Hybrid Dimer Research Articles

Surface Plasmon Coupling in Dimers of Gold Nanoparticles: Experiment and Theory for Ideal (Spherical) and Nonideal (Faceted) Building Blocks

The surface plasmon (SP) coupling in dimers of spherical and faceted gold nanoparticles was investigated experimentally and computationally at the single-particle level. Individual ideal dimers of two spherical gold nanoparticles with a constant gap, filled by a self-assembled monolayer of 1,8-octanedithiol linker molecules, exhibit highly uniform dark-field (DF) scattering spectra. In contrast, single nonideal dimers of two faceted gold nanoparticles with the same constant gap exhibit a high degree of spectral nonuniformity. We attribute this significant spectral heterogeneity to the many possible gap morphologies, that is, the many possible configurations of the crystal facet orientations at the junction of the two faceted particles in nonideal dimers. This configurational complexity is reduced in so-called hybrid dimers, which comprise an ideal spherical particle and a nonideal faceted particle. Hybrid dimers were therefore investigated theoretically and experimentally for revealing the influence of cr...

Versatile catalysts constructed from hybrid polyoxomolybdates for simultaneously detoxifying sulfur mustard and organophosphate simulants

Twelve new hybrid dimers based on carboxylic acid ligand modified polyoxomolybdates were prepared, which can rapidly oxidize the mustard gas simulant, CEES, and hydrolyze the nerve agent simulant, DECP, at room temperature.

Tunable optical pulling force mediated by resonant electromagnetic coupling.

In terms of the law of momentum conservation, the optical pulling force (OPF) is a counterintuitive phenomenon for optical manipulation. We investigate analytically and numerically the tunable OPF exerted on the low refractive index nanoparticle (NP) in a hybrid dimer system when it is illuminated by a plane wave based on the coupled dipole approximation method and the finite-difference time-domain method, respectively. The underlying physical mechanism relies on the near-field electromagnetic coupling between the low refractive index dielectric NP and the plasmonic NP. We further evaluate the dependence of the OPF on the geometrical parameters of the system. It is also numerically demonstrated that a Gaussian beam can be used to achieve pure OPF with no transverse force component. The proposed OPF offers an additional degree of freedom for optical sorting, transport, and trapping of NPs.

Hydrogen‐Bonded Siloxane Liquid Crystals for Hybrid Nanomaterials

The self‐assembly of molecular inorganic/organic hybrid building blocks into ordered hierarchical nanomaterials with a tunable morphology is an enormous challenge. Here, we describe the synthesis and characterization of a novel liquid crystalline hydrogen‐bonding hepta(dimethylsiloxane) azobenzene carboxylic acid dimer. This inorganic/organic hybrid dimer forms sub‐5 nm lamellar features in the bulk and at the liquid solid interface. When mixed with a complementary hydrogen‐bonding disk‐shaped small molecule, a columnar hexagonal phase is formed. When adding a block copolymer containing hydrogen bond‐accepting moieties, a hierarchical nanostructured material is obtained with a hexagonal columnar arrangement perpendicular to lamellae super structure. Our supramolecular approach shows that hierarchical hybrid nanomaterials can be fabricated with controlled properties which is appealing for applications such as nanoporous materials, organic electronics, and nanolithography.

Programmable Assembly of Hybrid Nanoclusters.

Hybrid nanoparticle clusters (often metallic) are interesting plasmonic materials with tunable resonances and a near-field electromagnetic enhancement at interparticle junctions. Therefore, in recent years, we have witnessed a surge in both the interest in these materials and the efforts to obtain them. However, a versatile fabrication of hybrid nanoclusters, that is, combining more than one material, still remains an open challenge. Current lithographical or self-assembly methods are limited to the preparation of hybrid clusters with up to two different materials and typically to the fabrication of hybrid dimers. Here, we provide a novel strategy to deposit and align not only hybrid dimers but also hybrid nanoclusters possessing more complex shapes and compositions. Our strategy is based on the downscaling of sequential capillarity-assisted particle assembly over topographical templates. As a proof of concept, we demonstrate dimers, linear trimers, and 2D nanoclusters with programmable compositions from a range of metallic nanoparticles. Our process does not rely on any specific chemistry and can be extended to a large variety of particles and shapes. The template also simultaneously aligns the hybrid (often anisotropic) nanoclusters, which could facilitate device integration, for example, for optical readout after transfer to other substrates by a printing step. We envisage that this new fabrication route will enable the assembly and positioning of complex hybrid nanoclusters of different functional nanoparticles to study coupling effects not only locally but also at larger scales for new nanoscale optical devices.

