Microtubules and catalytic motor proteins underlie the microscale actuation of living materials, and they have been used in reconstituted systems to harness chemical energy to drive new states of organization of soft matter (e.g., liquid crystals (LCs)). Such materials, however, are fragile and challenging to translate to technological contexts. Rapid (sub-second) and reversible changes in the orientations of LCs at room temperature using reactions between gaseous hydrogen and oxygen that are catalyzed by Pd/Au surfaces are reported. Surface chemical analysis and computational chemistry studies confirm that dissociative adsorption of H2 on the Pd/Au films reduces preadsorbed O and generates 1 ML of adsorbed H, driving nitrile-containing LCs from a perpendicular to a planar orientation. Subsequent exposure to O2 leads to oxidation of the adsorbed H, reformation of adsorbed O on the Pd/Au surface, and a return of the LC to its initial orientation. The roles of surface composition and reaction kinetics in determining the LC dynamics are described along with a proof-of-concept demonstration of microactuation of beads. These results provide fresh ideas for utilizing chemical energy and catalysis to reversibly actuate functional LCs on the microscale.

Toxic aggregation of proteins and peptides into amyloid fibers is the basis of several human diseases. In each disease, a particular peptide noncovalently assembles into long thin structures with an overall cross-β fold. Amyloids are not only related to disease: functional amyloids are found in many biological systems and artificial peptide amyloids are developed into novel nanomaterials. Amyloid fibers can act as template for the generation of more amyloids but are considered nonreactive in chemical catalysis. The perception of amyloids as chemically inert species was recently challenged by in vitro work on three human amyloid systems. With the use of model substrates, amyloid-β, α-synuclein and glucagon amyloids were found to catalyze biologically relevant chemical reactions. The detected catalytic activity was much less than that of \'real\' enzymes, but like that of designed (synthetic) catalytic amyloids. I here describe the current knowledge around this new activity of natural amyloids and the putative connection to metabolic changes in amyloid diseases. These pioneering studies imply that catalytic activity is an unexplored gain-of-function activity of disease amyloids. In fact, all biological amyloids may harbor intrinsic catalytic activity, tuned by each amyloid\'s particular fold, that await discovery.

Covalent organic frameworks (COFs) are new organic porous materials constructed by covalent bonds, with the advantages of pre-designable topology, adjustable pore size, and abundant active sites. Many research studies have shown that COFs exhibit great potential in gas adsorption, molecular separation, catalysis, drug delivery, energy storage, etc. However, the electrons and holes of intrinsic COF are prone to compounding in transport, and the carrier lifetime is short. The donor-acceptor (D-A) type COFs, which are synthesized by introducing D and A units into the COFs backbone, combine separated electron and hole migration pathway, tunable band gap and optoelectronic properties of D-A type polymers with the unique advantages of COFs and have made great progress in related research in recent years. Here, the synthetic strategies of D-A type COFs are first outlined, including the rational design of linkages and D-A units as well as functionalization approaches. Then the applications of D-A type COFs in catalytic reactions, photothermal therapy, and electronic materials are systematically summarized. In the final section, the current challenges, and new directions for the development of D-A type COFs are presented.

Lignocellulose, a kind of biological resource widely existing in nature, which can be transformed into value-added biochemical products through saccharification, fermentation or chemical catalysis. Pretreatments are the necessary step to increase the accessibility and digestibility of lignocellulose. This paper comprehensively reviewed different pretreatment progress of lignocellulose in recent year, including mechanical/thermal, biological, inorganic solvent, organic solvent and unconventional physical-chemical pretreatments, focusing on quantifying the influence of pretreatments on subsequent biomass conversion. In addition, related pretreatment techniques such as genetic engineering, reactor configurations, downstream process and visualization technology of pretreatment were discussed. Finally, this review presented the challenge of lignocellulose pretreatment in the future.

Further development of biomass conversions to viable chemicals and fuels will require improved atom utilization, process efficiency, and synergistic allocation of carbon feedstock into diverse products, as is the case in the well-developed petroleum industry. The integration of biological and chemical processes, which harnesses the strength of each type of process, can lead to advantaged processes over processes limited to one or the other. This synergy can be achieved through bioprivileged molecules that can be leveraged to produce a diversity of products, including both replacement molecules and novel molecules with enhanced performance properties. However, important challenges arise in the development of bioprivileged molecules. This review discusses the integration of biological and chemical processes and its use in the development of bioprivileged molecules, with a further focus on key hurdles that must be overcome for successful implementation.

