Role of Polymer Structures in Catalysis by Transition Metal and Metal Oxide Nanoparticle Composites.

Nanoparticle (NP)/polymer nanocomposites received considerable attention because of their important applications including catalysis. Metal and metal oxide NPs may impart catalytic properties to polymer nanocomposites, while polymers with a different structure, functionality, and architecture control the NP formation (size, shape, location, composition, etc.) and in this way, govern catalytic properties of nanocomposites. In this review we will discuss the influence of the polymer nanostructure (thin or grafted layers, polymer ordering, polymer nanopores), architecture (branched vs linear), functional groups (coordinating or ionic), specific properties (reducing, stimuli responsive, conductive), etc. on the formation of metal or metal oxide NPs and the catalytic behavior of the nanocomposites. The development of novel and efficient catalysts is crucial for progress in chemical sciences, and this explains a huge number of publications in this area in recent years. Taking into consideration previous review articles on NP/polymer catalysts, we limited this review to a discussion of a narrow temporal scope (2017-April 2019), while embracing a broad subject scope, i.e., considering any polymers and NPs which form catalytic nanocomposites. This gives us a unique view of the field of catalytic polymer nanocomposites and allows understanding of where the field is going.

Oriented Attachment Is a Major Control Mechanism To Form Nail-like Mn-Doped ZnO Nanocrystals.

Here, we present a controlled synthesis of Mn-doped ZnO nanoparticles (NPs) with predominantly nail-like shapes, whose formation occurs via tip-to-base-oriented attachment of initially formed nanopyramids, followed by leveling of sharp edges that lead to smooth single-crystalline "nails". This shape is prevalent in noncoordinating solvents such as octadecene and octadecane. Yet, the double bond in the former promotes oriented attachment. By contrast, Mn-doped ZnO NP synthesis in a weakly coordinating solvent, benzyl ether, results in dendritic structures because of random attachment of initial NPs. Mn-doped ZnO NPs possess a hexagonal wurtzite structure, and in the majority of cases, the NP surface is enriched with Mn, indicating a migration of Mn2+ ions to the NP surface during the NP formation. When the NP formation is carried out without the addition of octadecyl alcohol, which serves as a surfactant and a reaction initiator, large, concave pyramid dimers are formed whose attachment takes place via basal planes. UV-vis and photoluminescence spectra of these NPs confirm the utility of controlling the NP shape to tune electro-optical properties.

Multicore iron oxide mesocrystals stabilized by a poly(phenylenepyridyl) dendron and dendrimer: role of the dendron/dendrimer self-assembly.

We report the formation of multicore iron oxide mesocrystals using the thermal decomposition of iron acetyl acetonate in the presence of the multifunctional and rigid poly(phenylenepyridyl) dendron and dendrimer. We thoroughly analyze the influence of capping molecules of two different architectures and demonstrate for the first time that dendron/dendrimer self-assembly leads to multicore morphologies. Single-crystalline ordering in multicore NPs leads to cooperative magnetic behavior: mesocrystals exhibit ambient blocking temperatures, allowing subtle control over magnetic properties using a minor temperature change.

Magnetic Nanoparticle Support with an Ultra-Thin Chitosan Layer Preserves the Catalytic Activity of the Immobilized Glucose Oxidase.

Here, we developed magnetically recoverable biocatalysts based on magnetite nanoparticles coated with an ultra-thin layer (about 0.9 nm) of chitosan (CS) ionically cross-linked by sodium tripolyphosphate (TPP). Excessive CS amounts were removed by multiple washings combined with magnetic separation. Glucose oxidase (GOx) was attached to the magnetic support via the interaction with N-hydroxysuccinimide (NHS) in the presence of carbodiimide (EDC) leading to a covalent amide bond. These steps result in the formation of the biocatalyst for D-glucose oxidation to D-gluconic acid to be used in the preparation of pharmaceuticals due to the benign character of the biocatalyst components. To choose the catalyst with the best catalytic performance, the amounts of CS, TPP, NHS, EDC, and GOx were varied. The optimal biocatalyst allowed for 100% relative catalytic activity. The immobilization of GOx and the magnetic character of the support prevents GOx and biocatalyst loss and allows for repeated use.

