Investigation of lignin substructures participating in self-assembly for the synthesis of monodisperse lignin spherical particles.

The intricate structure of lignin, characterized by a mix of hydrophilic components and hydrophobic structures from its aliphatic and aromatic constituents, poses challenges in creating monodisperse particles. This is due to the need for precise modulation of self-assembly kinetics. Herein, we explore a correlation between the substructure of lignin and its capacity for self-assembly. We have conducted an in-depth investigation into the interactions between hydrophilic groups, such as phenolic and aromatic-OH, and monolignols with interunit linkages that are involved in the formation of lignin particles (LPs). A high degree of hydrophilicity with a condensed structure is crucial for high supersaturation levels, which in turn determines the growth phase and leads to small LPs. An approach based on tailoring the supersaturation level which is contingent on the structural characteristics of extracted organosolv lignin was used to obtain remarkably uniform LPs with mean diameters of approximately 230 and 480 nm. The results of this study have the potential to serve as a foundation for the preparation of monodisperse LPs derived from various lignin sources as well as for the development of methods to extract lignin containing a specific chemical substructure.

Facile and Efficient Production of Biomass-Derived Isosorbide Dioxides via Epoxidation Using In situ-generated DMDO under Ultrasonication.

Herein, we present a facile synthetic process for producing biomass-derived isosorbide (ISB) dioxides using dimethyl dioxirane (DMDO) as an efficient oxidizing agent, which was generated in situ from acetone and KHSO5 . To achieve high conversion and product yield, the KHSO5 concentration, KHSO5 flow rate, and reaction temperature were optimized. Under the optimal conditions, rapid and efficient epoxidation using the in situ-generated DMDO was observed under ultrasonication, yielding the desired product within 35 min at 0 °C. This study offers a convenient and efficient method for generating biomass-derived ISB building blocks, which have significant potential for the fabrication of bioplastics.

ß-Ketoadipic acid production from poly(ethylene terephthalate) waste via chemobiological upcycling.

The upcycling of poly(ethylene terephthalate) (PET) waste can simultaneously produce value-added chemicals and reduce the growing environmental impact of plastic waste. In this study, we designed a chemobiological system to convert terephthalic acid (TPA), an aromatic monomer of PET, to ß-ketoadipic acid (ßKA), a C6 keto-diacid that functions as a building block for nylon-6,6 analogs. Using microwave-assisted hydrolysis in a neutral aqueous system, PET was converted to TPA with Amberlyst-15, a conventional catalyst with high conversion efficiency and reusability. The bioconversion process of TPA into ßKA used a recombinant Escherichia coli ßKA expressing two conversion modules for TPA degradation (tphAabc and tphB) and ßKA synthesis (aroY, catABC, and pcaD). To improve bioconversion, the formation of acetic acid, a deleterious factor for TPA conversion in flask cultivation, was efficiently regulated by deleting the poxB gene along with operating the bioreactor to supply oxygen. By applying two-stage fermentation consisting of the growth phase in pH 7 followed by the production phase in pH 5.5, a total of 13.61 mM ßKA was successfully produced with 96% conversion efficiency. This efficient chemobiological PET upcycling system provides a promising approach for the circular economy to acquire various chemicals from PET waste.

Recent Advances in the Chemobiological Upcycling of Polyethylene Terephthalate (PET) into Value-Added Chemicals.

Polyethylene terephthalate (PET) is a plastic material commonly applied to beverage packaging used in everyday life. Owing to PET's versatility and ease of use, its consumption has continuously increased, resulting in considerable waste generation. Several physical and chemical recycling processes have been developed to address this problem. Recently, biological upcycling is being actively studied and has come to be regarded as a powerful technology for overcoming the economic issues associated with conventional recycling methods. For upcycling, PET should be degraded into small molecules, such as terephthalic acid and ethylene glycol, which are utilized as substrates for bioconversion, through various degradation processes, including gasification, pyrolysis, and chemical/biological depolymerization. Furthermore, biological upcycling methods have been applied to biosynthesize value-added chemicals, such as adipic acid, muconic acid, catechol, vanillin, and glycolic acid. In this review, we introduce and discuss various degradation methods that yield substrates for bioconversion and biological upcycling processes to produce value-added biochemicals. These technologies encourage a circular economy, which reduces the amount of waste released into the environment.

Recent Advances in Sustainable Plastic Upcycling and Biopolymers.

