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Ring-sliding behavior in polyrotaxanes imbues gels, elastomers, and glasses with remarkable stress-dissipation and actuation properties. Since these properties can be modulated and tuned by structural parameters, many efforts have been devoted to developing synthetic protocols that define the structures and properties of slide-ring materials. We introduce post-synthetic modifications of slide-ring gels derived from unmodified α-cyclodextrin and poly(ethylene glycol) polyrotaxanes that enable (i) actuation and control of the thermo-responsive lower critical solution temperature (LCST) behavior of ring-modified slide-ring hydrogels, and (ii) chemically bonding separate gels into hybrid or shape-reconfigured macro-structures with a slide-ring adhesive solution. The mechanical properties of the post-modified gels have been characterized by shear rheology and uniaxial tensile tests, while the corresponding xerogels were characterized by wide-angle X-ray scattering. These demonstrations show that post-synthetic modification offers a practical solution for re-configuring the properties and shapes of slide-ring gels.
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Wholly synthetic molecules involving both mechanical bonds and a folded secondary structure are one of the most promising architectures for the design of functional molecular machines with unprecedented properties. Here, we report dynamic single-molecule force spectroscopy experiments that explore the energetic details of donor-acceptor oligorotaxane foldamers, a class of molecular switches. The mechanical breaking of the donor-acceptor interactions responsible for the folded structure shows a high constant rupture force over a broad range of loading rates, covering three orders of magnitude. In comparison with dynamic force spectroscopy performed during the past 20 y on various (bio)molecules, the near-equilibrium regime of oligorotaxanes persists at much higher loading rates, at which biomolecules have reached their kinetic regime, illustrating the very fast dynamics and remarkable rebinding capabilities of the intramolecular donor-acceptor interactions. We focused on one single interaction at a time and probed the stochastic rupture and rebinding paths. Using the Crooks fluctuation theorem, we measured the mechanical work produced during the breaking and rebinding to determine a free-energy difference, ΔG, of 6 kcal·mol-1 between the two local conformations around a single bond.
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In spite of widespread interest in rotaxane-based molecular machines and materials, rotaxanes have not been attached covalently to proteins. We describe the near-quantitative aqueous synthesis of [2]rotaxanes based on neutral and charged aqueous hosts-cucurbit[7]uril (CB7) and cyclobis(paraquat-p-phenylene) (CBPQT4+), respectively-using the thiol-ene addition of cysteine and maleimide as a stoppering protocol. After verifying the high efficiency of the reaction using glutathione (GSH) as an oligopeptide stopper, we have employed cytochrome C (CytC) as a protein stopper to produce the first well-characterized protein-rotaxane bioconjugates. We anticipate that this methodology will enable the preparation of novel materials that combine the unique properties of proteins and mechanical bonds.
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Citocromos c/química , Glutatión/química , Oligopéptidos/química , Rotaxanos/síntesis química , Agua/química , Citocromos c/metabolismo , Estructura Molecular , Oligopéptidos/metabolismo , Rotaxanos/químicaRESUMEN
CONSPECTUS: More than two decades of investigating the chemistry of bistable mechanically interlocked molecules (MIMs), such as rotaxanes and catenanes, has led to the advent of numerous molecular switches that express controlled translational or circumrotational movement on the nanoscale. Directed motion at this scale is an essential feature of many biomolecular assemblies known as molecular machines, which carry out essential life-sustaining functions of the cell. It follows that the use of bistable MIMs as artificial molecular machines (AMMs) has been long anticipated. This objective is rarely achieved, however, because of challenges associated with coupling the directed motions of mechanical switches with other systems on which they can perform work. A natural source of inspiration for designing AMMs is muscle tissue, since it is a material that relies on the hierarchical organization of molecular machines (myosin) and filaments (actin) to produce the force and motion that underpin locomotion, circulation, digestion, and many other essential life processes in humans and other animals. Muscle is characterized at both microscopic and macroscopic length scales by its ability to generate forces that vary the distance between two points at the expense of chemical energy. Artificial muscles that mimic this ability are highly sought for applications involving the transduction of mechanical energy. Rotaxane-based molecular switches are excellent candidates for artificial muscles because their architectures intrinsically possess movable filamentous molecular components. In this Account, we describe (i) the different types of rotaxane "molecular muscle" architectures that express contractile and extensile motion, (ii) the molecular recognition motifs and corresponding stimuli that have been used to actuate them, and (iii) the progress made on integrating and scaling up these motions for potential applications. We identify three types of rotaxane muscles, namely, "daisy chain", "press", and "cage" rotaxanes, and discuss their mechanical actuation driven by ions, pH, light, solvents, and redox stimuli. Different applications of these rotaxane-based molecular muscles are possible at various length scales. On a molecular level, they have been harnessed to create adjustable receptors and to control electronic communication between chemical species. On the mesoscale, they have been incorporated into artificial muscle materials that amplify their concerted motions and forces, making future applications at macroscopic length scales look feasible. We emphasize how rotaxanes constitute a remarkably versatile platform for directing force and motion, owing to the wide range of stimuli that can be used to actuate them and their diverse modes of mechanical switching as dictated by the stereochemistry of their mechanical bonds, that is, their mechanostereochemistry. We hope that this Account will serve as an exposition that sets the stage for new applications and materials that exploit the capabilities of rotaxanes to transduce mechanical energy and help in paving the path going forward to genuine AMMs.
