Nano-architectures by covalent assembly of molecular building blocks

The construction of electronic devices from single molecular building blocks, which possess certain functions such as switching or rectifying and are connected by atomic-scale wires on a supporting surface, is an essential goal of molecular electronics. A key challenge is the controlled assembly of molecules into desired architectures by strong, that is, covalent, intermolecular connections, enabling efficient electron transport between the molecules and providing high stability. However, no molecular networks on surfaces 'locked' by covalent interactions have been reported so far. Here, we show that such covalently bound molecular nanostructures can be formed on a gold surface upon thermal activation of porphyrin building blocks and their subsequent chemical reaction at predefined connection points. We demonstrate that the topology of these nanostructures can be precisely engineered by controlling the chemical structure of the building blocks. Our results represent a versatile route for future bottom-up construction of sophisticated electronic circuits and devices, based on individual functionalized molecules.     

Carbon nanotube films as a platform to transduce molecular recognition events in metalloporphyrins

Porphyrins have been widely used for many years as functional materials for chemical sensors. Their outstanding chemical features are balanced by some restrictions in terms of transduction techniques. In particular, porphyrin layers are barely conductive, with the consequence that the fabrication of porphyrin based chemiresistors is not possible, except in few rare cases. On the other hand, carbon nanotubes (CNTs) have superior electric properties ranging from metallic to semiconductor in character. Although the conductivity of CNTs is very sensitive to adsorbed molecules, it should be considered that the adsorption onto carbon structures is also scarcely selective and cannot be modified unless other molecular recognition systems are coupled with the CNTs. Following this approach, in this paper we investigated the sensing properties of hybrid CNT-porphyrin films to explore the possibility of transducing the adsorption events occurring in a porphyrin layer into resistance changes of the CNT layers. The results obtained indicate that the presence of the porphyrin films increases the sensitivity of the electric resistance of the CNTs to the concentration of volatile compounds. This enhancement is probably due to the catalytic effect of the metalloporphyrin in conveying the charge transfer from the adsorbate molecule to the CNTs substrate. This property of metalloporphyrins may introduce a further differentiation between porphyrin based sensors that could be positively utilized in sensor array configurations.     

A selective optode membrane for histidine based on fluorescence enhancement of meso-meso-linked porphyrin dimer

A plasticized polymer film, poly(vinyl chloride) (PVC) incorporated with a specific porphyrin dimer, is shown to exhibit significant and analytical usefulness for optical response toward histidine. The porphyrin dimer containing a free-base porphyrin and a covalently linked metalloporphyrin is shown to be weakly fluorescent as a result of the photoinduced intramolecular electron transfer from the inner free-base porphyrin in singlet excited state to a low-spin cobalt(II). The fluorescence enhancement of the membrane by histidine is based on favorable extraction of histidine into the bulk organic membrane and complexation with the inner metallopophyrin moiety and inhibiting the electron transfer process. With the optode membrane described, histidine in a sample solution from 0.0045 to 1.53 mM can be determined. The calibration curve of the optode membrane for histidine shows a good correlation with the mathematically derived formalism and, thus, confirms the theoretically expected behavior. The sensor presented exhibits high selectivity toward histidine over several amino acids and common inorganic anions. The optical selectivity coefficients obtained for histidine over other biologically relevant amino acids and anions are shown to meet the selectivity requirements for the monitoring concentration levels of histidine in biological samples. The selective characteristic of the sensor has been discussed in the view of the coordination chemistry of metalloporphyrin.     

Substrate-induced magnetic ordering and switching of iron porphyrin molecules

To realize molecular spintronic devices, it is important to externally control the magnetization of a molecular magnet. One class of materials particularly promising as building blocks for molecular electronic devices is the paramagnetic porphyrin molecule in contact with a metallic substrate. Here, we study the structural orientation and the magnetic coupling of in-situ-sublimated Fe porphyrin molecules on ferromagnetic Ni and Co films on Cu(100). Our studies involve X-ray absorption spectroscopy and X-ray magnetic circular dichroism experiments. In a combined experimental and computational study we demonstrate that owing to an indirect, superexchange interaction between Fe atoms in the molecules and atoms in the substrate (Co or Ni) the paramagnetic molecules can be made to order ferromagnetically. The Fe magnetic moment can be rotated along directions in plane as well as out of plane by a magnetization reversal of the substrate, thereby opening up an avenue for spin-dependent molecular electronics.     

