Supramolecular Reaction Research Articles

Encapsulated Dye in Coordination-Assembled Octahedron for Visible-Light-Driven Proton Reduction and Nitroaromatic Hydrogenation.

To mimic the finely tuned natural photosynthetic systems, a large metal-organic octahedron was synthesized by one-pot self-assembly with modified triphenylamine ligands and redox-active cobalt ions. By encapsulating an organic dye, fluorescein (Fl), within the inner cavity of the octahedron, the host-guest supramolecular system was provided for light-driven hydrogen production. The intimate distance between the redox site and the photosensitizer in the supramolecular metal-organic cage allowed the photoinduced electrons to transfer from the excited state Fl* to the redox cobalt center in a pseudo-intramolecular pathway. The supramolecular system showed good performance in light-driven hydrogen production and the reduction of nitroaromatic compounds. Control experiments based on a mononuclear compound resembling a cobalt corner of the octahedron and inhibitor competition provided evidence of enzyme-like catalytic behavior. The supramolecular reaction pathways within confined spaces contribute to the superior activity of the host-guest system.

Preparation of a Novel Phosphorus–Nitrogen‐Containing Flame Retardant by Supramolecular Reaction and its Application in Epoxy Resin

Piperazine hexahydrate (PI) and diethylenetriamine penta(methylene phosphonic acid) (DTPMP) are used to synthesize flame‐retardant PI‐DTPMP through supramolecular reaction. The incorporation of PI‐DTPMP simultaneously improves the mechanical and flame‐retardant properties of epoxy resin (EP). With only 5 wt% loading of PI‐DTPMP, EP composites show excellent flame retardancy with a limiting oxygen index (LOI) of 36.4% and V‐0 rating in the UL‐94 test. The cone calorimetric test results demonstrates that the peak heat release rate, total heat release, and total smoke release of EP/5%PI‐DTPMP are reduced by 44.9%, 34.7%, and 37.7% compared with that of neat EP, respectively, owing to the formation of compact and insulating char layer during combustion. Moreover, EP/PI‐DTPMP composites show enhanced mechanical properties with the improved tensile and impact strength, as well as higher storage modulus, crosslink densities, and glass‐transition temperatures in dynamic mechanical analysis.

Illustrating the overall reaction network of the synthesis-gas-to-hydrocarbons process over iron-zeolite bifunctional catalysis

Since its discovery in the early 20 th century, Fischer-Tropsch synthesis (FTS) has opened a path, as an alternative to crude oil, to produce fuels and chemicals. When classical FTS catalysts are combined with acidic zeolites, the scope of this gas-phase polymerization can be narrowed, thus maximizing the production of value-added commodities and eliminating energy-consuming separation steps. However, from a mechanistic standpoint, even now, little is known about the role of the different reaction intermediates. Here, we present a comprehensive, in-depth, mechanistic investigation using solid-state NMR spectroscopy and well-designed control experiments on combining a classical Fe-based FTS catalyst and zeolites with different topologies to establish the impact of “co-catalytic” key organic carbon-based reaction intermediates, including carbonylated/oxygenated species (ester/ketone/alcohol/ether/epoxide/ketene). Consequently, this work provides experimental evidence supporting the “co-existence” of oxygenate (cf. surface-enol and CO-insertion) mechanisms (together with the traditional carbide-based FTS mechanism). The significance of “supramolecular reactive centers” within zeolite and host-guest chemistry has also been illuminated. • Zeolite topologies altered preferential hydrocarbon product selectivities • Mobility-based solid-state NMR identified crucial carbon-based reaction intermediates • Co-involvement of oxygenated/carbonylated species is evaluated during syngas conversion • Significance of inorganic-organic supramolecular reaction centers has been established To alleviate pressure from increased environmental regulations over carbon emissions, the direct hydrogenation of CO/CO 2 to diverse hydrocarbons over bifunctional catalysts is a priority research topic worldwide. Identifying new catalytic routes to valorize C1-feedstock is a key to combating climate change, whereby Fischer-Tropsch synthesis (FTS) over bifunctional metal-zeolite catalysts offers elegant solutions to diversify global fuel/chemical supply. However, their overall reaction network to deliver preferential final product selectivity remains elusive and controversial. Through this work, we achieve this goal by identifying key carbon-based reaction intermediates and establishing a full reaction network of the synthesis-gas-to-hydrocarbons process over Fe 2 O 3 @KO 2 /zeolite catalyst. This established structure-reactivity relationship can upgrade the current FTS process and improve the fundamental understanding of bifunctional catalysis. Identifying “descriptor”-style carbon-based reaction intermediates is significant in upgrading the current state of metal-zeolite bifunctional “cascade” catalysis. In this work, four different product selectivities (short olefins, light paraffins, long-chain hydrocarbons, and aromatics) were observed during the syngas-to-hydrocarbon process (Fischer-Tropsch type) over potassium superoxide-doped iron oxide/zeolite-based bifunctional catalysts. Here, we demonstrate that the zeolite topology and “co-catalytic” hybrid supramolecular reactive centers (i.e., organic hydrocarbons pool species trapped by the inorganic zeolite) regulate the reaction mechanism and the final product selectivity.