Hybrid dimers based on metal-substituted Keggin polyoxometalates (metal = Ti, Ln) for cyanosilylation catalysis.

Six novel organic-inorganic hybrid polyoxometalate derivatives, K[(H2O)4(3-Hpic)2Ce][(H2O)5(3-Hpic)2Ce][PW10Ti2O40]·11H2O 1, K[(H2O)4(3-Hpic)2Nd][(H2O)5(3-Hpic)2Nd][PW10Ti2O40]·12H2O 2, K[(H2O)4(3-Hpic)2Sm][(H2O)5(3-Hpic)2Sm][PW10Ti2O40]·8H2O 3, H[(H2O)7(4-Hpic)La][(4-Hpic)2LaPW11O39]·14.5H2O 4, H[(H2O)7(4-Hpic)Ce][(4-Hpic)2CePW11O39]·7.5H2O 5, and K(4-Hpic)0.5[(H2O)6(4-Hpic)Nd][(4-Hpic)2NdPW11O39]·10H2O 6, (3-Hpic = 3-picolinic acid; 4-Hpic = 4-picolinic acid) have been synthesized and characterized by elemental analysis, IR, solid state UV-vis spectroscopy, thermal gravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Isostructural compounds 1-3 are hybrid dimers that consist of two Ti-substituted Keggin-type polyoxoanions [PW10Ti2O40]7- and four Ln-3-Hpic coordination groups. The strong hydrogen bonds in 1-3 can make these dimers yield a 1D supramolecular chain. Compounds 4-6 are also dimers constructed from two lanthanide-substituted Keggin-type polyoxoanions [PW11LnO39]4- and four 4-Hpic ligands, which are further linked by two Ln-4-Hpic groups to form a bi-supporting structure. Then these subunits are joined together by strong hydrogen-bonding interactions between polyoxoanions and coordinated water molecules to produce a 2D supramolecular framework. All these compounds as heterogeneous Lewis acid-base catalysts show high activity and high selectivity for the cyanosilylation of different carbonyl compounds under solvent-free conditions, and can be recycled without any obvious inactivation.

Current Antimalarial Therapies and Advances in the Development of Semi-Synthetic Artemisinin Derivatives.

According to the World Health Organization, malaria remains one of the biggest public health problems in the world. The development of resistance is a current concern, mainly because the number of safe drugs for this disease is limited. Artemisinin-based combination therapy is recommended by the World Health Organization to prevent or delay the onset of resistance. Thus, the need to obtain new drugs makes artemisinin the most widely used scaffold to obtain synthetic compounds. This review describes the drugs based on artemisinin and its derivatives, including hybrid derivatives and dimers, trimers and tetramers that contain an endoperoxide bridge. This class of compounds is of extreme importance for the discovery of new drugs to treat malaria.

Rare Hybrid Dimers with Anti-Acetylcholinesterase Activities from a Safflower (Carthamus tinctorius L.) Seed Oil Cake.

Safflower (Carthamus tinctorius) is commercially cultivated for vegetable oil extracted from the seeds. However, during the production process of seed oil, a large amount of the oil cake is thrown away or fermented as fertilizer to improve the homing rate of pigeons. Therefore, to solve the ecological problem and develop its new function, we investigated the chemical constituents of a safflower seed oil cake, and six new hybrid dimers, (±)-carthatins A-F (1-6, respectively), with a phenylpropanoid and a feruloylserotonin fused via a dihydrofuran ring, together with four known compounds, including sinapyl alcohol (7), coniferyl alcohol (8), serotobenine (9), and feruloylserotonin (10), were isolated. The extensive nuclear magnetic resonance spectra, combined with electronic circular dichroism analysis and chiral high-performance liquid chromatography, allowed the complete structural assignments of (±)-carthatins A-F. Moreover, we evaluated their anti-acetylcholinesterase activities. Racemic carthatins A and B (1 and 2, respectively) showed anti-acetylcholinesterase effects with IC50 values of 17.96 and 66.83 μM, respectively. To some extent, our findings provide a new scaffold of acetylcholinesterase inhibitors, which could be beneficial for developing therapeutic molecules for the treatment of Alzheimer's disease and supporting folk application of a safflower seed oil cake.