Organic nanoporous structures

Research on microporous materials, hollow solids with channels and cavities that include small guest molecules, has advanced in fundamental and applied aspects during 1999–2000. The retrosynthesis of crystal structures in terms of robust supramolecular synthons (recognition motifs) and functionalised organic molecules (building blocks) has led to the design of new porous architectures and modification in the properties of existing host materials. Even as conventional O–H⋯O and N–H⋯O hydrogen bonds continue to be used to attain these goals, weak hydrogen bonds and heteroatom interactions, such as C–H⋯O, halogen⋯halogen, strengthened by multi-point recognition and cooperativity effects, have emerged in new design strategies. A proper understanding of pseudopolymorphism, the phenomenon of solvent inclusion in crystals, will promote the next phase of host–guest research.     

Synthesis of functional nanoassemblies in reactive plasmas

Synthesis of various functional nanoassemblies, by using a combination of low-pressure reactive plasma-enhanced chemical deposition and plasma-assisted rf magnetron sputtering deposition is reported. This paper details how selective generation and manipulation of the required building blocks and management of unwanted nanoparticle contaminants, can be used for plasma-aided nanofabrication of carbon nanotip microemitter structures, ultra-high aspect ratio semiconductor nanowires, ordered quantum dot arrays, and microporous hydroxyapatite bioceramics. Emerging challenges of the plasma-aided synthesis of functional nanofilms and nanoassemblies are also discussed.     

Directed Self‐Assembly of Liquid‐Crystalline Molecular Building Blocks for Sub‐5 nm Nanopatterning

The thin‐film directed self‐assembly of molecular building blocks into oriented nanostructure arrays enables next‐generation lithography at the sub‐5 nm scale. Currently, the fabrication of inorganic arrays from molecular building blocks is restricted by the limited long‐range order and orientation of the materials, as well as suitable methodologies for creating lithographic templates at sub‐5 nm dimensions. In recent years, higher‐order liquid crystals have emerged as functional thin films for organic electronics, nanoporous membranes, and templated synthesis, which provide opportunities for their use as lithographic templates. By choosing examples from these fields, recent progress toward the design of molecular building blocks is highlighted, with an emphasis on liquid crystals, to access sub‐5 nm features, their directed self‐assembly into oriented thin films, and, importantly, the fabrication of inorganic arrays. Finally, future challenges regarding sub‐5 nm patterning with liquid crystals are discussed.     

Excitation energy migration processes in various multi-porphyrin assemblies

The electronic interactions and excitation energy transfer (EET) processes of a variety of multi-porphyrin arrays with linear, cyclic and box architectures have been explored. Directly meso-meso linked linear arrays (Z(N)) exhibit strong excitonic coupling with an exciton coherence length of approximately 6 porphyrin units, while fused linear arrays (T(N)) exhibit extensive π-conjugation over the whole array. The excitonic coherence length in directly linked cyclic porphyrin rings (CZ(N)) was determined to be approximately 2.7 porphyrin units by simultaneous analysis of fluorescence intensities and lifetimes at the single-molecule level. By performing transient absorption (TA) and TA anisotropy decay measurements, the EET rates in m-phenylene linked cyclic porphyrin wheels C12ZA and C24ZB were determined to be 4 and 36 ps(-1), respectively. With increasing the size of C(N)ZA, the EET efficiencies decrease owing to the structural distortions that produce considerable non-radiative decay pathways. Finally, the EET rates of self-assembled porphyrin boxes consisting of directly linked diporphyrins, B1A, B2A and B3A, are 48, 98 and 361 ps(-1), respectively. The EET rates of porphyrin boxes consisting of alkynylene-bridged diporphyrins, B2B and B4B, depend on the conformation of building blocks (planar or orthogonal) rather than the length of alkynylene linkers.     

