: The generation of highly reactive oxygen species (ROS) at room temperature for application in organic synthesis and wastewater treatment represents a great challenge of the current chemical industry. In fact, the development of biodegradable scaffolds to support ROS-generating active sites is an important prerequisite for the production of environmentally benign catalysts. Herein, the electrostatic cocrystallization of a cationic phthalocyanine (Pc) and negatively charged tobacco mosaic virus (TMV) is described, together with the capacity of the resulting crystals to photogenerate ROS. To this end, a novel peripherally crowded zinc Pc (1) is synthesized. With 16 positive charges, this photosensitizer shows no aqueous aggregation, and is able to act as a molecular glue in the unidimensional assembly of TMV. A step-wise decrease of ionic strength in mixtures of both components results in exceptionally long fibers, constituted by hexagonally bundled viruses thoroughly characterized by electron and confocal microscopy. The fibers are able to produce ROS in a proof-of-concept microfluidic device, where they are immobilized and irradiated in several cycles, showing a resilient performance. The bottom-up approach also enables the light-triggered disassembly of fibers after use. This work represents an important example of a biohybrid material with projected application in light-mediated heterogeneous catalysis.
: The development of plant viral nanoparticles (VNP) loaded with different molecular versions of a photodynamic drug is described. Specifically, tobacco mosaic virus (TMV) and tobacco mild green mosaic virus (TMGMV) are developed as drug carriers that encapsulate the monocationic, dicationic, tricationic, and tetracationic versions of a porphyrin-based photosensitizer drug (Zn-Por). While TMV has been extensively explored for various nanotechnology applications, this is the first study investiga...
The development of photoactive and biocompatible nanomaterials is a current major challenge of materials science and nanotechnology, as they will contribute to promoting current and future biomedical applications. A growing strategy in this direction consists of using biologically inspired hybrid materials to maintain or even enhance the optical properties of chromophores and fluorophores in biological media. Within this area, porphyrinoids constitute the most important family of organic photose...
Cyclophanes are macrocyclic supramolecular hosts famous for their ability to bind atomic or molecular guests via noncovalent interactions within their well-defined cavities. In a similar way, porous crystalline networks, such as metal–organic frameworks, can create microenvironments that enable controlled guest binding in the solid state. Both types of materials often consist of synthetic components, and they have been developed within separate research fields. Moreover, the use of biomolecules ...
#1Amit A. Vernekar(MIT: Massachusetts Institute of Technology)H-Index: 10
#2Gilles Berger(MIT: Massachusetts Institute of Technology)H-Index: 13
Last. Stephen J. Lippard(MIT: Massachusetts Institute of Technology)H-Index: 158
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Efficient loading of drugs in novel delivery agents has the potential to substantially improve therapy by targeting the diseased tissue while avoiding unwanted side effects. Here we report the first systematic study of the loading mechanism of phenanthriplatin and its analogs into tobacco mosaic virus (TMV), previously used by our group as an efficient carrier for anticancer drug delivery. A detailed investigation of the preferential uptake of phenanthriplatin in its aquated form (∼2000 molecule...
Last. Wonwoo Nam(CAS: Chinese Academy of Sciences)H-Index: 91
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The oxidation of organic substrates is of fundamental importance in nature and includes key transformations in organic synthesis and industry. Dioxygen (O2) is potentially the greenest oxidant because O2 is available in air and its reduction product is water, which is environmentally the most benign substance. However, the direct thermal oxidation of organic substrates with O2 is spin-forbidden because the spin state of ground-state O2 is triplet and the spin state of most organic substrates is ...
The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here, we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy: the formation of catalytical...
Last. Tobias Beck(RWTH Aachen University)H-Index: 16
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The construction of defined nanostructured catalysts is challenging. In previous work, we established a strategy to assemble binary nanoparticle superlattices with oppositely charged protein containers as building blocks. Here, we show that these free-standing nanoparticle superlattices are catalytically active. The metal oxide nanoparticles inside the protein scaffold are accessible for a range of substrates and show oxidase-like and peroxidase-like activity. The stable superlattices can be reu...
#1Roy C. H. Wong(CUHK: The Chinese University of Hong Kong)H-Index: 8
#2Pui-Chi Lo(CityU: City University of Hong Kong)H-Index: 39
Last. Dennis K. P. Ng(CUHK: The Chinese University of Hong Kong)H-Index: 15
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Abstract Being a versatile class of functional dyes, phthalocyanines exhibit a range of intriguing properties enabling them to find practical applications in various disciplines. In the field of biomedicine, they can serve as selective fluorescent probes for bioanalysis and bioimaging, and as efficient photosensitizers for photodynamic therapy of cancer and other non-cancerous conditions. To enhance the selectivity and efficacy, phthalocyanines have been modified by incorporating control units t...