Development of Fe/Fe3O4 core-shell nanocubes as a promising magnetic resonance imaging contrast agent.

Here, we report the synthesis, characterization, and properties of Fe/Fe3O4 core-shell nanocubes prepared via a simple route. It includes NaBH4 reduction of FeCl3 in an ethylene glycol solution in the presence of 2-mercaptopropionic acid (surfactant) and trisodium citrate (cosurfactant) followed by surface oxidation with trimethylamine N-oxide. The morphology and structure of Fe/Fe3O4 core-shell nanocubes were characterized using transmission electron microscopy (TEM), high-resolution TEM, selected area electron diffraction, X-ray powder diffraction, and X-ray photoelectron spectroscopy. All of the methods confirm a Fe/Fe3O4 core-shell structure of nanocubes. Magnetic measurements revealed that the Fe/Fe3O4 core/shell nanocubes are superparamagnetic at 300 K with a saturation magnetization of 129 emu/g. The T2 weighted imaging and the T2 relaxation time showed high MRI contrast and sensitivity, making these nanocubes viable candidates as enhanced MRI contrast agents.

Functionalization of monodisperse iron oxide NPs and their properties as magnetically recoverable catalysts.

Here we report the functionalization of monodisperse iron oxide nanoparticles (NPs) with commercially available functional acids containing multiple double bonds such as linolenic (LLA) and linoleic (LEA) acids or pyridine moieties such as 6-methylpyridine-2-carboxylic acid, isonicotinic acid, 3-hydroxypicolinic acid, and 6-(1-piperidinyl)pyridine-3-carboxlic acid (PPCA). Both double bonds and pyridine groups can be reacted with noble metal compounds to form catalytically active species in the exterior of magnetic NPs, thus making them promising magnetically recoverable catalysts. We determined that both LLA and LEA stabilize magnetic iron oxide NPs, allowing the formation of π-complexes with bis(acetonitrile)dichloropalladium(II) in the NP shells. In both cases, this leads to the formation of NP aggregates because of interparticle complexation. In the case of pyridine-containing ligands, only PPCA with two N-containing rings is able to provide NP stabilization and functionalization whereas other pyridine-containing acids did now allow sufficient steric stabilization. The interaction of PPCA-based particles with Pd acetate also leads to aggregation because of interparticle interactions, but the aggregates that are formed are much smaller. Nevertheless, the catalytic properties in the selective hydrogenation of dimethylethynylcarbinol (DMEC) to dimethylvinylcarbinol were the best for the catalyst based on LLA, demonstrating that the NP aggregates in all cases are penetrable for DMEC. Easy magnetic separation of this catalyst from the reaction solution makes it promising as a magnetically recoverable catalyst.

Design of Bifunctional Nanocatalysts Based on Zeolites for Biomass Processing.

Bifunctional catalysts consisting of metal-containing nanoparticles (NPs) and zeolite supports have received considerable attention due to their excellent catalytic properties in numerous reactions, including direct (biomass is a substrate) and indirect (platform chemical is a substrate) biomass processing. In this short review, we discuss major approaches to the preparation of NPs in zeolites, concentrating on methods that allow for the best interplay (synergy) between metal and acid sites, which is normally achieved for small NPs well-distributed through zeolite. We focus on the modification of zeolites to provide structural integrity and controlled acidity, which can be accomplished by the incorporation of certain metal ions or elements. The other modification avenue is the adjustment of zeolite morphology, including the creation of numerous defects for the NP entrapment and designed hierarchical porosity for improved mass transfer. In this review, we also provide examples of synergy between metal and acid sites and emphasize that without density functional theory calculations, many assumptions about the interactions between active sites remain unvalidated. Finally, we describe the most interesting examples of direct and indirect biomass (waste) processing for the last five years.

Highly Selective CO2 Hydrogenation to Methanol over Complex In/Co Catalysts: Effect of Polymer Frame.

