Bioinspired Molecular Design of Light‐Harvesting Multiporphyrin Arrays

Choi, Myung–Seok; Yamazaki, Tomoko; Yamazaki, Iwao; Aida, Takuzo

doi:10.1002/anie.200301665

Cited by 418 publications

(200 citation statements)

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“…Giant porphyrin arrays and large porphyrin wheels via metal coordination for modeling light-harvesting antenna have been reported by . Aida and coworkers have investigated self-assembled nanometric porphyrin arrays (27)(28)(29). There are limited examples of porphyrin self-assembly by subtle forces, such as van der Waals and CH/ interactions in organic media, despite the fact that porphyrin possesses a flat and electron-rich surface that creates van der Waals, stacking, and charge transfer interactions that play a significant role in its self-assembly (30,31).…”

mentioning

confidence: 99%

Supramolecular polymer formed by reversible self-assembly of tetrakisporphyrin

Haino

Fujii

Watanabe

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

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S-shaped tetrakisporphyrin 2 forms supramolecular polymeric assemblies via a complementary affinity of its bisporphyrin units in solution. The self-association constant determined by applying the isodesmic model is >10 6 L mol ؊1 , which suggests that a sizable polymer forms at millimolar concentrations at room temperature. The electron deficient aromatic guest (TNF) binds within the molecular clefts provided by the bisporphyrin units via a chargetransfer interaction. This guest complexation completely disrupts supramolecular polymeric assembly. The long, fibrous fragments of the polymeric assemblies were characterized by atomic-force microscopy imaging of a film cast on a mica surface. The polymeric assemblies have lengths of >1m and show a coiled structure with a higher level of organization. The approach discussed in this report concerning the quick preparation of supramolecular polymeric assemblies driven by noncovalent forces sets the stage for the preparation of a previously undescribed class of macromolecular porphyrin architectures.porphyrin ͉ supramolecular chemistry S ignificant effort has been directed toward elucidating the energy transport phenomena occurring in natural lightharvesting complexes. A variety of porphyrin-based model compounds have been created to mimic natural light-harvesting complexes with the goal of applying them to artificial lightharvesting systems and molecular photonic devices (1-4). Among them, nanometric multiporphyrin arrays are the most challenging target, wherein, their covalent synthesis offers a high stability and a precisely controlled arrangement of multiporphyrin arrays (5, 6). Unfortunately, the growth of size and complexity of these systems makes their synthesis tedious and inefficient.In contrast, supramolecular self-assembly is a versatile alternative and offers the quick construction of 1-, 2-, or 3-dimensional nanometric architectures that have discrete structures, properties, and functions in which the molecular components are held together by reversible interactions (7-11). Self-assembled nanometric multiporphyrin arrays having well-defined shapes and dimensions provide unique optical and electrochemical properties for photochemical energy conversion and storage. As a consequence, their practical applications can be foreseen in the field of molecular electronics: conductive molecular wires, switches, and photovoltaic cells. These creative developments should pave the way for research directions in creating key materials for emerging field of nanotechnology and science.Coordination-driven self-assembly of porphyrin is one of the most useful approaches for developing large and elaborate molecular architectures (12, 13). Hunter and coworkers developed unique self-assembled porphyrin arrays (14-18). Giant porphyrin arrays and large porphyrin wheels via metal coordination for modeling light-harvesting antenna have been reported by . Aida and coworkers have investigated self-assembled nanometric porphyrin arrays (27-29). There are limited examples of porphyrin self...

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mentioning

confidence: 99%

Supramolecular polymer formed by reversible self-assembly of tetrakisporphyrin

Haino

Fujii

Watanabe

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

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“…The wheel-like and spherical structures of multiporphyrin and dendrimer arrays provide a scaffold for attaining directional energy transfer, allowing excitation energy to cascade efficiently from the periphery to the core. Furthermore, the highly branched nature of dendrimers and multiporphyrin wheels allows coupling of more than one donor moiety per acceptor moiety that can be used to increase the molar absorptivity (52,(75)(76)(77)(78). Building blocks for these structures have included transition metal complexes (ML n ), metal-free and metalchelated porphyrin groups, and various other conjugated photoactive units (20,42,52,76,77,79).…”

Section: Opportunities For Nanotechnology: Synthetic and Biomimetic Amentioning

confidence: 99%

Approaches for biological and biomimetic energy conversion

LaVan

Jennifer²

2006

Proc. Natl. Acad. Sci. U.S.A.

116

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This article highlights areas of research at the interface of nanotechnology, the physical sciences, and biology that are related to energy conversion: specifically, those related to photovoltaic applications. Although much ongoing work is seeking to understand basic processes of photosynthesis and chemical conversion, such as light harvesting, electron transfer, and ion transport, application of this knowledge to the development of fully synthetic and͞or hybrid devices is still in its infancy. To develop systems that produce energy in an efficient manner, it is important both to understand the biological mechanisms of energy flow for optimization of primary structure and to appreciate the roles of architecture and assembly. Whether devices are completely synthetic and mimic biological processes or devices use natural biomolecules, much of the research for future power systems will happen at the intersection of disciplines.biotechnology ͉ nanotechnology ͉ photosynthesis ͉ photovoltaic R ecently, the National Academies and the Keck Foundation held a meeting to discuss the development of new applications for nanotechnology ¶ with the goal of identifying challenges where the convergence of nanoscience and physical and biosciences could provide a revolutionary outcome. One area clearly in need of new technologies is biological and biomimetic methods of energy conversion. Within this broad area, focus was given to two specific applications: the conversion of solar energy into useful electrical or chemical energy and the production of power for in vivo medical devices. The following sections will provide both an economic perspective on current photovoltaic (PV) technology and an overview of the various research efforts toward using or mimicking biological systems to improve current and future energy-conversion systems.

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“…Steele in the late '50s to define an emerging interdisciplinary field linking biology and technological development, is now extending to areas beyond bio-medical applications [1]. Of particular interest in this work, natural photonic structures [2] and microfluidic surfaces [3] are rapidly developing multidisciplinary areas, covering lab-on-chip, sensing and energy harvesting technologies [4]. Even though studies on natural structures date back to the 17 th century, considerable attention is paid since the late 40's and more recently, owing to the deployment of new high-resolution microscopy tools.…”

Section: Introductionmentioning

confidence: 99%

Biomimetic microstructures for photonic and fluidic synergies

Vasileiou¹,

Μπατζάκα²,

Alexandropoulos³

et al. 2017

Optofluidics, Microfluidics and Nanofluidics

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Nature-inspired micro-and nano-structures offer a unique platform for the development of novel synergetic systems combining photonic and microfluidic functionalities. In this context, we examine the paradigm of butterfly Vanessa cardui and develop artificial diffractive microstructures inspired by its natural designs. Softlithographic and nanoimprint protocols are developed to replicate surfaces of natural specimens. Further to their optical behavior, interphases tailored by such microstructures exhibit enhanced hydrophobic properties, as compared to their planar counterparts made of the same materials. Such synergies exploited by new design approaches pave the way to prospective optofluidic, lab-on-chip and sensing applications.

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Bioinspired Molecular Design of Light‐Harvesting Multiporphyrin Arrays

Cited by 418 publications

References 63 publications

Supramolecular polymer formed by reversible self-assembly of tetrakisporphyrin

Supramolecular polymer formed by reversible self-assembly of tetrakisporphyrin

Approaches for biological and biomimetic energy conversion

Biomimetic microstructures for photonic and fluidic synergies

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