Advances in scientific technology in the early twentieth century have facilitated the development of synthetic plastics that are lightweight, rigid, and can be easily molded into a desirable shape without changing their material properties. Thus, plastics become ubiquitous and indispensable materials that are used in various manufacturing sectors, including clothing, automotive, medical, and electronic industries. However, strong physical durability and chemical stability of synthetic plastics, most of which are produced from fossil fuels, hinder their complete degradation when they are improperly discarded after use. In addition, accumulated plastic wastes without degradation have caused severe environmental problems, such as microplastics pollution and plastic islands. Thus, the usage and production of plastics is not free from environmental pollution or resource depletion. In order to lessen the impact of climate change and reduce plastic pollution, it is necessary to understand and address the current plastic life cycles. In this review, "sustainable biopolymers" are suggested as a promising solution to the current plastic crisis. The desired properties of sustainable biopolymers and bio-based and bio/chemical hybrid technologies for the development of sustainable biopolymers are mainly discussed.

Chitosan-Derived Porous Activated Carbon for the Removal of the Chemical Warfare Agent Simulant Dimethyl Methylphosphonate.

Methods for the rapid removal of chemical warfare agents are of critical importance. In this work, a porous activated carbon material (C-PAC) was prepared from chitosan flakes via single-step potassium carbonate (K2CO3) activation for the prompt adsorption of dimethyl methylphosphonate (DMMP). C-PAC samples were prepared using different carbonization temperatures (350, 550, and 750 °C) at a constant K2CO3/chitosan ratio (1:2) and using different activator ratios (K2CO3/chitosan ratios of 1:0.5, 1:1, 1:2, and 1:3) at 750 °C. Furthermore, we evaluated the effect of preparation conditions on the adsorption capacities of the various C-PAC materials for DMMP under ambient conditions (25 °C). Notably, for the C-PAC material prepared at 750 °C using a K2CO3/chitosan ratio of 1:2, the DMMP adsorption was saturated at approximately 412 mg·g-1 carbon after 48 h. The good performance of this material makes it a potential candidate for use in remedial applications or protective gear.

The Renewable and Sustainable Conversion of Chitin into a Chiral Nitrogen-Doped Carbon-Sheath Nanofiber for Enantioselective Adsorption.

Well-known hard-template methods for nitrogen (N)-doped chiral carbon nanomaterials require complicated construction and removal of the template, high-temperature pyrolysis, harsh chemical treatments, and additional N-doping processes. If naturally occurring chiral nematic chitin nanostructures [(C8 H13 NO5 )n ] in exoskeletons were wholly transformed into an N-doped carbon, this would be an efficient and sustainable method to obtain a useful chiral nanomaterial. Here, a simple, sacrificial-template-free, and environmentally mild method was developed to produce an N-doped chiral nematic carbon-sheath nanofibril hydrogel with a surface area >300 m2 g-1 and enantioselective properties from renewable chitin biomass. Calcium-saturated methanol physically exfoliated bulk chitin and produced a chiral nematic nanofibril hydrogel. Hydrothermal treatment of the chiral chitin hydrogel at 190 °C produced an N-doped chiral carbon-sheath nanofibril hydrogel without N-doping. This material preferentially adsorbed d-lactic acid over l-lactic acid and produced 16.3 % enantiomeric excess of l-lactic acid from a racemic mixture.

Five different chitin nanomaterials from identical source with different advantageous functions and performances.

Chitin is a renewable and sustainable biomass material that can be converted into various one-dimensional crystalline nanomaterials different in 1) length, 2) diameter, 3) charge density, 4) type of charge, and 5) crystallinity via diverse top-down synthetic methods. These nanomaterials have great potential as sustainable reinforcing and biologically functional materials. The proper design of chitin nanomaterials maximizes their performances in specific applications. Extensive efforts are devoted to understanding each type of chitin nanomaterial produced from different chitin sources; however, few studies have compared different chitin nanomaterials. Herein, we synthesize five different types of chitin nanomaterials from identical sources and compare their physical and chemical properties, including suitability for assorted purposes. Factors 1)-5) are discussed regarding their dominance in determining functionality depending on the specific goals of a) gas barriers, b) mechanical reinforcements, c) dispersibility in various pH aqueous buffers, d) thermal dimensional stability, and e) antibacterial activity. This study gives insights to design new chitin nanomaterial-based materials.

A ball milling-based one-step transformation of chitin biomass to organo-dispersible strong nanofibers passing highly time and energy consuming processes.

Chitin, a sustainable and functional biological macromolecule, can be converted into chitin nanofibers (ChNFs), and are applicable as a mechanically reinforcing and bioactive filler for polymer matrices. Improving the performance of ChNFs typically relies on their nanofibrilization and miscibility with matrices. To transform chitin biomass into organo-dispersible ChNFs, a series of time-/energy-consuming chemical and mechanical treatments are required: 1) deacetylation, 2) disintegration, 3) surface modification to minimize their aggregation through hydrogen bonds, 4) drying, and 5) re-dispersion. This paper presents a one-step method to transform chitin biomass to organo-dispersible acetylated ChNFs via a ball-milling method in the presence of relatively low toxic acetic anhydride without water. This method minimizes water contaminations and energy for dehydrating. The resulting chitin nanofiber material is mixed with poly(l­lactic acid) (PLLA) to produce all-bio-based nanocomposites. The composite indicated a 66% increase in Young's modulus and a 100% increase in tensile strength compared to the pristine PLLA. Furthermore, it did not exhibit any observable cytotoxic effect, thus potentially applicable as a biomedical material.