The growing demand for new energy sources governs the intensive research into CO2 hydrogenation to methanol, a valuable liquid fuel. Recently, indium-based catalysts have shown promise in this reaction, but they are plagued by shortcomings such as structural instability during the reaction and low selectivity. Here, we report a new strategy of controlling the selectivity and stability of bimetallic magnetically recoverable indium-based catalysts deposited onto a solid support. This was accomplished by the introduction of a structural promoter: a branched pyridylphenylene polymer (PPP). The selectivity of methanol formation for this catalyst reached 98.5%, while in the absence of PPP, the catalysts produced a large amount of methane, and the selectivity was about 70.2%. The methanol production rate was higher by a factor of twelve compared to that of a commercial Cu-based catalyst. Along with tuning selectivity, PPP allowed the catalyst to maintain a high stability, enhancing the CO2 sorption capacity and the protection of In against sintering and over-reduction. A careful evaluation of the structure-activity relationships allowed us to balance the catalyst composition with a high level of structural control, providing synergy between the support, magnetic constituent, catalytic species, and the stabilizing polymer layer. We also uncovered the role of each component in the ultimate methanol activity and selectivity.

Functionalization of magnetic nanoparticles with amphiphilic block copolymers: self-assembled thermoresponsive submicrometer particles.

For the first time the four block copolymers derived from 1-alkyl[2-(acryloyloxy)ethyl]dimethylammonium bromides with hexyl (ADA) or cetyl (ADHA) groups and 2-hydroxyethylacrylate (HEA) or N-isopropylacrylamide (NIPAM) were synthesized and employed for functionalization of monodisperse iron oxide nanoparticles (NPs). The polyADA (pADA) or polyADHA (pADHA) block consists of long hydrophobic tails (C(6) or C(16)) connected to a positively charged quaternary ammonium group, making this block amphiphilic. The second block was either fully hydrophilic (pHEA) or thermoresponsive (pNIPAM). The dependence of the NP coating on the length of the hydrophobic tail in the amphiphilic block, the composition of the hydrophilic block, and the NP sizes have been studied. Unusual self-assembling of iron oxide NPs into well-defined composite submicrometer particles was observed for pADHA-b-pNIPAM in the wide range of concentrations (at the pADHA repeating unit concentrations of 0.065 × 10(-2)-2.91 × 10(-2) mmol/mL per 1 mg/mL NPs) but only two concentrations, 1.62 × 10(-2) and 1.94 × 10(-2) mmol/mL, led to regular spherical particles. The thermoresponsive behavior of these composite particles was tested using ζ-potential and dynamic light scattering measurements, while the morphology of particles was characterized by transmission electron microscopy. Coating of NPs with pADHA-b-pHEA results in the formation of individually coated NPs. The different composite particle morphologies are explained by different properties of pHEA and pNIPAM. It is demonstrated that the composite particles based on pADHA-b-pNIPAM are responsive to a magnetic field and can be recommended as magnetic stoppers in biorelated membrane separations. The incorporation of Pd species in submicrometer particles makes them promising candidates for catalytic applications as magnetically recoverable catalysts with a high magnetic response.

Cellulase Immobilization on Nanostructured Supports for Biomass Waste Processing.

Nanobiocatalysts, i.e., enzymes immobilized on nanostructured supports, received considerable attention because they are potential remedies to overcome shortcomings of traditional biocatalysts, such as low efficiency of mass transfer, instability during catalytic reactions, and possible deactivation. In this short review, we will analyze major aspects of immobilization of cellulase-an enzyme for cellulosic biomass waste processing-on nanostructured supports. Such supports provide high surface areas, increased enzyme loading, and a beneficial environment to enhance cellulase performance and its stability, leading to nanobiocatalysts for obtaining biofuels and value-added chemicals. Here, we will discuss such nanostructured supports as carbon nanotubes, polymer nanoparticles (NPs), nanohydrogels, nanofibers, silica NPs, hierarchical porous materials, magnetic NPs and their nanohybrids, based on publications of the last five years. The use of magnetic NPs is especially favorable due to easy separation and the nanobiocatalyst recovery for a repeated use. This review will discuss methods for cellulase immobilization, morphology of nanostructured supports, multienzyme systems as well as factors influencing the enzyme activity to achieve the highest conversion of cellulosic biowaste into fermentable sugars. We believe this review will allow for an enhanced understanding of such nanobiocatalysts and processes, allowing for the best solutions to major problems of sustainable biorefinery.