Material properties depend critically on the packing and order of constituent units throughout length scales. Beyond classically explored molecular self-assembly, structure formation in the nanoparticle and colloidal length scales have recently been actively explored for new functions. Structure of colloidal assemblies depends strongly on the assembly process, and higher structural control can be reliably achieved only if the process is deterministic. Here we show that self-assembly of cationic ...
As a clean, inexpensive and widely available energy source, visible light has received increased attention and research interest from all around the world. In the field of synthetic organic chemistry, more and more groups are pursuing visible-light-mediated chemical transformations. Various types of reactions using visible light as an initiator have been described in the past several decades (mainly in the past ten years). It has become a powerful tool for constructing new chemical bonds and has...
#1Jie Zhu(UCSD: University of California, San Diego)H-Index: 26
#2Nicole Avakyan(UCSD: University of California, San Diego)
Last. Chung-Jui Yu(UCSD: University of California, San Diego)
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Proteins are nature's primary building blocks for the construction of sophisticated molecular machines and dynamic materials, ranging from protein complexes such as photosystem II and nitrogenase that drive biogeochemical cycles to cytoskeletal assemblies and muscle fibers for motion. Such natural systems have inspired extensive efforts in the rational design of artificial protein assemblies in the last two decades. As molecular building blocks, proteins are highly complex, in terms of both thei...
Design and synthesis of novel photosensitizer architectures is a key step toward new multifunctional molecular materials. Photoactive Janus-type molecules provide interesting building blocks for such systems by presenting two well-defined chemical functionalities that can be utilized orthogonally. Herein a multifunctional phthalocyanine is reported, bearing a bulky and positively charged moiety that hinders their aggregation while providing the ability to adhere on DNA origami nanostructures via...
#2Asma Rahali(UAM: Autonomous University of Madrid)H-Index: 1
Last. Petr Zimcik(Charles University in Prague)H-Index: 23
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Photodynamic therapy is a treatment modality of cancer based on the production of cytotoxic species upon the light activation of photosensitizers. Zinc phthalocyanine photosensitizers bearing four ...
Last. Thalappil Pradeep(Indian Institute of Technology Madras)H-Index: 85
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Directing the assembly of plasmonic nanoparticles into chiral superstructures has diverse applications including, chiroptical sensing, nonlinear optics, and biomedicine. Though soft template-mediat...
Last. Peter B. Crowley(National University of Ireland, Galway)H-Index: 27
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Precisely defined protein aggregates, as exemplified by crystals, have applications in functional materials. Consequently, engineered protein assembly is a rapidly growing field. Anionic calix[n]arenes are useful scaffolds that can mold to cationic proteins and induce oligomerization and assembly. Here, we describe protein-calixarene composites obtained via cocrystallization of commercially available sulfonato-calix[8]arene (sclx8) with the symmetric and "neutral" protein RSL. Cocrystallization ...
Last. Dirk M. Guldi(FAU: University of Erlangen-Nuremberg)H-Index: 113
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In the scientific race to build up photoactive electron donor-acceptor systems with increasing efficiencies, little is known about the interplay of their building blocks when integrated into supramolecular nanoscale arrays, particularly in aqueous environments. Here, we describe an aqueous donor-acceptor ensemble whose emergence as a nanoscale material renders it remarkably stable and efficient. We have focused on a tetracationic zinc phthalocyanine (ZnPc) featuring pyrenes, which shows an unpre...
In this communication, electrostatically assembled phthalocyanine (Pc)-DNA origami (DO) complexes are formed and their optical properties are demonstrated. The formation of the complex prevents the Pc aggregation, thus yielding an enhanced optical response and photooxidative resilience towards aggregation in biologically-related media. Simultaneously, the Pc protects the DO against enzymatic digestion. Both features solve previous drawbacks associated with phthalocyanine photosensitizers and DNA...
Last. Junqiu Liu(Hangzhou Normal University)H-Index: 2
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: With the increasing advances in the basic understanding of pathogenesis mechanism and fabrication of advanced biological materials, protein nanomaterials are being developed for their potential bioengineering research and biomedical applications. Among different fabrication strategies, supramolecular self-assembly provides a versatile approach to construct hierarchical nanostructures from polyhedral cages, filaments, tubules, monolayer sheets to even cubic crystals through rationally designed ...