Porphyrin colorimetric indicators in molecular and nano-architectures

One of the most important outcomes of organic nanotechnologies could be development of well-integrated systems for sensing of particular chemical species. Use of color indicators is an attractive approach to guest reporting. Of the known chromophores, porphyrin and its derivatives are the most widely studied functional chromophores in a diverse range of research fields. In this review, recent developments in colorimetric indicator functions of porphyrin derivatives and related compounds in their molecular and nano-architectures are reviewed according to the classification: (i) rather simple porphyrin derivatives, (ii) porphyrin conjugates, (iii) porphyrins embedded in bulk materials, and (iv) porphyrins in organized films. Porphyrin derivatives with unusual structures, such as expanded and N-confused ones have been used for color indicators in specific cases. Electron and energy transfers in porphyrins conjugated with other functional moieties resulted in dynamic sensing systems including switch-on and switch-off actions. Immobilization of porphyrin color indicators in appropriate matrices is important for practical applications. Use of supramolecular films such as self-assembled monolayers, Langmuir-Blodgett films, and layer-by-layer assemblies as porphyrin nanoarchitectures often offers opportunities for colorimetric outputs based on control of their aggregate structures.     

From jammed solids to mechanical metamaterials : A brief review

Here we review recent studies of mechanical metamaterials originating from or closely related to marginally jammed solids. Unlike previous approaches mainly focusing on the design of building blocks to form periodic metamaterials, the design and realization of such metamaterials exploit two special aspects of jammed solids, disorder and isostaticity. Due to the disorder, every single bond of jammed solids is unique. Such a bond uniqueness facilitates the flexible adjustment of the global and local elastic responses of unstressed spring networks derived from jammed solids, leading to auxetic materials with negative Poisson’s ratio and bionic metamaterials to realize allostery and flow controls. The disorder also causes plastic instabilities of jammed solids under load. The jammed networks are thus inherently metamaterials exhibiting multi-functions such as auxeticity, negative compressibility, and energy absorption. Taking advantage of isostaticity, topological mechanical metamaterials analogous to electronic materials such as topological insulators have also been realized, while jammed networks inherently occupy such topological features. The presence of disorder greatly challenges our understanding of jammed solids, but it also provides us with more freedoms and opportunities to design mechanical metamaterials.     

卟啉-多肽超分子组装体系的研究进展

近年来,卟啉-多肽的超分子组装体系的研究受到了国内外学者的广泛关注,已成为超分子化学、生物材料科学研究的前沿领域之一。卟啉-多肽超分子组装体系因具有结构和功能多样化以及良好的生物相容性等优点,在生物传感、药物治疗、分子识别和光电器件等方面展示出巨大的应用潜力。文章综述了卟啉和多肽超分子构筑模块的分子结构设计、组装体的形貌调控、组装体应用3个方面的主要研究进展,介绍了卟啉与多肽分子之间的主要非共价作用方式,包括分子间静电相互作用、氢键、配位键、亲水/疏水性等,分析了该领域当前研究的焦点及亟需解决的问题。     

Biological and chemical decoration of peptide nanostructures via biotin-avidin interactions

Novel architectures with nanometric dimensions hold an immense promise as building blocks for future nanotechnological applications. Biological nanostructures are of special interest due to their biocompatibility and because they allow the utilization of biochemical recognition interfaces. The ability to decorate bio-nanostructures with functional groups is highly important in order to utilize them in several applications including ultrasensitive sensors, drug delivery systems, and tissue engineering. Peptide-based nanostructures have a distinct advantage over other assemblies because they can be easily modified with chemical and biological elements. Aromatic dipeptide nanotubes (ADNT) are formed by the self-assembly of a very simple building block, the diphenylalanine peptide. These nanotubes have remarkable chemical and mechanical properties and their utilization in various applications has previously been demonstrated. Here we report on the chemical modification of ADNT with biotin moieties, in order to enable the selective decoration of the tubes with avidin-labeled species. First, ADNT were prepared in aqueous solution by self-assembly of the dipeptide building blocks. Next, they were modified using N-hydroxysuccinimido-biotin. The level of biotinylation was assessed by the interaction of the tubes with gold-labeled strepavidin and ultrastructural analysis by electron microscopy. The ability of the modified assemblies to serve as a generic functional platform was demonstrated by avidin-mediated conjugation. Avidin was added as a molecular linker to allow the decoration with biotin-labeled quantum dots. The efficient decoration was again probed by the imaging of the modified tubes using laser confocal microscopy. Taken together, we demonstrated the ability to decorate ADNT using a generic avidin-biotin adaptor. This decoration should lead to the integration and utilization of the tubes in various applications.     