Gold Nanocluster Functionalized with Peptide Dendron Thiolates: Acceleration of the Photocatalytic Oxidation of an Amino Alcohol in a Supramolecular Reaction Field

Herein, we report the synthesis of gold nanoclusters (AuNCs) functionalized by peptide dendron thiolate ligands forming a hydrogen bonding supramolecular reaction field. The prepared AuNCs act as efficient photocatalysts that promote the oxidative cyclization of an amino alcohol to afford the oxazolidine product. Circular dichroism (CD) spectroscopy and 1H NMR titration experiments revealed that the dynamic transformation of interdendron hydrogen bonds into intermolecular hydrogen bonds between the ligand and the substrate is the key to accelerating the photocatalytic reaction. This work introduces a concept for tuning the reactivities and selectivities of metal nanocluster catalysts that use supramolecular reaction fields created with dendritic thiolate ligands.

Charge Stabilization in Axially Linked Donor – Aluminum(III) Porphyrin – Fullerene Reaction Center Models

In supramolecular reaction center models, the lifetime of the charge-separated state depends on many factors. However, little attention has been paid to the redox potential of the species that lie between the donor and acceptor in the final charge-separated state. Recently, we reported a series of self-assembled aluminum porphyrin-based triads that provide a unique opportunity to study the influence of the porphyrin redox potential independently of other factors. The triads, Donor-AlPorFn-C60, were constructed by linking the fullerene (C60) and Donor to the aluminum(III) porphyrin. The porphyrin (AlPor, AlPorF3, or AlPorF5) redox potentials are tuned by the substitution of phenyl (Ph), 3,4,5-trifluorophenyl (PhF3), or 2,3,4,5,6-pentafluorophenyl (PhF5) groups in its meso positions. The C60 and Donor (BTMPA) units are bound axially to opposite faces of the porphyrin plane via covalent and coordination bonds, respectively. Excitation of all of the triads results in sequential electron transfer that generates the identical final charge-separated state, BTMPA•+-AlPorFn-Ph-C60 •−, which lies energetically 1.50 eV above the ground state. Although the radical pair is identical in all of the triads, remarkably, the lifetime of the BTMPA•+-AlPorFn-Ph-C60 •− radical pair was found to be very different in each of them. I will discuss some of these systems in terms of their design principles and photoinduced properties. Figure 1

Decelerating Charge Recombination Using Fluorinated Porphyrins in N,N-Bis(3,4,5-trimethoxyphenyl)Aniline-Aluminum(III)Porphyrin-Fullerene Reaction Center Models

In supramolecular reaction center models, the lifetime of the charge-separated state depends on many factors. However, little attention has been paid to the redox potential of the species that lie between the donor and acceptor in the final charge separated state. Here, we report on a series of self-assembled aluminum porphyrin-based triads that provide a unique opportunity to study the influence of the porphyrin redox potential independently of other factors. The triads, BTMPA-AlPor-C60, were constructed by linking the fullerene (C60) and bis(3,4,5-trimethoxyphenyl)aniline (BTMPA) to the aluminum(III) porphyrin. The redox potentials of aluminum(III) tetraphenylporphyrin (AlPor) are tuned by substitution of phenyl, 3,4,5-trifluorophenyl, or 2,3,4,5,6-pentafluorophenyl groups in its meso positions. The C60 and BTMPA units are bound axially to opposite faces of the porphyrin plane via covalent and coordination bonds, respectively. Excitation of all of the triads results in sequential electron transfer that generates the identical final charge separated state, BTMPA•+-AlPor-C60•-, which lies energetically 1.50 eV above the ground state. Despite the fact that the radical pair is identical in all of the triads, the lifetime of the radical pair was found to be very different in each of the different systems, that is, 1240, 740 and 56 ns for the pentafluorophenyl, trifluorophenyl, and phenyl substituted systems, respectively. These results imply that the charge recombination is an activated process that depends on the midpoint potential of the central aluminum(III) porphyrin.

