Rafal Klajn
Weizmann Institute of Science
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Chemical Society Reviews | 2010
Rafal Klajn; J. Fraser Stoddart; Bartosz A. Grzybowski
Nanoparticles (NPs) and molecular/supramolecular switches have attracted considerable interest during the past decade on account of their unique properties and prominent roles in the fields of organic chemistry and materials science. Materials derived from the combination of these two components are now emerging in the literature. This critical review evaluates materials which comprise NPs functionalised with well-defined self-assembled monolayers of molecular and supramolecular switches. We draw attention to the fact that immobilisation of switches on NPs does not, in general, hamper their switching ability, although it can impart new properties on the supporting particles. This premise leads us to the discussion of systems in which switching on the surfaces of NPs can be used to modulate reversibly a range of NP properties-optical, fluorescent, electrical, magnetic-as well as the controlled release of small molecules. Finally, we discuss examples in which molecular switches direct reversible self-assembly of NPs (308 references).
Proceedings of the National Academy of Sciences of the United States of America | 2007
Rafal Klajn; Kyle J. M. Bishop; Bartosz A. Grzybowski
Nanoparticles (NPs) decorated with ligands combining photoswitchable dipoles and covalent cross-linkers can be assembled by light into organized, three-dimensional suprastructures of various types and sizes. NPs covered with only few photoactive ligands form metastable crystals that can be assembled and disassembled “on demand” by using light of different wavelengths. For higher surface concentrations, self-assembly is irreversible, and the NPs organize into permanently cross-linked structures including robust supracrystals and plastic spherical aggregates.
Angewandte Chemie | 2009
Rafal Klajn; Paul J. Wesson; Kyle J. M. Bishop; Bartosz A. Grzybowski
Fans of the “Mission Impossible” movies might recall the selfdestructing messages used to brief the secret agent on the details of his new mission. Even beyond the realm of fictitious espionage, materials that store textual or graphical information for a prescribed period of time are desirable for applications in secure communications. 2] Furthermore, if such materials are rewritable, they can help to limit the use of traditional paper, thereby reducing the costs, both industrial and environmental, associated with paper production and recycling. To date, most research on self-erasing media has relied on the use of photochromic molecules—that is, molecules that isomerize and change color when exposed to light of appropriate wavelength—embedded in or attached to a polymeric or gel matrix. In one widely publicized example, Xerox Corporation recently announced the development of photochromic paper that self-erases in 16 to 24 h. While writing with light can be both rapid and accurate, 7] photochromic “inks” are not necessarily optimal for transforming light-intensity patterns into color variations, because they have relatively low extinction coefficients, are prone to photobleaching, and usually offer only two colors corresponding to the two states of photoisomerizing molecules. Herein, we describe a conceptually different self-erasing material in which both the “writing” and self-erasure of color images are controlled by the dynamic non-equilibrium aggregation of photoresponsive metal (here, gold and silver) nanoparticles (Au and AgNPs “inks”) embedded in thin, flexible organogel films. When exposed to UV light, the trans-azobenzene groups coating the NPs isomerize to cisazobenzene with a large dipole moment. As a result, the NPs aggregate into supraspherical (SS) assemblies, whose apparent color depends on the duration of UV irradiation (Figures 1 and 2). Since the SS are metastable and fall apart spontaneously in the absence of UV irradiation, the two-color and multicolor images written into the films gradually self-erase (Figures 2 and 3). The erasure times can be controlled by the number of dipoles induced on the nanoparticles and can also be accelerated by exposure to visible light or by heating the material. Multiple images can be written into the same film either concurrently or after erasure.