Metal–Dielectric Hybrid Dimer Nanoantenna: Coupling between Surface Plasmons and Dielectric Resonances for Fluorescence Enhancement

Dimers made of noble metal particles possess extraordinary field enhancements but suffer from large dissipation, whereas low-loss dielectric dimers are limited by relatively weak optical confinement. Hybrid systems could take advantages from both worlds. In this contribution, we study the mode coupling in a hybrid dimer with rigorous dipole–dipole interaction theory and explore its potential in fluorescence enhancement. We first discovered that the direct coupling between metal surface–plasmon resonance and dielectric electric–dipole mode creates a hybridized mode due to the strong electric–electric dipole–dipole interaction between the constituent nanoparticles, whereas the dielectric magnetic–dipole mode can only indirectly couple to the plasmons on the basis of the induced electric–magnetic dipole–dipole interaction. When an electric/magnetic quantum emitter couples to the hybrid dimer, the emitter selectively excites the electric/magnetic (magnetic/electric) resonant modes of the dimer for emitter ori...

Design of novel antimicrobial peptide dimer analogues with enhanced antimicrobial activity in vitro and in vivo by intermolecular triazole bridge strategy

Currently, antimicrobial peptides have attracted considerable attention because of their broad-sprectum activity and low prognostic to induce antibiotic resistance. In our study, for the first time, a series of side-chain hybrid dimer peptides J-AA (Anoplin-Anoplin), J-RR (RW-RW), and J-AR (Anoplin-RW) based on the wasp peptide Anoplin and the arginine- and tryptophan-rich hexapeptide RW were designed and synthesized by click chemistry, with the intent to improve the antimicrobial efficacy of peptides against bacterial pathogens. The results showed that all dimer analogues exhibited up to a 4–16 fold increase in antimicrobial activity compared to the parental peptides against bacterial strains. Furthermore, the antimicrobial activity was confirmed by time-killing kinetics assay with two strains which showed that these dimer analogues at 1, 2×MIC were rapidly bactericidal and reduced the initial inoculum significantly during the first 2–6h. Notably, dimer peptides showed synergy and additivity effects when used in combination with conventional antibiotics rifampin or penicillin respectively against the multidrug-resistant strains. In the Escherichia coli-infected mouse model, all of hybrid dimer analogues had significantly lower degree of bacterial load than the untreated control group when injected once i.p. at 5mg/kg. In addition, the infected mice by methicillin-resistant (MRSA) strain could be effectively treated with J-RR. All of dimer analogues had membrane-active action mode. And the membrane-dependent mode of action signifies that peptides functions freely and without regard to conventional resistant mechanisms. Circular dichroism analyses of all dimer analogues showed a general predominance of α-helix conformation in 50% trifluoroethanol (TFE). Additionally, the acute toxicities study indicated that J-RR or J-AR did not show the signs of toxicity when adult mice exposed to concentration up to 120mg/kg. The 50% lethal dose (LD50) of J-AA was 53.6mg/kg. In conclusion, to design and synthesize side chain-hybrid dimer analogues via click chemistry may offer a new strategy for antibacterial therapeutic option.

Approach for fine‐tuning of hybrid dimer antennas via laser melting at the nanoscale

Asymmetric metal‐dielectric nanostructures are demonstrated superior optical properties arising from the combination of strong enhancement of near‐fields and controllable scattering characteristics which originate from plasmonic and high‐index dielectric components. Here, being inspired by the recent advances of the asymmetric hybrid nanoparticles fabrication [Dmitry Zuev, et al., Adv. Mater. 28, 3087 (2016)], we suggest and study numerically a novel type of hybrid dimer nanoantennas. The nanoantennas consist of asymmetric metal‐dielectric (Au/Si) nanoparticles and allow tuning of the near‐ and far‐field properties via laser induced reshaping of the metal part at the nanoscale. We demonstrate an ability to modification of the scattering properties, near‐field distribution profilis, normalized local density of states, and radiation patterns of the nanoantenna upon the laser reshaping. The parameters used to investigate these effects correspond to experimentally demonstrated values. image