Chemoselective and Site-Selective Reductions Catalyzed by a Supramolecular Host and a Pyridine-Borane Cofactor.

Supramolecular catalysts emulate the mechanism of enzymes to achieve large rate accelerations and precise selectivity under mild and aqueous conditions. While significant strides have been made in the supramolecular host-promoted synthesis of small molecules, applications of this reactivity to chemoselective and site-selective modification of complex biomolecules remain virtually unexplored. We report here a supramolecular system where coencapsulation of pyridine-borane with a variety of molecules including enones, ketones, aldehydes, oximes, hydrazones, and imines effects efficient reductions under basic aqueous conditions. Upon subjecting unprotected lysine to the host-mediated reductive amination conditions, we observed excellent ε-selectivity, indicating that differential guest binding within the same molecule is possible without sacrificing reactivity. Inspired by the post-translational modification of complex biomolecules by enzymatic systems, we then applied this supramolecular reaction to the site-selective labeling of a single lysine residue in an 11-amino acid peptide chain and human insulin.

One Ball Tips the Balance toward Three-Component Borromean Ring Systems

In this issue of <i>Chem</i>, Metrangolo and colleagues describe the selective mechanochemical formation of three-component halogen-bonded ionic co-crystals that adopt a Borromean ring topology. Intriguingly, a seemingly minor adjustment of the milling conditions results in profound changes to the supramolecular reaction trajectory and final product, as monitored by <i>in situ</i> synchrotron diffraction.

Open versus Interpenetrated: Switchable Supramolecular Trajectories in Mechanosynthesis of a Halogen-Bonded Borromean Network

Summary Precise control over topologically intricate molecular architectures remains an open challenge for chemists due to their inherent structural complexity. We report a simple solvent-free strategy to selectively prepare two multi-component supramolecular crystalline systems based on the halogen bond, endowed with either an unknot topology or a Borromean-type entanglement. Real-time in situ monitoring of the solvent-free mechanochemical synthesis of these three-component halogen-bonded ionic co-crystals reveals that the choice of milling conditions leads to a switch in the supramolecular reaction trajectory, resulting in the selective formation of an open halogen-bonded network or a halogen-bonded Borromean-type assembly.

Decelerating Charge Recombination Using Fluorinated Porphyrins in N,N-Bis(3,4,5-trimethoxyphenyl)aniline—Aluminum(III) Porphyrin—Fullerene Reaction Center Models

In supramolecular reaction center models, the lifetime of the charge-separated state depends on many factors. However, little attention has been paid to the redox potential of the species that lie between the donor and acceptor in the final charge separated state. Here, we report on a series of self-assembled aluminum porphyrin-based triads that provide a unique opportunity to study the influence of the porphyrin redox potential independently of other factors. The triads, BTMPA-Im→AlPorFn-Ph-C60 (n = 0, 3, 5), were constructed by linking the fullerene (C60) and bis(3,4,5-trimethoxyphenyl)aniline (BTMPA) to the aluminum(III) porphyrin. The porphyrin (AlPor, AlPorF3, or AlPorF5) redox potentials are tuned by the substitution of phenyl (Ph), 3,4,5-trifluorophenyl (PhF3), or 2,3,4,5,6-pentafluorophenyl (PhF5) groups in its meso positions. The C60 and BTMPA units are bound axially to opposite faces of the porphyrin plane via covalent and coordination bonds, respectively. Excitation of all of the triads results in sequential electron transfer that generates the identical final charge separated state, BTMPA•+-Im→AlPorFn-Ph-C60•-, which lies energetically 1.50 eV above the ground state. Despite the fact that the radical pair is identical in all of the triads, remarkably, the lifetime of the BTMPA•+-Im→AlPorFn-Ph-C60•- radical pair was found to be very different in each of them, that is, 1240, 740, and 56 ns for BTMPA-Im→AlPorF5-Ph-C60, BTMPA-Im→AlPorF3-Ph-C60, and BTMPA-Im→AlPor-Ph-C60, respectively. These results clearly suggest that the charge recombination is an activated process that depends on the midpoint potential of the central aluminum(III) porphyrin (AlPorFn).

Metal Active Sites and Their Catalytic Functions in Zeolites: Insights from Solid-State NMR Spectroscopy.

