scholarly journals (Metallo)porphyrins for potential materials science applications

2017 ◽  
Vol 8 ◽  
pp. 1786-1800 ◽  
Author(s):  
Lars Smykalla ◽  
Carola Mende ◽  
Michael Fronk ◽  
Pablo F Siles ◽  
Michael Hietschold ◽  
...  

The bottom-up approach to replace existing devices by molecular-based systems is a subject that attracts permanently increasing interest. Molecular-based devices offer not only to miniaturize the device further, but also to benefit from advanced functionalities of deposited molecules. Furthermore, the molecules itself can be tailored to allow via their self-assembly the potential fabrication of devices with an application potential, which is still unforeseeable at this time. Herein, we review efforts to use discrete (metallo)porphyrins for the formation of (sub)monolayers by surface-confined polymerization, of monolayers formed by supramolecular recognition and of thin films formed by sublimation techniques. Selected physical properties of these systems are reported as well. The application potential of those ensembles of (metallo)porphyrins in materials science is discussed.

1994 ◽  
Vol 351 ◽  
Author(s):  
Nir Kossovsky ◽  
A. Gelman ◽  
H.J. Hnatyszyn ◽  
E. Sponsler ◽  
G.-M. Chow

ABSTRACTIntrigued by the deceptive simplicity and beauty of macromolecular self-assembly, our laboratory began studying models of self-assembly using solids, glasses, and colloidal substrates. These studies have defined a fundamental new colloidal material for supporting members of a biochemically reactive pair.The technology, a molecular transportation assembly, is based on preformed carbon ceramic nanoparticles and self assembled calcium-phosphate dihydrate particles to which glassy carbohydrates are then applied as a nanometer thick surface coating. This carbohydrate coated core functions as a dehydroprotectant and stabilizes surface immobilized members of a biochemically reactive pair. The final product, therefore, consists of three layers. The core is comprised of the ceramic, the second layer is the dehydroprotectant carbohydrate adhesive, and the surface layer is the biochemically reactive molecule for which delivery is desired.We have characterized many of the physical properties of this system and have evaluated the utility of this delivery technology in vitro and in animal models. Physical characterization has included standard and high resolution transmission electron microscopy, electron and x-ray diffraction and ζ potential analysis. Functional assays of the ability of the system to act as a nanoscale dehydroprotecting delivery vehicle have been performed on viral antigens, hemoglobin, and insulin. By all measures at present, the favorable physical properties and biological behavior of the molecular transportation assembly point to an exciting new interdisciplinary area of technology development in materials science, chemistry and biology.


Nanomaterials ◽  
2020 ◽  
Vol 10 (10) ◽  
pp. 2047
Author(s):  
Xuehui Yan ◽  
Shujing Huang ◽  
Yong Wang ◽  
Yuanyuan Tang ◽  
Ye Tian

Manipulating materials at the atomic scale is one of the goals of the development of chemistry and materials science, as it provides the possibility to customize material properties; however, it still remains a huge challenge. Using DNA self-assembly, materials can be controlled at the nano scale to achieve atomic- or nano-scaled fabrication. The programmability and addressability of DNA molecules can be applied to realize the self-assembly of materials from the bottom-up, which is called DNA nanotechnology. DNA nanotechnology does not focus on the biological functions of DNA molecules, but combines them into motifs, and then assembles these motifs to form ordered two-dimensional (2D) or three-dimensional (3D) lattices. These lattices can serve as general templates to regulate the assembly of guest materials. In this review, we introduce three typical DNA self-assembly strategies in this field and highlight the significant progress of each. We also review the application of DNA self-assembly and propose perspectives in this field.


Biosensors ◽  
2020 ◽  
Vol 10 (11) ◽  
pp. 165
Author(s):  
Hongda Lu ◽  
Shi-Yang Tang ◽  
Guolin Yun ◽  
Haiyue Li ◽  
Yuxin Zhang ◽  
...  