Electrochemical Synthesis of Photoelectrodes and Catalysts for Use in Solar Water Splitting.

This review focuses on introducing and explaining electrodepostion mechanisms and electrodeposition-based synthesis strategies used for the production of catalysts and semiconductor electrodes for use in water-splitting photoelectrochemical cells (PECs). It is composed of three main sections: electrochemical synthesis of hydrogen evolution catalysts, oxygen evolution catalysts, and semiconductor electrodes. The semiconductor section is divided into two parts: photoanodes and photocathodes. Photoanodes include n-type semiconductor electrodes that can perform water oxidation to O2 using photogenerated holes, while photocathodes include p-type semiconductor electrodes that can reduce water to H2 using photoexcited electrons. For each material type, deposition mechanisms were reviewed first followed by a brief discussion on its properties relevant to electrochemical and photoelectrochemical water splitting. Electrodeposition or electrochemical synthesis is an ideal method to produce individual components and integrated systems for PECs due to its various intrinsic advantages. This review will serve as a good resource or guideline for researchers who are currently utilizing electrochemical synthesis as well as for those who are interested in beginning to employ electrochemical synthesis for the construction of more efficient PECs.

Combined biomass valorization and hydrogen production in a photoelectrochemical cell.

In a typical hydrogen-producing photoelectrochemical cell (PEC), water reduction at the cathode (producing hydrogen) is accompanied by water oxidation at the anode (producing oxygen). This anode reaction is, however, not kinetically favourable. Here we investigate the possibility of utilizing solar energy for biomass conversion by performing the oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) at the anode of a PEC. HMF is a key intermediate in biomass conversion, and FDCA is an important monomer for the production of numerous polymers. Using 2,2,6,6-tetramethylpiperidine-1-oxyl as a mediator, we obtained a near-quantitative yield and 100% Faradaic efficiency at ambient conditions without the use of precious-metal catalysts. This reaction is also thermodynamically and kinetically more favourable than water oxidation. Our results suggest that solar-driven biomass conversion can be a viable anode reaction that has the potential to increase both the efficiency and the utility of PECs constructed for solar-fuel production.

Manual assembly of nanocrystals for enhanced photoelectrochemical efficiency of hematite film.

To improve the optoelectronic properties of hematite film as a photoanode, hematite film was orientated on the (012) plane by the secondary growth of organized microcrystals. The resultant film showed promising photoelectrochemical effects compared with a randomly oriented one, with a maximum photocurrent of 0.8 mA cm(-2) at 1.23 V vs. RHE under the illumination of 1 sun.

Fabrication of hollow metal oxide nanocrystals by etching cuprous oxide with metal(II) ions: approach to the essential driving force.

Hollow metal oxide nanocrystals were prepared by etching cuprous oxide with metal ions and were applied as photoelectrodes. As a hard template, polyvinylpyrrolidone stabilized cuprous oxide (PVP-Cu2O) and non-stabilized cuprous oxide (nPVP-Cu2O) were synthesized by a precipitation method. Hollow iron oxide and cobalt oxide nanocrystals with a truncated octahedral morphology were fabricated by an etching reaction with transition metal(II) ions (Fe(2+) or Co(2+)). In the etching reaction process, a cationic exchange reaction occurs between the divalent metal ion and Cu(+) due to the higher Lewis acidity. Facet selective etching of cuprous oxide has been observed during the ionic exchange reaction of Cu(+) and O(2-) ions in PVP-Cu2O complexes with transition metal(II) ions (Fe(2+) or Co(2+)) at the surface of a (110) facet. Amorphous states of hollow metal oxide products were annealed to form α-Fe2O3 (hematite) and Co3O4 and their crystal structure was examined with X-ray diffraction and HR-TEM. The optical absorption behavior of semiconductor nanocrystals was measured with UV-vis spectroscopy to define band gap energy. The hollow hematite structure has a 2.08 eV band gap and Co3O4 (Co(II,III) oxide) has a 1.80 eV indirect band gap. Using these hollow nanocrystals, a metal oxide monolayer film was fabricated with a secondary growth approach and was studied for its photocatalytic properties.

One-dimensional ferromagnetic dendritic iron wire array growth by facile electrochemical deposition.

