease. In contrast, the spike was not efficiently processed when expressed in mammalian cells as a control, although the co-expression of furin improved processing considerably. This study demonstrates the feasibility of molecular engineering to improve the production of viral glycoproteins in plants, and supports plant-based production of SARS-CoV-2 spike-based vaccines and reagents for serological assays.


2001 ◽  
Vol 703 ◽  
Author(s):  
Kazuyuki Kuroda ◽  
Atsushi Shimojima

ABSTRACTVarious layered hybrid films prepared from organoalkoxysilanes with long organic chains, based on the self-assembly of the hydrolyzed species, are reviewed. Morphological control of transparent and oriented films was achieved by cohydrolysis and polycondensation with tetraalkoxysilanes, followed by dip- or spin-coating. In addition to alkyltrialkoxysilanes, alkyldimethylmonoalkoxy- and alkylmethyldialkoxy-silanes were also used as the structural units, implying that the inorganic-organic interface can be designed at a molecular level. In these cases, co-condensation in the precursor solution plays an essential role in the formation of homogeneous and ordered films. Alkenyltriethoxysilanes with terminal C=C bonds were also employed to prepare layered hybrid films. Interlayer chains were polymerized upon UV irradiation, and the resulting films exhibited a significant increase in the hardness if compared with the films before polymerization. Hybrid films thus obtained are a new class of materials and of great interest for a wide range of materials chemistry.


2013 ◽  
Vol 2013 ◽  
pp. 1-13 ◽  
Author(s):  
K. Pradeesh ◽  
Nageswara Rao Kotla ◽  
Shahab Ahmad ◽  
Vindesh K. Dwivedi ◽  
G. Vijaya Prakash

Self-assembly has the advantage of fabricating structures of complex functionalities, from molecular levels to as big as macroscopic levels. Natural self-assembly involves self-aggregation of one or more materials (organic and/or inorganic) into desired structures while templated self-assembly involves interstitial space filling of diverse nature entities into self-assembled ordered/disordered templates (both from molecular to macro levels). These artificial and engineered new-generation materials offer many advantages over their individual counterparts. This paper reviews and explores the advantages of such naturally self-assembled hybrid molecular level systems and template-assisted macro-/microstructures targeting simple and low-cost device-oriented fabrication techniques, structural flexibility, and a wide range of photonic applications.


2020 ◽  
Author(s):  
Viraj kirinda ◽  
Scott Hartley

The self-assembly of foldamers into macrocycles is a simple approach to non-biological higher-order structure. Previous work on the co-assembly of ortho-phenylene foldamers with rod-shaped linkers has shown that folding and self-assembly affect each other; that is, the combination leads to new emergent behavior, such as access to otherwise unfavorable folding states. To this point this relationship has been passive. Here, we demonstrate control of self-assembly by manipulating the foldamers’ conformational energy surfaces. A series of o-phenylene decamers and octamers have been assembled into macrocycles using imine condensation. Product distributions were analyzed by gel-permeation chromatography and molecular geometries extracted from a combination of NMR spectroscopy and computational chemistry. The assembly of o-phenylene decamers functionalized with alkoxy groups or hydrogens gives both [2+2] and [3+3] macrocycles. The mixture results from a subtle balance of entropic and enthalpic effects in these systems: the smaller [2+2] macrocycles are entropically favored but require the oligomer to misfold, whereas a perfectly folded decamer fits well within the larger [3+3] macrocycle that is entropically disfavored. Changing the substituents to fluoro groups, however, shifts assembly quantitatively to the [3+3] macrocycle products, even though the structural changes are well-removed from the functional groups directly participating in bond formation. The electron-withdrawing groups favor folding in these systems by strengthening arene–arene stacking interactions, increasing the enthalpic penalty to misfolding. The architectural changes are substantial even though the chemical perturbation is small: analogous o-phenylene octamers do not fit within macrocycles when perfectly folded, and quantitatively misfold to give small macrocycles regardless of substitution. Taken together, these results represent both a high level of structural control in structurally complex foldamer systems and the demonstration of large-amplitude structural changes as a consequence of a small structural effects.


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