Virus-based nanoparticles with inorganic cargo: what does the future hold?

An analysis of the accumulated knowledge on virus-based nanoparticles (VNPs) consisting of virus protein capsids and inorganic cargo, such as nanoparticles (NPs), nanowires, and thin layers, is presented. Virus capsids (VCs) can serve either as templates or nanoreactors when inorganic materials are formed outside or inside VCs. The third possibility is when inorganic NPs nucleate the formation of VCs. The structural and mechanistic studies of VNP formation are paving the way to a better understating of virus structure and behavior, and these facilitate promising applications of VNPs in biomedical and materials research.

Nanoparticles by decomposition of long chain iron carboxylates: from spheres to stars and cubes.

In this paper, we report the influence of reaction conditions and the chain length on the nanoparticle (NP) size and morphology for thermal decomposition of long-chain iron carboxylates such as Fe(III) oleate, palmitate, and myristate. In the majority of cases, spherical NPs are obtained; however, nonspherical morphologies were observed in some "extreme" conditions. For example, iron oxide nanostars are formed in eicosane at the Fe oleate/oleic acid ratio of 0.49 g/mL: the highest oleic acid content when NPs still form. The cubic NPs with flat facets are obtained by decomposition of iron palmitate at the lowest palmitic acid fractions, but the most monodisperse cubes are formed at the Fe palmitate/palmitic acid ratio of 1.19 g/mL. Elliptical NPs are formed from Fe myristate with the most well-defined structure. Easy transformation of these NPs from wüstite to maghemite without aggregation and loss of solubility makes them excellent candidates for biomedical applications after proper functionalization described in our preceding papers.

Magnetic Nanoparticle-Containing Supports as Carriers of Immobilized Enzymes: Key Factors Influencing the Biocatalyst Performance.

In this short review (Perspective), we identify key features of the performance of biocatalysts developed by the immobilization of enzymes on the supports containing magnetic nanoparticles (NPs), analyzing the scientific literature for the last five years. A clear advantage of magnetic supports is their easy separation due to the magnetic attraction between magnetic NPs and an external magnetic field, facilitating the biocatalyst reuse. This allows for savings of materials and energy in the biocatalytic process. Commonly, magnetic NPs are isolated from enzymes either by polymers, silica, or some other protective layer. However, in those cases when iron oxide NPs are in close proximity to the enzyme, the biocatalyst may display a fascinating behavior, allowing for synergy of the performance due to the enzyme-like properties shown in iron oxides. Another important parameter which is discussed in this review is the magnetic support porosity, especially in hierarchical porous supports. In the case of comparatively large pores, which can freely accommodate enzyme molecules without jeopardizing their conformation, the enzyme surface ordering may create an optimal crowding on the support, enhancing the biocatalytic performance. Other factors such as surface-modifying agents or special enzyme reactor designs can be also influential in the performance of magnetic NP based immobilized enzymes.

Utilizing Stimuli Responsive Linkages to Engineer and Enhance Polymer Nanoparticle-Based Drug Delivery Platforms.

The devastating nature of cancer continues to be one of the leading causes of death in the world. Chemotherapy is among the most common forms of cancer treatment but comes with a host of adverse effects caused by the therapeutic agents damaging healthy tissue and organs. To limit these side effects, scientists have been designing stimuli responsive drug delivery vessels for targeted release. This Review focuses on the incorporation of stimuli responsive linkages in targeted drug delivery systems to enhance therapeutic efficiency. These platforms are primarily employed to control the distribution of anticancer agents in the body to reduce the adverse side effects caused by their toxicities. We will outline how drug delivery vessels are constructed so that exposure to select environmental and external stimuli releases the enclosed drug only at the target site. Stimuli responsive components are integrated within drug delivery vessels in the form of cross-linkers, polymers, and surface modifications. The changes, these moieties undergo upon stimuli exposure, cascade into larger scale alterations to the platforms, resulting in complete disassembly, reversible morphological variations, and enhanced cellular uptake. The ability for these modes of delivery to be initiated exclusively under stimuli exposure allows for release of toxic therapeutic agents to be confined only to the affected area.