Manipulation of self-assembled structures by shape-designed polygonal colloids in 2D

Manipulating self-assembled structures through shape-control of constitute particles is a fascinating yet quite challenging route to make new functional materials that can be used in a variety of applications. Toward this goal, the physics underlying the relation between the shape of constitute building blocks and their self-assembled structures (shape-structure relation) is the key and need to be better understood first. With the advances in particle fabrication techniques, our library of available anisotropic building blocks has expanded enormously, which opens up new opportunities for studying the shape-structure relation. There have been extensive studies performed to explore the self-assembly of anisotropic building blocks and tremendous progress has been made. In this mini-review, we will report recent progress on the self-assembly of non-spherical colloids both in experiments and in simulations. We focus on the self-assembly of polygonal platelets with a variety of shapes in two dimensions including regular polygonal shapes and a specific type of shape, kite-shape. Associated models that are helpful to understand the shape-structure relation are also summarized. We conclude this review with a brief discussion of current challenges in the field.     

Exploring the transferability of large supramolecular assemblies to the vacuum-solid interface

We present an interplay of high-resolution scanning tunneling microscopy imaging and the corresponding theoretical calculations based on elastic scattering quantum chemistry techniques of the adsorption of a gold-functionalized rosette assembly and its building blocks on a Au(111) surface with the goal of exploring how to fabricate functional 3-D molecular nanostructures on surfaces. The supramolecular rosette assembly stabilized by multiple hydrogen bonds has been sublimed onto the Au(111) surface under ultra-high vacuum conditions; the resulting surface nanostructures are distinctly different from those formed by the individual molecular building blocks of the rosette assembly, suggesting that the assembly itself can be transferred intact to the surface by in situ thermal sublimation. This unanticipated result will open up new perspectives for growth of complex 3-D supramolecular nanostructures at the vacuum-solid interface. This article is published with open access at Springerlink.com     

Tuning the Amphiphilicity of Building Blocks: Controlled Self‐Assembly and Disassembly for Functional Supramolecular Materials

Amphiphilicity is one of the molecular bases for self‐assembly. By tuning the amphiphilicity of building blocks, controllable self‐assembly can be realized. This article reviews different routes for tuning amphiphilicity and discusses different possibilities for self‐assembly and disassembly in a controlled manner. In general, this includes irreversible and reversible routes. The irreversible routes concern irreversible reactions taking place on the building blocks and changing their molecular amphiphilicity. The building blocks are then able to self‐assemble to form different supramolecular structures, but cannot remain stable upon loss of amphiphilicity. Compared to the irreversible routes, the reversible routes are more attractive due to the good control over the assembly and disassembly of the supramolecular structure formed via tuning of the amphiphilicity. These routes involve reversible chemical reactions and supramolecular approaches, and different external stimuli can be used to trigger reversible changes of amphiphilicity, including light, redox, pH, and enzymes. It is anticipated that this line of research can lead to the fabrication of new functional supramolecular assemblies and materials.     

Self‐Assembly of Functional Molecules into 1D Crystalline Nanostructures

Self‐assembled functional nanoarchitectures are employed as important nanoscale building blocks for advanced materials and smart miniature devices to fulfill the increasing needs of high materials usage efficiency, low energy consumption, and high‐performance devices. One‐dimensional (1D) crystalline nanostructures, especially molecule‐composed crystalline nanostructures, attract significant attention due to their fascinating infusion structure and functionality which enables the easy tailoring of organic molecules with excellent carrier mobility and crystal stability. In this review, we discuss the recent progress of 1D crystalline self‐assembled nanostructures of functional molecules, which include both a small molecule‐derived and a polymer‐based crystalline nanostructure. The basic principles of the molecular structure design and the process engineering of 1D crystalline nanostructures are also discussed. The molecular building blocks, self‐assembly structures, and their applications in optical, electrical, and photoelectrical devices are overviewed and we give a brief outlook on crucial issues that need to be addressed in future research endeavors.     