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The ability to design and confer control over the kinetics of theprocesses involved in the mechanisms of artificial molecular machines is at the heart of the challenge to create ones that can carry out useful work on their environment, just as Nature is wont to do. As one of the more promising forerunners of prototypical artificial molecular machines, chemists have developed bistable redox-active donor-acceptor mechanically interlocked molecules (MIMs) over the past couple of decades. These bistable MIMs generally come in the form of [2]rotaxanes, molecular compounds that constitute a ring mechanically interlocked around a dumbbell-shaped component, or [2]catenanes, which are composed of two mechanically interlocked rings. As a result of their interlocked nature, bistable MIMs possess the inherent propensity to express controllable intramolecular, large-amplitude, and reversible motions in response to redox stimuli. In this Account, we rationalize the kinetic behavior in the ground state for a large assortment of these types of bistable MIMs, including both rotaxanes and catenanes. These structures have proven useful in a variety of applications ranging from drug delivery to molecular electronic devices. These bistable donor-acceptor MIMs can switch between two different isomeric states. The favored isomer, known as the ground-state co-conformation (GSCC) is in equilibrium with the less favored metastable state co-conformation (MSCC). The forward (kf) and backward (kb) rate constants associated with this ground-state equilibrium are intimately connected to each other through the ground-state distribution constant, KGS. Knowing the rate constants that govern the kinetics and bring about the equilibration between the MSCC and GSCC, allows researchers to understand the operation of these bistable MIMs in a device setting and apply them toward the construction of artificial molecular machines. The three biggest influences on the ground-state rate constants arise from (i) ground-state effects, the energy required to breakup the noncovalent bonding interactions that stabilize either the GSCC or MSCC, (ii) spacer effects, where the structures overcome additional barriers, either steric or electrostatic or both, en route from one co-conformation to the other, and (iii) the physical environment of the bistable MIMs. By managing all three of these effects, chemists can vary these rate constants over many orders of magnitude. We also discuss progress toward achieving mechanostereoselective motion, a key principle in the design and realization of artificial molecular machines capable of doing work at the molecular level, by the strategic implementation of free energy barriers to intramolecular motion.
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Catenanos/química , Rotaxanos/química , Cinética , Conformación Molecular , Oxidación-Reducción , Electricidad Estática , EstereoisomerismoRESUMEN
"Molecular flasks" are well-defined supramolecular cages that can encapsulate one or more molecular guests within their cavities and, in so doing, change the physical properties and reactivities of the guests. Although molecular flasks are powerful tools for manipulating matter on the nanoscale, most of them are limited in their scope because of size restrictions. Recently, however, increasingly large and diverse supramolecular cages have become available with enough space in their cavities for larger chemical systems such as polymers, nanoparticles, and biomolecules. Here we report how a class of metallosupramolecular cages known as M12L24 polyhedra have been adapted to serve as nanometer-scale containers for solutions of a pseudorotaxane host-guest complex based on a tetracationic cyclophane host, cyclobis(paraquat-p-phenylene) (CBPQT(4+)), and a 1,5-dioxynaphthalene (DNP) guest. Remarkably, the hierarchical integration of pseudorotaxanes and M12L24 superhosts causes the system to express stimulus-responsive behavior, a property which can be described as emergent because neither the DNPâCBPQT(4+) nor the M12L24 assemblies exhibit this behavior independently. The DNP-containing M12L24 molecular flasks are effectively "sealed off" to CBPQT(4+) until ions are added as a stimulus to "open" them. The electrolyte stimulus reduces the electrostatic screening distance in solution, allowing favorable DNPâCBPQT(4+) host-guest interactions to overcome repulsive Coulombic interactions between the cationic M12L24 cages and CBPQT(4+) rings. This unusual example of ion-gated transport into chemical nanocontainers is reminiscent of transmembrane ion channels which act as gates to the cell, with the important difference that this system is reversible and operates at equilibrium.