The use of molecular dynamics simulations to evaluate the DNA sequence-selectivity of G–A cross-linking PBD–duocarmycin dimers

The pyrrolobenzodiazepine (PBD) and duocarmycin families are DNA-interactive agents that covalently bond to guanine (G) and adenine (A) bases, respectively, and that have been joined together to create synthetic dimers capable of cross-linking G–G, A–A, and G–A bases. Three G–A alkylating dimers have been reported in publications to date, with defined DNA-binding sites proposed for two of them. In this study we have used molecular dynamics simulations to elucidate preferred DNA-binding sites for the three published molecular types. For the PBD–CPI dimer UTA-6026 (1), our simulations correctly predicted its favoured binding site (i.e., 5′-C(G)AATTA-3′) as identified by DNA cleavage studies. However, for the PBD–CI molecule (‘Compound 11’, 3), we were unable to reconcile the results of our simulations with the reported preferred cross-linking sequence (5′-ATTTTCC(G)-3′). We found that the molecule is too short to span the five base pairs between the A and G bases as claimed, but should target instead a sequence such as 5′-ATTTC(G)-3′ with two less base pairs between the reacting G and A residues. Our simulation results for this hybrid dimer are also in accord with the very low interstrand cross-linking and in vitro cytotoxicity activities reported for it. Although a preferred cross-linking sequence was not reported for the third hybrid dimer (‘27eS’, 2), our simulations predict that it should span two base pairs between covalently reacting G and A bases (e.g., 5′-GTAT(A)-3′).

Regulatory network of the allosteric ATP inhibition of E.coli phosphofructokinase-2 studied by hybrid dimers.

We have proposed an allosteric ATP inhibition mechanism of Pfk-2 determining the structure of different forms of the enzyme together with a kinetic enzyme analysis. Here we complement the mechanism by using hybrid oligomers of the homodimeric enzyme to get insights about the allosteric communication pathways between the same sites or different ones located in different subunits. Kinetic analysis of the hybrid enzymes indicate that homotropic interactions between allosteric sites for ATP or between substrate sites for fructose-6-P have a minor effect on the enzymatic inhibition induced by ATP. In fact, the sigmoid response for fructose-6-P observed at elevated ATP concentrations can be eliminated even though the enzymatic inhibition is still operative. Nevertheless, leverage coupling analysis supports heterotropic interactions between the allosteric ATP and fructose-6-P binding occurring between and within each subunit.

Optical tuning of near and far fields form hybrid dimer nanoantennas via laser-induced melting

Hybrid nanophotonics based on metal-dielectric nanostructures unifies the advantages of plasmonics and all-dielectric nanophotonics providing strong localization of light, magnetic optical response and specifically designed scattering properties. Here, we propose a new method for optical properties tuning of hybrid dimer nanoantenas via laser-induced melting at the nanoscale. We demonstrate numerically that near- and farfield properties of a hybrid nanoantenna dramatically changes with fs-laser modification of Au particle. The results lay the groundwork for the fine-tuning of hybrid nanoantennas and can be applied for effective light manipulation at the nanoscale, as well as biomedical and energy applications.

Competition and compromise between discotic and calamitic mesogens in triphenylene and azobenzene based shape-amphiphilic liquid crystals

Nirvana Phoenix: a shot showing the transformation from dendritic to focal conic fan-shaped POM texture of different type of lamello-columnar mesophases of a typical disc-rod hybrid dimer TP6–AZO6 reminiscent of the sacred scene of nirvana phoenix.

Iterative Mechanism of Macrodiolide Formation in the Anticancer Compound Conglobatin

SummaryConglobatin is an unusual C2-symmetrical macrodiolide from the bacterium Streptomyces conglobatus with promising antitumor activity. Insights into the genes and enzymes that govern both the assembly-line production of the conglobatin polyketide and its dimerization are essential to allow rational alterations to be made to the conglobatin structure. We have used a rapid, direct in vitro cloning method to obtain the entire cluster on a 41-kbp fragment, encoding a modular polyketide synthase assembly line. The cloned cluster directs conglobatin biosynthesis in a heterologous host strain. Using a model substrate to mimic the conglobatin monomer, we also show that the conglobatin cyclase/thioesterase acts iteratively, ligating two monomers head-to-tail then re-binding the dimer product and cyclizing it. Incubation of two different monomers with the cyclase produces hybrid dimers and trimers, providing the first evidence that conglobatin analogs may in future become accessible through engineering of the polyketide synthase.