Nanoparticles (NPs) and microparticles (MPs) have been widely used in different areas of research such as materials science, energy, and biotechnology. On-demand synthesis of NPs and MPs with desired chemical and physical properties is essential for different applications. However, most of the conventional methods for producing NPs/MPs require bulky and expensive equipment, which occupies large space and generally need complex operation with dedicated expertise and labour. These limitations hinder inexperienced researchers to harness the advantages of NPs and MPs in their fields of research. When problems individual researchers accumulate, the overall interdisciplinary innovations for unleashing a wider range of directions are undermined. In recent years, modular and integrated systems are developed for resolving the ongoing dilemma. In this review, we focus on the development of modular and integrated systems that assist the production of NPs and MPs. We categorise these systems into two major groups: systems for the synthesis of (1) NPs and (2) MPs; systems for producing NPs are further divided into two sections based on top-down and bottom-up approaches. The mechanisms of each synthesis method are explained, and the properties of produced NPs/MPs are compared. Finally, we discuss existing challenges and outline the potentials for the development of modular and integrated systems.


2008 ◽  
Vol 80 (3) ◽  
pp. 639-658 ◽  
Author(s):  
Jing Lv ◽  
Huibiao Liu ◽  
Yuliang Li

Building supramolecular architectures with well-defined shapes and functions is of great importance in materials science, nanochemistry, and biomimetic chemistry. In recent years, we have devoted much effort to the construction of well-defined supramolecular structures through noncovalent forces such as hydrogen bonding, π-stacking, metal-ligand bonds, and hydrophilic and hydrophobic interactions, with the aid of functional building blocks. The morphologies and their physical properties were studied, and new methods for the construction of one-dimensional nanoscale structures have been developed. In this review, we summarize our recent studies on the design and synthesis of the supramolecular systems, as well as the physical properties of nanoscale structures.


2002 ◽  
Vol 74 (9) ◽  
pp. 1621-1630 ◽  
Author(s):  
Murali Sastry

Nanotechnology is witnessing impressive advances on many different fronts. One of the key areas with important commercial implications concerns the assembly of nanoparticles to form thin films and superstructures by what is commonly known as the "bottom-up" approach. This paper covers some of the more recent developments in this fascinating field with particular emphasis on the work from the author's laboratory on assembly of nanoparticles using electrostatic interactions. The use of electrostatic interactions enables extension of the assembly protocols to the immobilization of biomacromolecules such as proteins/enzymes and DNA with exciting application potential.


Author(s):  
Seungwon Song ◽  
Yoon Hyung Hur ◽  
Ye Min Park ◽  
Eugene N. Cho ◽  
Hyeuk Jin Han ◽  
...  

Directed self-assembly of vertically aligned block copolymer (BCP) thin films have extensively been explored as one of the possible bottom-up routes for sub-10 nm patterning technology. To achieve a vertical...


2019 ◽  
Author(s):  
Mark Workentin ◽  
François Lagugné-Labarthet ◽  
Sidney Legge

In this work we present a clean one-step process for modifying headgroups of self-assembled monolayers (SAMs) on gold using photo-enabled click chemistry. A thiolated, cyclopropenone-caged strained alkyne precursor was first functionalized onto a flat gold substrate through self-assembly. Exposure of the cyclopropenone SAM to UV-A light initiated the efficient photochemical decarbonylation of the cyclopropenone moiety, revealing the strained alkyne capable of undergoing the interfacial strain-promoted alkyne-azide cycloaddition (SPAAC). Irradiated SAMs were derivatized with a series of model azides with varied hydrophobicity to demonstrate the generality of this chemical system for the modification and fine-tuning of the surface chemistry on gold substrates. SAMs were characterized at each step with polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) to confirm successful functionalization and reactivity. Furthermore, to showcase the compatibility of this approach with biochemical applications, cyclopropenone SAMs were irradiated and modified with azide-bearing cell adhesion peptides to promote human fibroblast cell adhesion, then imaged by live cell fluorescence microscopy. Thus, the “photoclick” methodology reported here represents an improved, versatile, catalyst-free protocol that allows for a high degree of control over the modification of material surfaces, with applicability in materials science as well as biochemistry.<br>


2018 ◽  
Author(s):  
Erik Leonhardt ◽  
Jeff M. Van Raden ◽  
David Miller ◽  
Lev N. Zakharov ◽  
Benjamin Aleman ◽  
...  