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We report the one-pot synthesis and electrochemical switching mechanism of a family of electrochemically bistable 'daisy chain' rotaxane switches based on a derivative of the so-called 'blue box' (BB(4+)) tetracationic cyclophane cyclobis(paraquat-p-phenylene). These mechanically interlocked molecules are prepared by stoppering kinetically the solution-state assemblies of a self-complementary monomer comprising a BB(4+) ring appended with viologen (V(2+)) and 1,5-dioxynaphthalene (DNP) recognition units using click chemistry. Six daisy chains are isolated from a single reaction: two monomers (which are not formally 'chains'), two dimers, and two trimers, each pair of which contains a cyclic and an acyclic isomer. The products have been characterized in detail by high-field (1)H NMR spectroscopy in CD3CN-made possible in large part by the high symmetry of the novel BB(4+) functionality-and the energies associated with certain aspects of their dynamics in solution are quantified. Cyclic voltammetry and spectroelectrochemistry have been used to elucidate the electrochemical switching mechanism of the major cyclic daisy chain products, which relies on spin-pairing interactions between V(â¢+) and BB(2(â¢+)) radical cations under reductive conditions. These daisy chains are of particular interest as electrochemically addressable molecular switches because, in contrast with more conventional bistable catenanes and rotaxanes, the mechanical movement of the ring between recognition units is accompanied by significant changes in molecular dimensions. Whereas the self-complexed cyclic monomer-known as a [c1]daisy chain or molecular 'ouroboros'-conveys sphincter-like constriction and dilation of its ultramacrocyclic cavity, the cyclic dimer ([c2]daisy chain) expresses muscle-like contraction and expansion along its molecular length.
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Although motor proteins are essential cellular components that carry out biological processes by converting chemical energy into mechanical motion, their functions have been difficult to mimic in artificial synthetic systems. Daisy chains are a class of rotaxanes which have been targeted to serve as artificial molecular machines because their mechanically interlocked architectures enable them to contract and expand linearly, in a manner that is reminiscent of the sarcomeres of muscle tissue. The scope of external stimuli that can be used to control the musclelike motions of daisy chains remains limited, however, because of the narrow range of supramolecular motifs that have been utilized in their templated synthesis. Reported herein is a cyclic daisy chain dimer based on π-associated donor-acceptor interactions, which can be actuated with either thermal or electrochemical stimuli. Molecular dynamics simulations have shown the daisy chain's mechanism of extension/contraction in the ground state in atomistic detail.
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Incorporation of two biphenylene-bridged 4,4'-bipyridinium extended viologen units into a para-phenylene-based cyclophane results in a synthetic receptor that is ~2 nm long and adopts a box-like geometry. This cyclophane, Ex(2)Box(4+), possesses the ability to form binary and ternary complexes with a myriad of guest molecules ranging from long π-electron-rich polycyclic aromatic hydrocarbons, such as tetracene, tetraphene, and chrysene, to π-electron-poor 2,6-dinitrotoluene, 1,2,4-trichlorobenzene, and both the 9,10- and 1,4-anthraquinone molecules. Moreover, Ex(2)Box(4+) is capable of forming one-to-one complexes with polyether macrocycles that consist of two π-electron-rich dioxynaphthalene units, namely, 1,5-dinaphtho[38]crown-10. This type of broad molecular recognition is possible because the electronic constitution of Ex(2)Box(4+) is such that the pyridinium rings located at the "ends" of the cyclophane are electron-poor and prefer to enter into donor-acceptor interactions with π-electron-rich guests, while the "middle" of the cyclophane, consisting of the biphenylene spacer, is more electron-rich and can interact with π-electron-poor guests. In some cases, these different modes of binding can act in concert to generate one-to-one complexes which possess high stability constants in organic media. The binding affinity of Ex(2)Box(4+) was investigated in the solid state by way of single-crystal X-ray diffraction and in solution by using UV-vis and NMR spectroscopy for 12 inclusion complexes consisting of the tetracationic cyclophane and the corresponding guests of different sizes, shapes, and electronic compositions. Additionally, density functional theory was carried out to elucidate the relative energetic differences between the different modes of binding of Ex(2)Box(4+) with anthracene, 9,10-anthraquinone, and 1,4-anthraquinone in order to understand the degree with which each mode of binding contributes to the overall encapsulation of each guest.