Zeolites are important heterogeneous catalysts widely used in the modern chemical and petrochemical industries. Metal-containing zeolites show distinct performance in the catalytic processes such as fluid catalytic cracking, activation and conversion of light alkanes, methanol-to-aromatics conversion, biomass transformation, and so on. The metal speciation, distribution, and interactions on zeolites have enormous impact on their property and catalytic performance. Significant efforts have been devoted to the synthesis of more active and selective zeolites by engineering the metal active sites. However, the nature of metal species and their role in the reactions are still poorly understood, which makes it difficult to establish the structure-activity relationship toward the rational design and application of zeolites. For example, synergic active sites are often present on the metal-containing zeolites, but their structure, property and quantification still remain to be resolved. Solid-state NMR is a powerful tool for the characterization of heterogeneous catalysts and catalytic reactions by providing information about both molecular structure and dynamics. The heterogeneity and low concentration of the metal sites on zeolites usually leads to a great challenge for their characterization. In this Account, we will describe our effort to study the metal active sites, host-guest interactions, and reaction intermediates by using solid-state NMR spectroscopy, with the aim to highlight recent advances in solid-state NMR techniques for probing the structure and property of metal-containing zeolites as well as the relevant reaction mechanisms. Using sensitivity-enhanced NMR methods such as 67Zn, 71Ga, and 119Sn, NMR enables the identification of metal speciation on zeolites. The synergic active sites constituted by metal species (as Lewis acid sites) and acidic protons (as Brønsted acid sites) on zeolites that amount to only a small fraction of the whole system can be directly probed and quantified with advanced 1H-67Zn or 1H-71Ga double-resonance solid-state NMR. We developed NMR methods to study the host-guest interactions in zeolites by observing the spatial interaction/proximity between aluminum sites (associated with Brønsted or Lewis acid sites) in zeolite host and carbon atoms in organic molecule guest formed during catalytic reaction, which leads to the formation of supramolecular reaction centers in the methanol-to-olefins reaction. The mechanisms underlying the catalytic reactions on metal-modified zeolite are revealed by the identification of key reaction intermediates with in situ 13C MAS NMR spectroscopy. Our discussion based on the representative examples shows how the metal species serving as active sites significantly affect the property and activity of zeolites and related reaction pathways. The structural information obtained by the state-of-the-art solid-state NMR techniques provides new insights into the structure-activity relationship of zeolites in heterogeneous catalysis, which should be beneficial for rational design of highly efficient zeolite catalysts.

Supramolecular synthesis of coumarin derivatives catalyzed by a coordination-assembled cage in aqueous solution

A self-assembled Pd4L2 cage is employed as a water-soluble molecular flask for the synthesis of functionalized coumarins from a series of salicylaldehyde derivatives and cyanoacetates/malononitrile. The catalytic reaction features mild aqueous conditions and broad substrate scope. Crystal structures of the host-guest complexes for two substrates and one analogous intermediate have been obtained, shedding light on the supramolecular reaction mechanism. Michaelis-Menten kinetic studies were performed in one typical case, revealing that the rate of product formation has been enhanced by over 23-fold in contrast to the background reaction without cage. Moreover, the same reaction catalyzed by a smaller Pd6L4 cage gives a mixture of products and much lower yields, suggesting that fine-tuning on the size and symmetry of the cages’ cavity is crucial for their applications in supramolecular catalysis.

Differentially Activated Amino Acid Coordination Polymers by Amino Acids

Two amino acid coordination polymers were synthesized using a single-step self-organization process, both of which were found to have three-dimensional, enantiomeric structures. They could be differentially activated by four amino acids(aq), cysteine, arginine, histidine and lysine, but were inactive for the other naturally occurring amino acids. This supramolecular reaction system provides a deep insight into the unique responses of such advanced materials.

Avoiding irreversible 5-fluorocytosine hydration via supramolecular synthesis of pharmaceutical cocrystals

Supramolecular reaction of 5-FC with caffeine, p-aminobenzoic and caprylic acid gave rise to solid forms physically stable in humid environments.

