Temporal dynamics of lignin degradation in Quercus acutissima sawdust during Ganoderma lucidum cultivation.

Despite a fair amount of lignin conversion during mycelial growth, previous structural analyses have not yet revealed how lignin changes continuously and what the relationship is between lignin and ligninolytic enzymes. To clarify these aspects, Quercus acutissima sawdust attaching Ganoderma lucidum mycelium collected from different growth stage was subjected to analysis of lignin structure and ligninolytic enzyme activity. Two key periods of lignin degradation are found during the cultivation of G. lucidum: hypha rapid growth period and primordium formation period. In the first stage, laccase activity is associated with the opening of structures such as methoxyls, ß-O-4' substructures and guaiacyl units in lignin, as well as the shortening of lignin chains. Manganese peroxidases and lignin peroxidases are more suitable for degrading short chain lignin. The structure of phenylcoumarans and syringyl changes greatly in the second stage. The results from sawdust attaching mycelium provide new insights to help improve the cultivation substrate formulation of G. lucidum and understand biomass valorization better.

A Study of Electroplated Nanoporous Copper Using Aberration-Corrected Transmission Electron Microscopy.

Nanoporous Cu foam is widely applied in many fields such as the packaging of electronic power devices. In this study, a sandwich-structured Cu-Zn eutectic alloy precursor composed of Cu0.53Zn0.47/Cu5Zn8/Cu0.53Zn0.47 is prepared through electroplating. The surface layer of the precursor, Cu0.53Zn0.47, has a flat surface with numerous grain boundaries, which effectively promotes its dealloying behavior. By contrast, Cu5Zn8 has a porous structure, which promotes the dealloying behavior at the center of the precursor. The dealloying of Cu0.53Zn0.47 is dominated by the coherent surface diffusion of Cu atoms, and the crystal lattice and orientation show no changes before and after dealloying. By contrast, the dealloying behavior of Cu5Zn8 requires the renucleation of Cu crystals; in this process, Cu atoms are transported to the surface of the layer by capillary forces to form clusters, which nucleate and grow.

Confinement-Modulated Clusterization-Triggered Time-Dependent Phosphorescence Color from Xylan-Carbonized Polymer Dots.

Achieving time-dependent phosphorescence color (TDPC) in organic materials is attractive but extremely challenging due to the nonradiative decay and modulation puzzle of triplet state. Herein, xylan, a hemicellulose waste from the paper mill, was used to construct carbonized polymer dots (CPDs) with clusterization-triggered room-temperature phosphorescence (RTP). CPDs were endowed with tuneable triplet energy levels by through-space conjugation of heteroatom groups, which could be confined in silica to simultaneously activate surface oxide-related low-energy and cross-linked core N-related high-energy emissive centers. Thus, the blue emissive center with a lifetime of 425.6 ms and green emissive center with a longer lifetime of 1506 ms coexisted in the confined CPDs; the former was the dominant contribution to RTP at first, and the latter became dominant over time, leading to a typical TDPC evolution with large color contrast from blue to blue-green and then to green. Meanwhile, the TDPC could remain unobstructed after the confined CPDs were soaked in water for more than a month. The CPDs were successfully applied in location and deformation imaging of hydrogel and advanced dynamic information encryption and anticounterfeiting. The work may shed new light on the design of TDPC materials and broaden the high-value use of paper-mill waste xylan.

Effect of CoSn3 nanocrystals on Sn3Ag plating for electronic packaging.

Plating Sn3Ag on copper substrates represents a crucial electronic packaging technique. In this study, we propose a novel composite plating approach, wherein CoSn3 nanocrystals are deposited within the Sn3Ag coating. The resulting reflowed Sn3Ag joints exhibit a range of distinctive properties. Notably, CoSn3 nanocrystals dissolve in Sn during the reflow process, thereby lowering the supercooling required for Sn nucleation. Consequently, Sn crystals grow in six-fold cyclic twins. Additionally, the dissolution of Co atoms in Sn leads to a reduced solubility of Cu atoms in Sn, consequently lowering the supercooling required for the nucleation of Cu6Sn5. Simultaneously, this phenomenon promotes the nucleation of Cu6Sn5, resulting in a considerable precipitation of Cu6Sn5 nanoparticles within the joints. Therefore, the mechanical properties of the joints are significantly enhanced, leading to a notable 20% increase in shear strength. Furthermore, the presence and distribution of Co elements within Sn induce changes in the growth pattern of interfacial Cu6Sn5. The growth process of Cu6Sn5 is dominated by the interfacial reaction, leading to its growth in a faceted shape. During the aging process, the dissolution of Co elements in Sn impedes the continuous growth of Cu6Sn5 at the interface, causing Cu6Sn5 to be distributed in the form of islands inside the joint. Remarkably, elemental Co acts as an inhibitor for the development of Cu3Sn and reduces the occurrence of Kirkendall voids.

Synthesis and Atomic Transport of CoSn3 NanoIMC by In Situ TEM.