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A template-directed protocol, which capitalizes on donor-acceptor interactions, is employed to synthesize a semi-rigid cyclophane (ExBox(4+)) that adopts a box-like geometry and is comprised of π-electron-poor 1,4-phenylene-bridged ("extended") bipyridinium units (ExBIPY(2+)). ExBox(4+) functions as a high-affinity scavenger of an array of different polycyclic aromatic hydrocarbons (PAHs), ranging from two to seven fused rings, as a result of its large, accommodating cavity (approximately 3.5 Å in width and 11.2 Å in length when considering the van der Waals radii) and its ability to form strong non-covalent bonding interactions with π-electron-rich PAHs in either organic or aqueous media. In all, 11 PAH guests were observed to form inclusion complexes with ExBox(4+), with coronene being the largest included guest. Single-crystal X-ray diffraction data for the 11 inclusion complexes ExBox(4+)âPAH as well as UV/vis spectroscopic data for 10 of the complexes provide evidence of the promiscuity of ExBox(4+) for the various PAHs. Nuclear magnetic resonance spectroscopy and isothermal titration calorimetric analyses of 10 of the inclusion complexes are employed to further characterize the host-guest interactions in solution and determine the degree with which ExBox(4+) binds each PAH compound. As a proof-of-concept, a batch of crude oil from Saudi Arabia was subjected to extraction with the water-soluble form of the PAH receptor, ExBox·4Cl, resulting in the isolation of different aromatic compounds after ExBox·4Cl was regenerated.
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Hidrocarburos Policíclicos Aromáticos/química , Cristalografía por Rayos X , Modelos Moleculares , Estructura Molecular , Hidrocarburos Policíclicos Aromáticos/síntesis químicaRESUMEN
Fashioned through billions of years of evolution, biological molecular machines, such as ATP synthase, myosin, and kinesin, use the intricate relative motions of their components to drive some of life's most essential processes. Having control over the motions in molecules is imperative for life to function, and many chemists have designed, synthesized, and investigated artificial molecular systems that also express controllable motions within molecules. Using bistable mechanically interlocked molecules (MIMs), based on donor-acceptor recognition motifs, we have sought to imitate the sophisticated nanoscale machines present in living systems. In this Account, we analyze the thermodynamic characteristics of a series of redox-switchable [2]rotaxanes and [2]catenanes. Control and understanding of the relative intramolecular movements of components in MIMs have been vital in the development of a variety of applications of these compounds ranging from molecular electronic devices to drug delivery systems. These bistable donor-acceptor MIMs undergo redox-activated switching between two isomeric states. Under ambient conditions, the dominant translational isomer, the ground-state coconformation (GSCC), is in equilibrium with the less favored translational isomer, the metastable-state coconformation (MSCC). By manipulating the redox state of the recognition site associated with the GSCC, we can stimulate the relative movements of the components in these bistable MIMs. The thermodynamic parameters of model host-guest complexes provide a good starting point to rationalize the ratio of GSCC to MSCC at equilibrium. The bistable [2]rotaxanes show a strong correlation between the relative free energies of model complexes and the ground-state distribution constants (K(GS)). This relationship does not always hold for bistable [2]catenanes, most likely because of the additional steric and electronic constraints present when the two rings are mechanically interlocked with each other. Measuring the ground-state distribution constants of bistable MIMs presents its own set of challenges. While it is possible, in principle, to determine these constants using NMR and UV-vis spectroscopies, these methods lack the sensitivity to permit the determination of ratios of translational isomers greater than 10:1 with sufficient accuracy and precision. A simple application of the Nernst equation, in combination with variable scan-rate cyclic voltammetry, however, allows the direct measurement of ground-state distribution constants across a wide range (K(GS) = 10-10(4)) of values.