Magnetically Recoverable Nanoparticulate Catalysts for Cross-Coupling Reactions: The Dendritic Support Influences the Catalytic Performance.

Carbon-carbon cross-coupling reactions are among the most important synthetic tools for the preparation of pharmaceuticals and bioactive compounds. However, these reactions are normally carried out using copper, phosphines, and/or amines, which are poisonous for pharmaceuticals. The use of nanocomposite catalysts holds promise for facilitating these reactions and making them more environmentally friendly. In the present work, the PEGylated (PEG stands for poly(ethylene glycol) pyridylphenylene dendrons immobilized on silica loaded with magnetic nanoparticles have been successfully employed for the stabilization of Pd2+ complexes and Pd nanoparticles. The catalyst developed showed excellent catalytic activity in copper-free Sonogashira and Heck cross-coupling reactions. The reactions proceeded smoothly in green solvents at low palladium loading, resulting in high yields of cross-coupling products (from 80% to 97%) within short reaction times. The presence of magnetic nanoparticles allows easy magnetic separation for repeated use without a noticeable decrease of catalytic activity due to the strong stabilization of Pd species by rigid and bulky dendritic ligands. The PEG dendron periphery makes the catalyst hydrophilic and better suited for green solvents. The minor drop in activity upon the catalyst reuse is explained by the formation of Pd nanoparticles from the Pd2+ species during the catalytic reaction. The magnetic separation and reuse of the nanocomposite catalyst reduces the cost of target products as well as energy and material consumption and diminishes residual contamination by the catalyst. These factors as well as the absence of copper in the catalyst makeup pave the way for future applications of such catalysts in cross-coupling reactions.

Chitosan as capping agent in a robust one-pot procedure for a magnetic catalyst synthesis.

Here, we report a one-pot solvothermal method for the development of magnetically recoverable catalysts with Ru or Ag nanoparticles (NPs) capped by chitosan (CS), a derivative of natural chitin. The formation of iron oxide NPs was carried out in situ in the presence of CS and iron acetylacetonate in boiling triethyleneglycol (TEG) due to CS solubilization in warm TEG. Coordination with Ru or Ag species and the NP formation take place in the same reaction solution, eliminating intermediate steps. In optimal conditions the method developed allows stabilization of 2.2 nm monodisperse Ru NPs (containing both Ru0 and Ru4+ species) that are evenly distributed through the catalyst, while for Ag NPs, this stabilizing medium is inferior, leading to exceptionally large Ag nanocrystals. Catalytic testing of CS-Ru magnetically recoverable catalysts in the reduction of 4-nitrophenol to 4-aminophenol with excess NaBH4 revealed that the catalyst with 2.2 nm Ru NPs exhibits the highest catalytic activity compared to samples with larger Ru NPs (2.9-3.2 nm). Moreover, this catalyst displayed extraordinary shelf-life in the aqueous solution (up to ten months) and excellent reusability in ten consecutive reactions with easy magnetic separation at each step which were assigned to its conformational rigidity at a constant pH. These characteristics as well as favorable environmental factors of the catalyst fabrication, make it promising for nitroarene reduction.

Theranostics Based on Magnetic Nanoparticles and Polymers: Intelligent Design for Efficient Diagnostics and Therapy.

Theranostics is a fast-growing field due to demands for new, efficient therapeutics which could be precisely delivered to the target site using multimodal imaging with enhancing auxiliary actions. In this review article we discuss theranostic nanoplatforms containing polymers and magnetic nanoparticles along with other components. Magnetic nanoparticles allow for both diagnostic and therapeutic (hyperthermia) capabilities, while polymers can be reservoirs for drugs and are easily functionalized for cell targeting. We focus on the most important design strategies to achieve optimal theranostic effects as well as the roles of different components included in theranostics, reviewing the literature from the last 5 years.