Host–Guest Interactions and Their Catalytic Consequences in Methanol to Olefins Conversion on Zeolites Studied by 13C–27Al Double-Resonance Solid-State NMR Spectroscopy

Methanol conversion over zeolites with different topologies (H-ZSM-5, H-SSZ-13, and H-MOR) was studied using solid-state NMR spectroscopy and gas chromatrography mass spectroscopy (GC-MS). Host–guest interactions between active hydrocarbon pool (HP) species and zeolite framework (Bronsted acid/base site) were observed, and the supramolecular reaction centers (SMCs) generated by the interactions were unambiguously identified by 13C–27Al double-resonance NMR. The internuclear spatial interaction/proximity between the 13C nuclei (associated with HP species) and the 27Al nuclei (associated with Bronsted acid/base site) was analyzed and compared over the three zeolites. The product shape selectivity of zeolites greatly influences the catalytic performance that can be linked to the nature of HP species and the host–guest interactions. Closer spatial proximity and stronger interaction between methylbenzenes (MBs) and Bronsted acid/base sites were observed over H-SSZ-13 and H-MOR zeolites, which facilitate aromat...

Assembling Coordination Frameworks of Tetrakis[meso-(3,5-biscarboxyphenyl)]-Metalloporphyrins with Polynuclear Metallic Nodes: Mechanistic Insights into the Synthesis and Crystallization Process

The article provides a deep insight into an improved synthetic methodology of crystalline framework solids with octa-topic tetrakis(3,5-dicarboxyphenyl)-zinc/cobalt-porphyrin linkers and a variety of metallic nodes, using NaOH as a modulator to enhance crystal growth. In the given conditions of the supramolecular reaction polynuclear metallic clusters were formed in situ, leading to the construction of metalloporphyrin frameworks (MPFs) of diverse architectures perforated by wide intralattice voids. Synthetic procedures with Pr3+ ions yielded two different frameworks, labeled as PrMPF-1 (1) and PrMPF-2 (2). The former is sustained by heterometallic {NaPr(COO)4}n pillared synthons, revealing tetragonal interporphyrin channel voids. In the latter the porphyrin units are intercoordinated by heterometallic tetranuclear {PrNa3(H2O)6(COO)9}3– clusters and the resulting structure exhibits hexagonal voids. Additional crystalline materials could be obtained with In3+ and Ga3+ cations as the inorganic component, yielding open 3D framework-structures InMPF (3) and GaMPF (4). These were found to be stabilized by the heterometallic In2Na(μ3-H2O)(COO)7 cluster-type and {NaGa(COO)4}n chain-type interaction synthons, respectively. When the transition metal ions Fe3+ or Mn3+ were used as the connecting reagents, homometallic trinuclear oxo-centered clusters (Fe/Mn)3(μ3-O) (COO)7 were formed in the corresponding polymeric structures FeMPF (5) and MnMPF (6). In 6, adjacent trinuclear clusters are further interconnected by a formate bridge to form covalently linked [Mn3(μ3-O)]2 dimers. Similar reactions in the presence of the NaOH additive, but with Co2+ or Zr4+, yielded two isomorphous 3D supramolecular architectures (7; NaMPF-1 and 8; NaMPF-2) with tetragonally shaped interporphyrin channel voids. Yet, in these structures the porphyrin-bridging {Na(COO)2}−n-chains were found to contain Na+ ions only. The solvent (DMF, water, and possibly dissociation products of hydrolyzed DMF) accessible voids in the metal–organic frameworks 1–8 account for >50% of the crystal volume. Mechanistic aspects of the NaOH-modulated synthetic approach are discussed, characterizing the products at each step in the synthetic course and proposing a plausible reaction mechanism.

Direct Detection of Supramolecular Reaction Centers in the Methanol-to-Olefins Conversion over Zeolite H-ZSM-5 by (13)C-(27)Al Solid-State NMR Spectroscopy.

Hydrocarbon-pool chemistry is important in methanol to olefins (MTO) conversion on acidic zeolite catalysts. The hydrocarbon-pool (HP) species, such as methylbenzenes and cyclic carbocations, confined in zeolite channels during the reaction are essential in determining the reaction pathway. Herein, we experimentally demonstrate the formation of supramolecular reaction centers composed of organic hydrocarbon species and the inorganic zeolite framework in H-ZSM-5 zeolite by advanced (13)C-(27)Al double-resonance solid-state NMR spectroscopy. Methylbenzenes and cyclic carbocations located near Brønsted acid/base sites form the supramolecular reaction centers in the zeolite channel. The internuclear spatial interaction/proximity between the (13)C nuclei (associated with HP species) and the (27) Al nuclei (associated with Brønsted acid/base sites) determines the reactivity of the HP species. The closer the HP species are to the zeolite framework Al, the higher their reactivity in the MTO reaction.