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Catenanos/química , Rotaxanos/química , Termodinámica , Oxidación-ReducciónRESUMEN
Using impedance spectroscopy, we demonstrate that the low fill factor (FF) typically observed in small molecule solar cells is due to hindered carrier transport through the active layer and hindered charge transfer through the anode interfacial layer (IFL). By carefully tuning the active layer thickness and anode IFL in BDT(TDPP)2 solar cells, the FF is increased from 33 to 55% and the PCE from 1.9 to 3.8%. These results underscore the importance of simultaneously optimizing active layer thickness and IFL in small molecule solar cells.
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Espectroscopía Dieléctrica , Suministros de Energía Eléctrica , Fulerenos/química , Compuestos Heterocíclicos con 3 Anillos/química , Tiofenos/química , Energía Solar , Soluciones/químicaRESUMEN
We explore the mechanics and damage of slide-ring gels by developing a discrete model for the mechanics of chain-ring polymer systems that accounts for both crosslink motion and internal chain sliding. The proposed framework utilizes an extendable Langevin chain model to describe the constitutive behavior of polymer chains undergoing large deformation and includes a rupture criterion to innately capture damage. Similarly, crosslinked rings are described as large molecules that also store enthalpic energy during deformation and thus have their own rupture criterion. Using this formalism, we show that the realized mode of damage in a slide-ring unit is a function of the loading rate, distribution of segments, and inclusion ratio (number of rings per chain). After analyzing an ensemble of representative units under different loading conditions, we find that failure is driven by damage to crosslinked rings at slow loading rates, but polymer chain scission at fast loading rates. Our results indicate that increasing the strength of the crosslinked rings may improve the toughness of the material.
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Slide-ring materials are polymer networks with mobile cross-links that exhibit impressive stress dissipation and fracture resistance owing to the pulley effect. On account of their remarkable ability to dissipate the energy of deformation, these materials have found their way into advanced materials such as abrasion-resistant coatings and elastic battery electrode binders. In this work, we explore the role of mobile cross-links on the properties of a biofriendly pressure-sensitive adhesive made using composites of cyclodextrin-based macromolecules and poly(lipoic acid). We modify cyclodextrin-based hosts and polyrotaxanes with pendant groups of lipoic acid (a commonly ingested antioxidant) to incorporate them as cross-links in poly(lipoic acid) networks obtained by simple heating in open air. By systematically varying the adhesive formulations while probing their mechanical and adhesive properties, we uncover trends in structure-property relationships that enable one to tune network properties and access biofriendly, high-tack adhesives.
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Soil health is one of the key factors in determining the sustainability of global agricultural systems and the stability of natural ecosystems. Microbial decomposition activity plays an important role in soil health; and gaining spatiotemporal insights into this attribute is critical for understanding soil function as well as for managing soils to ensure agricultural supply, stem biodiversity loss, and mitigate climate change. Here, a novel in situ electronic soil decomposition sensor that relies on the degradation of a printed conductive composite trace utilizing the biopolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) as a binder is presented. This material responds selectively to microbially active environments with a continuously varying resistive signal that can be readily instrumented with low-cost electronics to enable wide spatial distribution. In soil, a correlation between sensor response and intensity of microbial decomposition activity is observed and quantified by comparison with respiration rates over 14 days, showing that devices respond predictably to both static conditions and perturbations in general decomposition activity.
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Mechanically interlocked objects are ubiquitous in our world. They can be spotted on almost every scale of matter and in virtually every sector of society, spanning cultural, temporal, and physical boundaries the world over. From art to machinery, to biological entities and chemical compounds, mechanical interlocking is being used and admired every day, inspiring creativity and ingenuity in art and technology alike. The tiny world of mechanically interlocked molecules (MIMs), which has been established and cultivated over the past few decades, has connected the ordinary and molecular worlds symbolically with creative research and artwork that subsumes the molecular world as a miniaturization of the ordinary one. In this review, we highlight how graphical representations of MIMs have evolved to this end, and discuss various other aspects of their beauty as chemists see them today. We argue that the many aspects of beauty in MIMs are relevant, not only to the pleasure chemists derive from their research, but also to the progress of the research itself.