Rearrangement of a Krebs-type polyoxometalate upon coordination of N,O-bis(bidentate) ligands.

Selective coordination of 2,3-pyzdc to the Krebs-type [{Ni(H2O)3}2(WO2)2(SbW9O33)2](10-) anion promotes a skeletal rearrangement that results in the [(2,3-pyzdc)2{NaNi2(H2O)4Sb2W20O70}2](22-) (Ni4) hybrid dimer showing a novel dinickel containing a 20-tungsto-2-antimonate(III) framework stabilized by N,O-bis(bidentate) bridging ligands. The solution stability and magnetism of Ni4 is discussed.

A New 1-D Organic–Inorganic Hybrid Dimer Chain Complex Constructed by Manganese(III)-(Schiff-base) and [WO4]2− Unit

The reaction between Metal-Schiff-base complexes and lacunary POM moieties leads to the isolation of a new organic–inorganic hybrid dimer chain complex, [Mn(salen)]2[WO4]·2CH3OH (1) (salen = N,N′-ethylene-bis(salicylideneiminate)), which have been characterized by elemental analyses, IR spectra, and single-crystal X-ray diffraction. Crystal data for 1: Triclinic, P-1, a = 13.502(5) A, b = 16.342(5) A, c = 16.902(5) A, α = 90.323(5)°, β = 107.835(5)°, γ = 97.185(5)°. Structural analyses reveal that 1 represents the first example of out-of-plane manganese dimer chain complex linked by pure inorganic radical. Magnetic susceptibility study reveals that there was overall antiferromagnetic coupling in the complex.

Cooperative Recruitment of Amphotericin B Mediated by a Cyclodextrin Dimer

γ-Cyclodextrin (γ-CD) and hydroxypropyl-γ-CD (HP-γ-CD) improve the bioavailability of amphotericin B (AmB) while reducing its toxicity. In a recent study, AmB was found to possess two sites within its prolonged macrolide ring, binding to γ-CD. In the present contribution, cooperative binding of AmB to a γ-CD dimer, a hydroxypropyl-γ-CD (HP-γ-CD) dimer and a hybrid dimer formed by the latter two cyclic oligosaccharides was examined by molecular dynamics simulations and free-energy calculations in an aqueous solution. The potentials of mean force (PMFs) characterizing the dimerization of the CDs on the macrolide ring of AmB were determined for four different spatial arrangements, namely head-to-head (H–H), head-to-tail (H–T), tail-to-head (T–H), and tail-to-tail (T–T). The PMFs allowed the most stable supramolecular organization to be identified along the transition coordinate for every possible orientation of the participating cyclic oligosaccharides. To estimate the absolute binding free energy of each sp...

Bulk Synthesis of Metal–Organic Hybrid Dimers and Their Propulsion under Electric Fields

Metal-organic hybrid particles have great potential in applications such as colloidal assembly, autonomous microrobots, targeted drug delivery, and colloidal emulsifiers. Existing fabrication methods, however, typically suffer from low throughput, high operation cost, and imprecise property control. Here, we report a facile and bulk synthesis platform that makes a wide range of metal-organic colloidal dimers. Both geometric and interfacial anisotropy on the particles can be tuned independently and conveniently, which represents a key advantage of this method. We further investigate the self-propulsion of platinum-polystyrene dimers under perpendicularly applied electric fields. In 1 × 10(-4) M KCl solution, the dimers exhibit both linear and circular motion with the polystyrene lobes facing toward the moving direction, due to the induced-charge electroosmotic flow surrounding the metal-coated lobes. Surprisingly, in deionized water, the same dimers move in an opposite direction, i.e., the metallic lobes face the forward direction. This is because of the impact of another type of electrokinetic flow: the electrohydrodynamic flow arising from the induced charges on the conducting substrate. The competition between the electrohydrodynamic flow along the substrate and the induced-charge electroosmotic flow along the metallic lobe dictates the propulsion direction of hybrid dimers under electric fields. Our synthetic approach will provide potential opportunities to study the combined impacts of the geometric and interfacial anisotropy on the propulsion, assembly, and other applications of anisotropic particles.