One-dimensional ferromagnetic iron dendritic wire array film is prepared by facile electrodeposition. The space hindrance effect caused by neighbouring crystals resists the free growth directions parallel to the substrate, which is considered as a possible growth mechanism of one-dimensional morphology. Dendritic iron wire can be transformed into α-Fe(2)O(3) without destroying the dendritic morphology by thermal oxidation.

Hydrothermal synthesis of anatase TiO2 nanorods with high crystallinity using ammonia solution as a solvent.

Anatase TiO2 nanorods with high crystallinity were synthesized using ammonia solution (28%) as a solvent by through the hydrothermal method. The X-ray diffraction pattern confirmed the product's anatase phase and high crystallinity, and the transmission electron microscope (TEM) image demonstrated the unique morphologies of the two ends of the TiO2 nanorods (two tringle-horn shapes and one round-horn shape), whose lengths and widths were within the ranges of 200-300 and 60-110 nm, respectively. The high-resolution TEM image clearly displayed the crystal lattices of the (101) planes lying along the direction of the lengthes of the TiO2 nanorods. The energy dispersive X-ray spectrum of a TiO2 nanorod revealed the presence of about 4 atm% nitrogen element as a trace in the anatase TiO2 nanorod. The Raman spectrum of the TiO2 nanorods also showed the typical bands of anatase TiO2 and very weak peaks resulting from the TiN first-order defect-induced Raman scattering. The UV-vis diffuse-reflectance spectra showed a slight red shift (about 3 nm) of the anatase TiO2 nanorods compared with P25, which probably resulted from the trace of TiN on the surfaces of the anatase TiO2 nanorods. A three-stage-process mechanism model is proposed for the formation of the nanorods: Rhombus crystallites bounded by four {101} faces are first formed through anisotropic growth, then longer rhombus crystallites are grown via oriented attachment, finally, nanorods with a unique morphology are self-assembled by Van Der Waals forces.

Facile preparation of Fe2O3 thin film with photoelectrochemical properties.

We report a simple approach for preparing undoped and Pt-doped Fe(2)O(3) thin films with excellent photoactivity via facile hydrothermal growth. The photocurrent densities of undoped and Pt-doped Fe(2)O(3) thin films were recorded up to 1.2 and 1.38 mA cm(-2) at 0.23 V Ag/AgCl under 1 sun illumination, respectively.

Template assisted growth of cobalt ferrite nanowires.

Cobalt ferrite nanowires with a diameter of about 30 nm have been prepared inside anodized aluminum oxide (AAO) templates with one end closed nanopores using a vacuum infiltration method. The ferrite phase formation was confirmed by X-ray diffraction. Field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) were employed to characterize the morphology and structure of nanowires. SQUID magnetometer measurement showed that the nanowires to have both ferrimagnetic and superparamagnetic characteristics. A model for formation of discontinuous nanowires and particle agglomeration inside the template is discussed to explain these results.

Gamma-ray irradiation on microsized Nd-Fe-B and Sr-ferrite magnets at low temperature.

The gamma-ray irradiation on microsized Nd-Fe-B and Sr-Fe permanent magnet at low temperature and room temperature was investigated. The change of shape and magnetic properties of two kinds of magnet powder before and after irradiation at low temperature was measured. The crystal structure of each permanent magnet powders was analyzed using X-ray powder diffraction (XRD) and the size and shape were characterized by scanning electron microscope (SEM). The changed magnetic properties of magnet such as saturation magnetization (M(s)) and coercivity (H(c)) were measured by VSM.

Characterization of Ag nanoparticle superlattice structure prepared using two carboxylic acids.

One-step hydrothermal process is introduced for the synthesis of highly ordered self-assembled Ag nanoparticles. Ag nanoparticles with same diameter and narrow size distribution are synthesized in the presence of the mixture of two capping molecules, the combination of sodium oleate and aromatic carboxylic acid. Self-assembled 3D superlattice structures of Ag nanoparticles are synthesized in aqueous system without any post-procedure. Effects of aromatic carboxylic acid to sodium oleate and the nature of interaction between nanoparticles in superlattices are characterized with TEM examinations and FT-IR spectra.

New avenues to efficient chemical synthesis of exchange coupled hard/soft nanocomposite magnet.

Nd-Fe-B ultrafine amorphous alloy particles were prepared by reaction of metal ions with borohydride in aqueous solution. Monodispersed Fe nanoparticles were synthesized under an argon atmosphere via thermal decomposition of Fe(2+)-oleate2. Exchange coupled Nd2Fe14B/Fe nanocomposite magnets have been prepared by self-assembly using surfactant. The crystal structure of the synthesized nanoparticles was identified by using X-ray powder diffraction (XRD). The size and shape of nanoparticles were obtained by transmission electron microscope (TEM). Thermogravimetry using a microbalance with magnetic field gradient positioned below the sample was used for the measurement of a thermomagnetic analysis (TMA) curve showing the downward magnetic force versus temperature.