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Arte , Fenómenos Mecánicos , Naturaleza , Humanos , Apoyo SocialRESUMEN
Despite hundreds of studies involving slide-ring gels derived from cyclodextrin (CD)-based polyrotaxanes (PRs), their covalent cross-linking kinetics are not well characterized. We employ chemorheology as a tool to measure the gelation kinetics of a model slide-ring organogel derived from α-cyclodextrin/poly (ethylene glycol) PRs cross-linked with hexamethylenediisocyanate (HMDI) in DMSO. The viscoelastic properties of the gels were monitored in situ by small-amplitude oscillatory shear (SAOS) rheology, enabling us to estimate the activation barrier and rate law for cross-linking while mapping experimental parameters to kinetics and mechanical properties. Gelation time, gel point, and final gel elasticity depend on cross-linker concentration, but polyrotaxane concentration only affects gelation time and elasticity (not gel point), while temperature only affects gelation time and gel point (not final elasticity). These measurements facilitate the rational design of slide-ring networks by simple parameter selection (temperature, cross-linker concentration, PR concentration, reaction time).
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The cycloparaphenylene (CPP) nanocarbons are an appealing family of macrocyclic organic semiconductors with size-tunable structures and unique optoelectronic properties, which can be further modulated by complexation with guest molecules. While many π-π-stabilized CPP-fullerene host-guest complexes are known, CPPs can also host polycyclic guests stabilized by aromatic CH-π interactions. Here we combine experimental and computational results to report that CH-π interactions can also be tapped to include redox-active metallocene guests in [8]cycloparaphenylene ([8]CPP). Oxidation of a metallocene guest is accompanied by an increase in binding affinity and tilt angle. Crystallographically determined solid-state structures reveal CH-π interactions in the ferrocene complex (Fcâ[8]CPP) and additional π-π interactions in the cobaltocenium complex (CoCp2+â[8]CPP). Functionalizing Fc with oxygen-bearing side chains also improves complex stability to a similar extent as oxidation, due to the formation of CH-O hydrogen bonds with the host's p-phenylene units. This work shows that CH-π bonding can be generalized as a driving force for CPP host-guest complexes and combined with other supramolecular forces to enhance stability. Owing to their semiconducting nature, amenability to functionalization, and reversible redox-dependent behavior, the [8]CPP-metallocene host-guest complexes may expand the library of synthons available for designing bespoke nanoelectronics and artificial molecular machines.
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We report the synthesis, characterization, and first implementation of a naphtho[2,3-b:6,7-b']dithiophene (NDT)-based donor molecule in highly efficient organic photovoltaics (OPVs). When NDT(TDPP)(2) (TDPP = thiophene-capped diketopyrrolopyrrole) is combined with the electron acceptor PC(61)BM, a power conversion efficiency (PCE) of 4.06 ± 0.06% is achieved-a record for a PC(61)BM-based small-molecule OPV. The substantial PCE is attributed to the broad, high oscillator strength visible absorption, the ordered molecular packing, and an exceptional hole mobility of NDT(TDPP)(2).
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Suministros de Energía Eléctrica , Naftalenos/química , Pirroles/química , Energía Solar , Tiofenos/química , Naftalenos/síntesis química , Pirroles/síntesis química , Tiofenos/síntesis químicaRESUMEN
This work reports the development of a mechanochemistry activated covalent conjugation (MACC) reaction that shows areas of interfacial failure in soft hydrogels. Hydrogels are prone to delamination from rigid substrates due to the competition between swelling and adhesion, which can lead to bonding failure in a mechanism similar to crack propagation in harder materials. In this work, reductive amination was shown to occur when a ketone-bearing fluorescein derivative was bonded to an amine-functionalized hydrogel, as both of these moieties were found to be necessary for covalent conjugation into the gel network. For thin, circular polyacrylamide hydrogels, wrinkle patterns and regions of subsequent delamination at the edge of the gel were found to be selectively tagged by the dye. This reaction was then used to explore the effect of gel properties on patterns of interfacial failure. As cross-linker loading increased, the propagation of the delamination front and the area fraction of delamination were both found to increase, as shown by fluorescence images of gels. Increasing the thickness of the gel increased the fraction of delaminated area but did not change its propagation toward the center of the gel. This MACC reaction shows how mechanochemical reactions can be used for fluorescence tagging without incorporating mechanophores into the polymer gel matrix.