Encapsulation of enzymes in metal-organic frameworks (MOFs) is often obstructed by the small size of the orifices typical of most reported MOFs, which prevent the passage of larger-size enzymes. Here, the preparation of hierarchical micro- and mesoporous Zn-based MOFs via the templated emulsification method using hydrogels as a template is presented. Zinc-based hydrogels featuring a 3D interconnecting network are first produced via the formation of hydrogen bonds between melamine and salicylic acid in which zinc ions are well distributed. Further coordination with organic linkers followed by the removal of the hydrogel template produces hierarchical Zn-based MOFs containing both micropores and mesopores. These new MOFs are used for the encapsulation of glucose oxidase and horseradish peroxidase to prove the concept. The immobilized enzymes exhibit a remarkably enhanced increased operational stability and enzymatic activity with a kcat /km value of 85.68 mm s-1 . This value is 7.7-fold higher compared to that found for the free enzymes in solution, and 2.7-fold higher than enzymes adsorbed on conventional microporous MOFs. The much higher catalytic activity of the mesoporous conjugate for Knoevenagel reactions is demonstrated, since the large pores enable easier access to the active sites, and compared with that observed for catalysis using microporous MOFs.

The transformation of low cost sugar feedstocks into market chemicals and monomers for existing or novel high performance polymers by chemical catalysis is reviewed. Emphasis is given to industrially relevant, continuous flow, trickle bed processes. Since long-term catalyst stability under hydrothermal conditions is an important issue to be addressed in liquid phase catalysis using carbohydrate feedstocks, we will primarily discuss the results of catalytic performance for prolonged times on stream. In particular, the selective aerobic oxidation of glucose to glucaric acid and the subsequent selective hydrogenation to adipic acid is reviewed. Hydroxymethylfurfural (HMF), which is readily available from fructose, can be upgraded by oxidation to furan dicarboxylic acid (FDCA) or by consecutive reduction and hydrogenolysis to hexanetriol (HTO) followed by hydrogenolysis to biobased hexanediol (HDO). Direct amination of HDO yields biobased hexamethylene diamine (HMDA). Aerobic oxidation of HDO represents an alternative route to biobased adipic acid. HMDA and adipic acid are the monomers required for the production of nylon- 6,6, a major polymer for engineering and fibre applications.

Furan-2,5-dicarboxylic acid (FDCA) has been ranked among the top 12 bio-based building-block chemicals by the Department of Energy in the US. The molecule was first synthesized in 1876, but large-scale production has only become possible since the development of modern bio- and chemical catalysis techniques. The structures of two FDCA solvates, namely, FDCA dimethylformamide (DMF) disolvate, C6H4O5·2C3H7NO, (I), and FDCA dimethyl sulfoxide (DMSO) monosolvate, C6H4O5·C2H6OS, (II), are reported. Solvate (I) crystallizes in the orthorhombic Pbcn space group and solvate (II) crystallizes in the monoclinic P-1 space group. In (I), hydrogen bonds form between the carbonyl O atom in DMF and a hydroxy H atom in FDCA. Whilst in (II), the O atom in one DMSO molecule hydrogen bonds with hydroxy H atoms in two FDCA molecules. Combined with intermolecular S...O interactions, FDCA molecules form a two-dimensional network coordinated by DMSO.

Nanoalloys (NAs), which are distinctly different from bulk alloys or single metals, take on intrinsic features including tunable components and ratios, variable constructions, reconfigurable electronic structures, and optimizable performances, which endow NAs with fascinating prospects in the catalysis field. Here, the focus is on NA materials for chemical catalysis (except photocatalysis or electrocatalysis). In terms of composition, NA systems are divided into three groups, noble metal, base metal, and noble/base metal mixed NAs. Their design and fabrication for the optimization of catalytic performance are systematically summarized. Additionally, the correlations between the composition/structure and catalytic properties are also mentioned. Lastly, the challenges faced in current research are discussed, and further pathways toward their development are suggested.