Pd Catalyst Based on Hyperbranched Polypyridylphenylene Formed In Situ on Magnetic Silica Allows for Excellent Performance in Suzuki-Miyaura Reaction.

Here, for the first time, we developed a catalytic composite by forming a thin layer of a cross-linked hyperbranched pyridylphenylene polymer (PPP) on the surface of mesoporous magnetic silica (Fe3O4-SiO2, MS) followed by complexation with Pd species. The interaction of Pd acetate (PdAc) with pyridine units of the polymer results in the formation of Pd2+ complexes which are evenly distributed through the PPP layer. The MS-PPP-PdAc catalyst was tested in the Suzuki-Miyaura cross-coupling reaction with four different para-Br-substituted arenes, demonstrating enhanced catalytic properties for substrates containing electron withdrawing groups, and especially, for 4-bromobenzaldehyde. In this case, 100% selectivity and conversion were achieved with TOF of >23 000 h-1 at a very low Pd loading (0.032 mol %), a remarkable performance in this reaction. We believe these exceptional catalytic properties are due to the hyperbranched polymer architecture, which allows excellent stabilization of catalytic species as well as a favorable space for reacting molecules. Additionally, the magnetic character of the support allows for easy magnetic separation during the catalyst synthesis, purification, and reuse, resulting in energy and materials savings. These factors and excellent reusability of MS-PPP-PdAc in five consecutive uses make this catalyst promising for a variety of catalytic reactions.

Selective Hydrogenation of Biomass-Derived Furfural: Enhanced Catalytic Performance of Pd-Cu Alloy Nanoparticles in Porous Polymer.

Here, the development of a new catalyst is reported for the selective furfural (FF) hydrogenation to furfuryl alcohol (FA) based on about 7 nm sized Pd-Cu alloy nanoparticles (NPs) formed in inexpensive, commercially available micro/mesoporous hypercrosslinked polystyrene (HPS). A comparison of the catalytic properties of as-synthesized and reduced (denoted "r") catalysts as well as Pd-Cu alloy and monometallic palladium NPs showed a considerable enhancement of the catalytic performance of Pd-Cu/HPS-r compared to other catalysts studied, resulting in about 100 % FF conversion, 95.2 % selectivity for FA and a TOF of 1209 h-1 . This was attributed to the enrichment of the NP surface with copper atoms, disrupting the furan ring adsorption, and to the presence of both zerovalent and cationic palladium and copper species, resulting in optimal hydrogen and FF adsorption. These factors along with exceptional stability of the catalyst in ten consecutive catalytic cycles make it highly promising in practical applications.

Glucose Oxidase Immobilized on Magnetic Zirconia: Controlling Catalytic Performance and Stability.

Here, we report the structures and properties of biocatalysts based on glucose oxidase (GOx) macromolecules immobilized on the mesoporous zirconia surface with or without magnetic iron oxide nanoparticles (IONPs) in zirconia pores. Properties of these biocatalysts were studied in oxidation of d-glucose to d-gluconic acid at a wide range of pH and temperatures. We demonstrate that the calcination temperature (300, 400, or 600 °C) of zirconia determines its structure, with crystalline materials obtained at 400 and 600 °C. This, in turn, influences the catalytic behavior of immobilized GOx, which was tentatively assigned to the preservation of GOx conformation on the crystalline support surface. IONPs significantly enhance the biocatalyst activity due to synergy with the enzyme. At the same time, neither support porosity nor acidity/basicity shows correlations with the properties of this biocatalyst. The highest relative activity of 98% (of native GOx) at a pH 6-7 and temperature of 40-45 °C was achieved for the biocatalyst based on ZrO2 calcined at 600 °C and containing IONPs. This process is green as it is characterized by a high atom economy due to the formation of a single product with high selectivity and conversion and minimization of waste due to magnetic separation of the catalyst from an aqueous solution. These and an exceptional stability of this catalyst in 10 consecutive reactions (7% relative activity loss) make it favorable for practical applications.