Fabrication of Nanoreaction Clusters with Dual‐Functionalized Protein Cage Nanobuilding Blocks

Fabrication of functional nanostructures is a prominent issue in nanotechnology, because they often exhibit unique properties that are different from the individual building blocks. Protein cage nanoparticles are attractive nanobuilding blocks for constructing nanostructures due to their well‐defined symmetric spherical structures, polyvalent nature, and functional plasticity. Here, a lumazine synthase protein cage nanoparticle is genetically modified to be used as a template to generate functional nanobuilding blocks and covalently display enzymes (β‐lactamase) and protein ligands (FKBP12/FRB) on its surface, making dual‐functional nanobuilding blocks. Nanoreaction clusters are subsequently created by ligand‐mediated alternate deposition of two complementary building blocks using layer‐by‐layer (LbL) assemblies. 3D nanoreaction clusters provide enhanced enzymatic activity compared with monolayered building block arrays. The approaches described here may provide new opportunities for fabricating functional nanostructures and nanoreaction clusters, leading to the development of new protein nanoparticle‐based nanostructured biosensor devices.     

Molecular Kondo chain

An important development in recent synthesis strategies is the formation of electronically coupled one and two-dimensional organic systems for potential applications in nanoscale molecule-based devices. Here, we assemble one-dimensional spin chains by covalently linking basic molecular building blocks on a Au(111) surface. Their structural properties are studied by scanning tunneling microscopy and the Kondo effect of the basic molecular blocks inside the chains is probed by scanning tunneling spectroscopy. Tunneling spectroscopic images reveal the existence of separate Kondo regions within the chains while density functional theory calculations unveil antiferromagnetic coupling between the spin centers.     

An optical fiber chemical sensor for mercury ions based on a porphyrin dimer

The synthesis of a novel fluoroionophore, 5-p-[[4-(10',15',20'-triphenyl-5'-porphinato) phenyloxyl]-1-butyloxyl]phenyl-10,15,20-triphenylporphine (DTPP), and its application for preparation of a Hg(II)-sensitive optical fiber chemical sensor are described. The response of the sensor is based on the fluorescence quenching of DTPP by coordination with Hg(II). The porphyrin dimer-based sensor shows a linear response toward Hg(II) in the concentration range 5.2 x 10(-7)-3.1 x 10(-4) mol x L(-1), with a working pH range from 2.4 to 8.0. The sensor shows excellent selectivity for Hg(II) over transition metal cations including Cd(II), Co(II), Cu(II), Ni(II), Pb(II), Zn(II), and Fe(III). As a sensing agent, the porphyrin dimer shows obviously better fluorescence response characteristics toward Hg(II) compared to porphyrin monomer or metalloporphyrin. The effect of the composition of the sensor membrane was studied, and the experimental conditions were optimized. The sensor has been used for determination of Hg(II) in water samples.     

Biphasic Janus particles with nanoscale anisotropy

Advances in the field of nanotechnology have fuelled the vision of future devices spawned from tiny functional components that are able to assemble according to a master blueprint. In this concept, the controlled distribution of matter or 'patchiness' is important for creating anisotropic building blocks and introduces an extra design parameter--beyond size and shape. Although the reliable and efficient fabrication of building blocks with controllable material distributions will be of interest for many applications in research and technology, their synthesis has been addressed only in a few specialized cases. Here we show the design and synthesis of polymer-based particles with two distinct phases. The biphasic geometry of these Janus particles is induced by the simultaneous electrohydrodynamic jetting of parallel polymer solutions under the influence of an electrical field. The individual phases can be independently loaded with biomolecules or selectively modified with model ligands, as confirmed by confocal microscopy and transmission electron microscopy. The fact that the spatial distribution of matter can be controlled at such small length scales will provide access to unknown anisotropic materials. This type of nanocolloid may enable the design of multicomponent carriers for drug delivery, molecular imaging or guided self-assembly.