Extended carbon nanostructures, such as carbon nanotubes (CNTs), exhibit remarkable properties but are difficult to synthesize uniformly. Herein, we present a new class of carbon nanomaterials constructed via the bottom-up self-assembly of cylindrical, atomically-precise small molecules. Guided by supramolecular design principles and circle packing theory, we have designed and synthesized a fluorinated nanohoop that, in the solid-state, self-assembles into nanotube-like arrays with channel diameters of precisely 1.63 nm. A mild solution-casting technique is then used to construct vertical “forests” of these arrays on a highly-ordered pyrolytic graphite (HOPG) surface through epitaxial growth. Furthermore, we show that a basic property of nanohoops, fluorescence, is readily transferred to the bulk phase, implying that the properties of these materials can be directly altered via precise functionalization of their nanohoop building blocks. The strategy presented is expected to have broader applications in the development of new graphitic nanomaterials with π-rich cavities reminiscent of CNTs.


2018 ◽  
Author(s):  
Claudia Contini ◽  
Russell Pearson ◽  
Linge Wang ◽  
Lea Messager ◽  
Jens Gaitzsch ◽  
...  

<div><div><div><p>We report the design of polymersomes using a bottom-up approach where the self-assembly of amphiphilic copolymers poly(2-(methacryloyloxy) ethyl phosphorylcholine)–poly(2-(diisopropylamino) ethyl methacrylate) (PMPC-PDPA) into membranes is tuned using pH and temperature. We study this process in detail using transmission electron microscopy (TEM), nuclear magnetic resonance (NMR) spectroscopy, dynamic light scattering (DLS), and stop-flow ab- sorbance disclosing the molecular and supramolecular anatomy of each structure observed. We report a clear evolution from disk micelles to vesicle to high-genus vesicles where each passage is controlled by pH switch or temperature. We show that the process can be rationalised adapting membrane physics theories disclosing important scaling principles that allow the estimation of the vesiculation minimal radius as well as chain entanglement and coupling. This allows us to propose a new approach to generate nanoscale vesicles with genus from 0 to 70 which have been very elusive and difficult to control so far.</p></div></div></div>


2018 ◽  
Author(s):  
Claudia Contini ◽  
Russell Pearson ◽  
Linge Wang ◽  
Lea Messager ◽  
Jens Gaitzsch ◽  
...  

<div><div><div><p>We report the design of polymersomes using a bottom-up approach where the self-assembly of amphiphilic copolymers poly(2-(methacryloyloxy) ethyl phosphorylcholine)–poly(2-(diisopropylamino) ethyl methacrylate) (PMPC-PDPA) into membranes is tuned using pH and temperature. We study this process in detail using transmission electron microscopy (TEM), nuclear magnetic resonance (NMR) spectroscopy, dynamic light scattering (DLS), and stop-flow ab- sorbance disclosing the molecular and supramolecular anatomy of each structure observed. We report a clear evolution from disk micelles to vesicle to high-genus vesicles where each passage is controlled by pH switch or temperature. We show that the process can be rationalised adapting membrane physics theories disclosing important scaling principles that allow the estimation of the vesiculation minimal radius as well as chain entanglement and coupling. This allows us to propose a new approach to generate nanoscale vesicles with genus from 0 to 70 which have been very elusive and difficult to control so far.</p></div></div></div>


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