Science | 2014
Gurvinder Singh; Henry Chan; Artem Baskin; Elijah Gelman; Nikita Repnin; Petr Král; Rafal Klajn
Tuning the twisting in helical nanowires Assembly of inorganic nanoparticles into complex structures often requires a template. Researchers can now assemble helical nanowires out of cubic magnetite nanocrystals by tuning interactions that bind or separate them. Singh et al. floated the nanocrystals on a liquid and aligned them with a magnetic field. After the liquid evaporated, different twisted nanowires remained. The helices varied according to the concentration of nanocrystals, their shape, and the strength of the magnetic field. Competition between weak forces drives this self-assembly and can lead to arrays with the same twist direction. Science, this issue p. 1149 The presence of a magnetic field helps control the balance among different assembly forces. Organizing inorganic nanocrystals into complex architectures is challenging and typically relies on preexisting templates, such as properly folded DNA or polypeptide chains. We found that under carefully controlled conditions, cubic nanocrystals of magnetite self-assemble into arrays of helical superstructures in a template-free manner with >99% yield. Computer simulations revealed that the formation of helices is determined by the interplay of van der Waals and magnetic dipole-dipole interactions, Zeeman coupling, and entropic forces and can be attributed to spontaneous formation of chiral nanocube clusters. Neighboring helices within their densely packed ensembles tended to adopt the same handedness in order to maximize packing, thus revealing a novel mechanism of symmetry breaking and chirality amplification.
Nature | 2009
Hideyuki Nakanishi; Kyle J. M. Bishop; Bartlomiej Kowalczyk; Abraham Nitzan; Emily A. Weiss; Konstantin V. Tretiakov; Mario M. Apodaca; Rafal Klajn; J. Fraser Stoddart; Bartosz A. Grzybowski
In traditional photoconductors, the impinging light generates mobile charge carriers in the valence and/or conduction bands, causing the material’s conductivity to increase. Such positive photoconductance is observed in both bulk and nanostructured photoconductors. Here we describe a class of nanoparticle-based materials whose conductivity can either increase or decrease on irradiation with visible light of wavelengths close to the particles’ surface plasmon resonance. The remarkable feature of these plasmonic materials is that the sign of the conductivity change and the nature of the electron transport between the nanoparticles depend on the molecules comprising the self-assembled monolayers (SAMs) stabilizing the nanoparticles. For SAMs made of electrically neutral (polar and non-polar) molecules, conductivity increases on irradiation. If, however, the SAMs contain electrically charged (either negatively or positively) groups, conductivity decreases. The optical and electrical characteristics of these previously undescribed inverse photoconductors can be engineered flexibly by adjusting the material properties of the nanoparticles and of the coating SAMs. In particular, in films comprising mixtures of different nanoparticles or nanoparticles coated with mixed SAMs, the overall photoconductance is a weighted average of the changes induced by the individual components. These and other observations can be rationalized in terms of light-induced creation of mobile charge carriers whose transport through the charged SAMs is inhibited by carrier trapping in transient polaron-like states. The nanoparticle-based photoconductors we describe could have uses in chemical sensors and/or in conjunction with flexible substrates.
Nature Chemistry | 2015
Pintu K. Kundu; Dipak Samanta; Ron Leizrowice; Baruch Margulis; Hui Zhao; Martin Börner; Thumu Udayabhaskararao; Debasish Manna; Rafal Klajn
The ability to guide the assembly of nanosized objects reversibly with external stimuli, in particular light, is of fundamental importance, and it contributes to the development of applications as diverse as nanofabrication and controlled drug delivery. However, all the systems described to date are based on nanoparticles (NPs) that are inherently photoresponsive, which makes their preparation cumbersome and can markedly hamper their performance. Here we describe a conceptually new methodology to assemble NPs reversibly using light that does not require the particles to be functionalized with light-responsive ligands. Our strategy is based on the use of a photoswitchable medium that responds to light in such a way that it modulates the interparticle interactions. NP assembly proceeds quantitatively and without apparent fatigue, both in solution and in gels. Exposing the gels to light in a spatially controlled manner allowed us to draw images that spontaneously disappeared after a specific period of time.
