Multifunctional Catalysts for Cascade Reactions in Biomass Processing.

Multifunctional catalysts have received considerable attention in the cascade reactions of biomass processing. A cascade (or tandem) reaction is realized when multiple reaction steps that require different catalysts are performed in a one-step process. These reactions require bi- or multifunctional catalysts or catalyst mixtures to serve successfully at each reaction step.

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.

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

The growing demand for new energy sources governs the intensive research into CO 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.

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.

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.

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.

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.

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.

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.

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.

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 .

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.

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 (FeO-SiO, MS) followed by complexation with Pd species. The interaction of Pd acetate (PdAc) with pyridine units of the polymer results in the formation of Pd 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.

Cellulose Conversion Into Hexitols and Glycols in Water: Recent Advances in Catalyst Development.

Conversion of biomass cellulose to value-added chemicals and fuels is one of the most important advances of green chemistry stimulated by needs of industry. Here we discuss modern trends in the development of catalysts for two processes of cellulose conversion: (i) hydrolytic hydrogenation with the formation of hexitols and (ii) hydrogenolysis, leading to glycols. The promising strategies include the use of subcritical water which facilitates hydrolysis, bifunctional catalysts which catalyze not only hydrogenation, but also hydrolysis, retro-aldol condensation, and isomerization, and pretreatment (milling) of cellulose together with catalysts to allow an intimate contact between the reaction components.

Zn Ion Surface Enrichment in Doped Iron Oxide Nanoparticles Leads to Charge Carrier Density Enhancement.

Here, we report the development of monodisperse Zn-doped iron oxide nanoparticles (NPs) with different amounts of Zn (Zn Fe O, 0 < < 0.43) by thermal decomposition of a mixture of zinc and iron oleates. The as-synthesized NPs show a considerable fraction of wüstite (FeO) which is transformed to spinel upon 2 h oxidation of the NP reaction solutions.

Facile Synthesis of Magnetically Recoverable Pd and Ru Catalysts for 4-Nitrophenol Reduction: Identifying Key Factors.

This paper reports the development of robust Pd- and Ru-containing magnetically recoverable catalysts in a one-pot procedure using commercially available, branched polyethyleneimine (PEI) as capping and reducing agent. For both catalytic metals, ∼3 nm nanoparticles (NPs) are stabilized in the PEI shell of magnetite NPs, whose aggregation allows for prompt magnetic separation. The catalyst properties were studied in a model reaction of 4-nitrophenol hydrogenation to 4-aminophenol with NaBH.

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.

Magnetic Drug Delivery: Where the Field Is Going.

Targeted delivery of anticancer drugs is considered to be one of the pillars of cancer treatment as it could allow for a better treatment efficiency and less adverse effects. A promising drug delivery approach is magnetic drug targeting which can be realized if a drug delivery vehicle possesses a strong magnetic moment. Here, we discuss different types of magnetic nanomaterials which can be used as magnetic drug delivery vehicles, approaches to magnetic targeted delivery as well as promising strategies for the enhancement of the imaging-guided delivery and the therapeutic action.

Immobilized glucose oxidase on magnetic silica and alumina: Beyond magnetic separation.

Here we report immobilization of glucose oxidase (GOx) on magnetic silica (FeO-SiO) and alumina (FeO-AlO) functionalized with amino groups using glutaraldehyde as a linker. Magnetic support based biocatalysts demonstrate high catalytic activity in d-glucose oxidation to D-gluconic acid at pH 5-7.5 and temperature of 30-50 °C with the best activities of 95% and 91% for magnetic silica and alumina, respectively.

Magnetically Recoverable Catalysts: Beyond Magnetic Separation.

Here, we discuss several important aspects of magnetically recoverable catalysts which can be realized when magnetic oxide nanoparticles are exposed to catalytic species and catalytic reaction media. In such conditions magnetic oxides can enhance performance of catalytic nanoparticles due to (i) electronic effects, (ii) catalyzing reactions which are beneficial for the final reaction outcome, or (iii) providing a capacity to dilute catalytic metal oxide species, leading to an increase of oxygen vacancies. However, this approach should be used when the magnetic oxides are stable in reaction conditions and do not promote side reactions.

Graphene Derivative in Magnetically Recoverable Catalyst Determines Catalytic Properties in Transfer Hydrogenation of Nitroarenes to Anilines with 2-Propanol.

Here, we report transfer hydrogenation of nitroarenes to aminoarenes using 2-propanol as a hydrogen source and Ag-containing magnetically recoverable catalysts based on partially reduced graphene oxide (pRGO) sheets. X-ray diffraction and X-ray photoelectron spectroscopy data demonstrated that, during the one-pot catalyst synthesis, formation of magnetite nanoparticles (NPs) is accompanied by the reduction of graphene oxide (GO) to pRGO. The formation of Ag NPs on top of magnetite nanoparticles does not change the pRGO structure.

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.

Metal-Ion Distribution and Oxygen Vacancies That Determine the Activity of Magnetically Recoverable Catalysts in Methanol Synthesis.

Here, we report on the development of novel Zn-, Zn-Cr-, and Zn-Cu-containing catalysts using magnetic silica (FeO-SiO) as the support. Transmission electron microscopy, powder X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) showed that the iron oxide nanoparticles are located in mesoporous silica pores and the magnetite (spinel) structure remains virtually unchanged despite the incorporation of Zn and Cr. According to XPS data, the Zn and Cr species are intermixed within the magnetite structure.

Enhancing the Catalytic Activity of Zn-Containing Magnetic Oxides in a Methanol Synthesis: Identifying the Key Factors.

A new family of Ni-, Co-, and Cr-doped Zn-containing magnetic oxide nanoparticles (NPs) stabilized by polyphenylquinoxaline (PPQ) and hyperbranched pyridylphenylene polymer (PPP) has been developed. These NPs have been synthesized by thermal decomposition of Zn and doping metal acetylacetonates in the reaction solution of preformed magnetite NPs, resulting in single-crystal NPs with spinel structure. For the PPQ-capped NPs, it was demonstrated that all three types of metal species (Fe, Zn, and a doping metal) reside within the same NPs, the surface of which is enriched with Zn and a doping metal, while the deeper layers are enriched with Fe.

Ru-Containing Magnetically Recoverable Catalysts: A Sustainable Pathway from Cellulose to Ethylene and Propylene Glycols.

Biomass processing to value-added chemicals and biofuels received considerable attention due to the renewable nature of the precursors. Here, we report the development of Ru-containing magnetically recoverable catalysts for cellulose hydrogenolysis to low alcohols, ethylene glycol (EG) and propylene glycol (PG). The catalysts are synthesized by incorporation of magnetite nanoparticles (NPs) in mesoporous silica pores followed by formation of 2 nm Ru NPs.