Direct Detection of Supramolecular Reaction Centers in the Methanol‐to‐Olefins Conversion over Zeolite H‐ZSM‐5 by 13C–27Al Solid‐State NMR Spectroscopy

AbstractHydrocarbon‐pool chemistry is important in methanol to olefins (MTO) conversion on acidic zeolite catalysts. The hydrocarbon‐pool (HP) species, such as methylbenzenes and cyclic carbocations, confined in zeolite channels during the reaction are essential in determining the reaction pathway. Herein, we experimentally demonstrate the formation of supramolecular reaction centers composed of organic hydrocarbon species and the inorganic zeolite framework in H‐ZSM‐5 zeolite by advanced 13C–27Al double‐resonance solid‐state NMR spectroscopy. Methylbenzenes and cyclic carbocations located near Brønsted acid/base sites form the supramolecular reaction centers in the zeolite channel. The internuclear spatial interaction/proximity between the 13C nuclei (associated with HP species) and the 27Al nuclei (associated with Brønsted acid/base sites) determines the reactivity of the HP species. The closer the HP species are to the zeolite framework Al, the higher their reactivity in the MTO reaction.

Medicinal facilities to B16F10 melanoma cells for distant metastasis control with a supramolecular complex by DEAE-dextran-MMA copolymer/paclitaxel.

The resistance of cancer cells to chemotherapeutic drugs (MDR) is a major problem to be solved. A supramolecular DEAE-dextran-MMA copolymer (DDMC)/paclitaxel (PTX) complex was obtained by using PTX as the guest and DDMC as the host having 50-300 nm in diameter. The drug resistance of B16F10 melanoma cells to paclitaxel was observed, but there is no drug resistance of melanoma cells to the DDMC/PTX complex in vitro. The cell death rate was determined using Michaelis-Menten kinetics, as the DDMC/PTX complex promoted allosteric supramolecular reaction to tubulin. The DDMC/PTX complex showed a very superior anti-cancer activity to paclitaxel alone in vivo. The median survival time (MST) of the saline, PTX, DDMC/PTX4 (particle size, 50 nm), and DDMC/PTX5 (particle size, 290 nm) groups were 120 h (T/C, 1.0), 176 h (T/C, 1.46), 328 h (T/C, 2.73), and 280 h (T/C, 2.33), respectively. The supramolecular DDMC/PTX complex showed the twofold effectiveness of PTX alone (p < 0.036). Histochemical analysis indicated that the administration of DDMC/PTX complex decreased distant metastasis and increased the survival of mice. A mouse of DDMC/PTX4 group in vivo was almost curing after small dermatorrhagia owing to its anti-angiogenesis, and it will be the hemorrhagic necrotic symptom of tumor by the release of "tumor necrosis factor alpha (TNF-α)" cytokine. As the result, the medicinal action of the DDMC/PTX complex will suppress the tumor-associated action of M2 macrophages and will control the metastasis of cancer cells.

Anticancer efficacy of a supramolecular complex of a 2-diethylaminoethyl-dextran-MMA graft copolymer and paclitaxel used as an artificial enzyme.

The anticancer efficacy of a supramolecular complex that was used as an artificial enzyme against multi-drug-resistant cancer cells was confirmed. A complex of diethylaminoethyl–dextran–methacrylic acid methylester copolymer (DDMC)/paclitaxel (PTX), obtained with PTX as the guest and DDMC as the host, formed a nanoparticle 50–300 nm in size. This complex is considered to be useful as a drug delivery system (DDS) for anticancer compounds since it formed a stable polymeric micelle in water. The resistance of B16F10 melanoma cells to PTX was shown clearly through a maximum survival curve. Conversely, the DDMC/PTX complex showed a superior anticancer efficacy and cell killing rate, as determined through a Michaelis–Menten-type equation, which may promote an allosteric supramolecular reaction to tubulin, in the same manner as an enzymatic reaction. The DDMC/PTX complex showed significantly higher anticancer activity compared to PTX alone in mouse skin in vivo. The median survival times of the saline, PTX, DDMC/PTX4 (particle size 50 nm), and DDMC/PTX5 (particle size 290 nm) groups were 120 h (treatment (T)/control (C), 1.0), 176 h (T/C, 1.46), 328 h (T/C, 2.73), and 280 h (T/C, 2.33), respectively. The supramolecular DDMC/PTX complex showed twice the effectiveness of PTX alone (p < 0.036). Above all, the DDMC/PTX complex is not degraded in cells and acts as an intact supramolecular assembly, which adds a new species to the range of DDS.