Current Organic Chemistry | 2004
Dariusz Witt; Rafal Klajn; Piotr Barski; Bartosz A. Grzybowski
Self-assembled monolayers (SAMs) of alkane thiols on gold and other metals are versatile constructs with which to study interfacial phenomena and reactions at surfaces. Surface properties of SAMs - e.g., wettability, stability in diverse environments, propensity to interact with or to resist adsorption of macromolecules -- depend on and can be controlled flexibly by the properties of the functional (head) groups in the ω position of the alkyl chain. SAMs provide a basis for many important scientific and technological applications, ranging from micropatterning methods, through sensing, to biological recognition. Despite their importance, the literature on SAMs and the synthesis of molecules that constitute them remains scattered and often conflicting. The purpose of this Review is (i) to summarize the applications and physical properties of SAMs and (ii) to systematize the strategies of synthesis of ω-functionalized alkane thiols. Generic retrosynthetic scheme is developed that allows efficient synthetic planning. Issues related to the selection of appropriate protecting groups and the ways of introduction of the thiol functionality are discussed in detail, and illustrated with examples of syntheses of several complex alkane thiols.
Pure and Applied Chemistry | 2010
Rafal Klajn
The immobilization of molecular switches onto inorganic supports has recently become a hot topic as it can give rise to novel hybrid materials in which the properties of the two components are mutually enhanced. Even more attractive is the concept of “transferring” the switchable characteristics of single layers of organic molecules onto the underlying inorganic components, rendering them responsive to external stimuli as well. Of the various molecular switches studied, azobenzene (AB) has arguably attracted most attention due to its simple molecular structure, and because its “trigger” (light) is a noninvasive one, it can be delivered instantaneously, and into a precise location. In order to fully realize its potential, however, it is necessary to immobilize AB onto solid supports. It is the goal of this manuscript to comprehensively yet concisely review such hybrid systems which comprise AB forming well-defined self-assembled monolayers (SAMs) on planar and curved (colloidal and nanoporous) inorganic surfaces. I discuss methods to immobilize AB derivatives onto surfaces, strategies to ensure efficient AB isomerization, ways to monitor the switching process, properties of these switchable hybrid materials, and, last but not least, their emerging applications.
Journal of the American Chemical Society | 2009
Rafal Klajn; Lei Fang; Ali Coskun; Mark A. Olson; Paul J. Wesson; J. Fraser Stoddart; Bartosz A. Grzybowski
Weakly protected metal nanoparticles (MNPs) are used as precursors for the preparation of catenane- and pseudorotaxane-decorated NPs of various compositions (gold, palladium, platinum). When attached to the surface of MNPs, the molecular switches retain their switching abilities. The redox potentials of these switches depend on and can be regulated by the composition of the mixed self-assembled monolayers covering the MNPs.
Nature Nanotechnology | 2016
Hui Zhao; Soumyo Sen; Thumu Udayabhaskararao; Michał Sawczyk; Kristina Kučanda; Debasish Manna; Pintu K. Kundu; Ji-Woong Lee; Petr Král; Rafal Klajn
The chemical behaviour of molecules can be significantly modified by confinement to volumes comparable to the dimensions of the molecules. Although such confined spaces can be found in various nanostructured materials, such as zeolites, nanoporous organic frameworks and colloidal nanocrystal assemblies, the slow diffusion of molecules in and out of these materials has greatly hampered studying the effect of confinement on their physicochemical properties. Here, we show that this diffusion limitation can be overcome by reversibly creating and destroying confined environments by means of ultraviolet and visible light irradiation. We use colloidal nanocrystals functionalized with light-responsive ligands that readily self-assemble and trap various molecules from the surrounding bulk solution. Once trapped, these molecules can undergo chemical reactions with increased rates and with stereoselectivities significantly different from those in bulk solution. Illumination with visible light disassembles these nanoflasks, releasing the product in solution and thereby establishes a catalytic cycle. These dynamic nanoflasks can be useful for studying chemical reactivities in confined environments and for synthesizing molecules that are otherwise hard to achieve in bulk solution.