In order to optimize the interfacial properties by adding Co to the bumps of copper pillars and to overcome the strong tendency of Co to oxidize, an intermetallic compound (IMC) "capsule" was developed for the purpose of transporting elements through the intermetallic compound. In this study, we present a comprehensive analysis of the transformation process of CoSn2 nanoparticles into CoSn3 at the nanoscale using in situ heating transmission electron microscopy (TEM). The experimental results reveal that CoSn2 nanoparticle growth occurs through polymerization, whereas CoSn3 nanoparticle formation relies on the reaction between CoSn2 and Sn. During the initial stages of the reaction, Co dissolves and diffuses into Sn, leading to the nucleation and growth of CoSn2 in Sn via Ostwald ripening. As the input energy increases, vacancies in CoSn2 drive a reaction at the Sn/CoSn2 interface, resulting in the generation of CoSn3. In this process, Sn nanoparticles enter the CoSn2 structure through the "Anti Structure Bridge (ASB) mechanism" to fill vacancies. Following the codeposition process, CoSn3 nanoparticles were successfully plated within the Sn layer of the Cu-pillar bumps. Upon reflow heating, the CoSn3 nanoparticles exhibited a preference for precipitating the vacant sites within the Sn layer. This process facilitated the release of Co atoms from CoSn2, enabling their diffusion throughout the entire Sn layer.

Xylan Plastic.

The increasing accumulation of plastic waste has brought serious environmental issues. Biodegradable plastics are promising candidates to solve the problem but still remain a scientific challenge. Here, xylan plastic (XP) was fabricated by a strategy of double cross-linking through etherification combined with hot pressing. The mechanical properties, particularly the toughness of XP, were significantly enhanced by the incorporation of chemical and physical cross-linking domains. The tensile strength, toughness, and modulus of XP can reach up to 55 MPa, 2.2 MJ/m3, and 1.7 GPa, respectively, which are superior to most traditional plastics. Dynamic mechanical analysis (DMA) characterizations confirmed that XP is thermoplastic and can be hot formed. Additionally, the reversible hydrogen bond interaction between xylan chains could be simply regulated by water molecules, rendering XP readily transformed and repeatedly reprogrammed into versatile 2D/3D shapes. Moreover, XP showed a low thermal expansion coefficient and excellent optical properties. Cytotoxicity and degradability tests demonstrated that XP had excellent nontoxicity and can be biodegraded in 60 days. This work thus suggests an avenue for the scalable production of high-performance xylan-based plastics, in which the raw material comes from industrial wastes and exhibits great potential in response to plastic pollution.

Unveiling lignin structures and lignin-carbohydrate complex (LCC) linkages of bamboo (Phyllostachys pubescens) fibers and parenchyma cells.

Bamboo (Phyllostachys pubescens) is an attractive biomass block to develop biorefining industry, however, less emphasis has been placed on elucidating the chemical linkage variations of lignin and LCC between different bamboo cell walls. Here, purified milled wood lignin (MWLp) and lignin-carbohydrate complex (LCC) were isolated from bamboo (Phyllostachys pubescens) fibers (BF) and parenchyma cells (PC), respectively. The variations of structure features and chemical linkages of lignin and LCC were investigated via FT-IR, 2D HSQC NMR, and 31P NMR techniques. 2D HSQC NMR revealed that ß-O-4 alkyl-aryl ether linkages and resinol (ß-ß) substructure were the main substructures in BF-MWLp and PC-MWLp. ß-1 linkages existed in the PC-MWLp (3.18/100 Ar), but not in BF-MWLp. Moreover, tricin, as a flavonoid compound, was only detected in the BF-MWLp. The amount of the syringyl (S) units of PC-MWLp was higher than BF-MWLp. The results indicated that phenyl glycoside (PhGlc) bonds (mainly lignin and xylan) were the predominant chemical linkage type of LCC bonds in BF-LCC and PC-LCC, and the high contents of PhGlc bonds (45.53/100 Ar) were presented in PC. Our finding can provide a reference for the structural variations of lignin and LCC between the different bamboo cell walls.

Microencapsulated phase change material via Pickering emulsion based on xylan nanocrystal for thermoregulating application.

Phase change materials (PCM) are promising for thermal regulation and energy storage, but suffer from the deformation and leakage of capsules. Herein, inspired by cellulose nanocrystal (CNC), xylan nanocrystal (XNC) with a dimension of 25-60 nm was successfully prepared through oxalic acid hydrolysis of high-crystalline xylan as raw materials via a top-down approach. With the introduction of hydrophobic groups, compared to XNC, succinylated XNC showed more remarkable emulsifying property over 7 days of storage at room temperature. Microencapsulated PCM composite consisting of sodium alginate (SA) as "matrix" and succinylated xylan nanocrystal (XNC) stabilized paraffin-based Pickering capsule (PCM beads) as "core" was facilely fabricated. PCM composite with the latent heat of 105.59 J·g-1 showed excellent thermoregulating performance. Our work suggests a new pathway toward sustainability of hemicelluloses in the application of food emulsion and thermal energy management.

Rapid, selective, and room temperature dissolution of crystalline xylan by a hydrotrope.

Selective dissolution of industrial biowaste is of significant importance for the valorization of biomass. Especially, fractionation of polysaccharides with similar structures is more challenging. Herein, a new kind of cationic hydrotrope, tetraethylammonium hydroxide (TEAH), has been developed for rapid, efficient, and selective dissolution of industrial biowastes-xylan type hemicelluloses from viscose fiber mills. When the concentration of TEAH is 15 wt%, the solubility of industrial crystalline xylan reaches to 13.39 wt% at room temperature. Crystalline or amorphous xylan can be regenerated by adding water or ethanol, with 57.98 % and 95.45 % yields, respectively. Additionally, we showcase hemicelluloses were near-completely extracted from holocellulose without degrading cellulose under ambient temperature by simply adjusting the concentration of TEAH, demonstrating the advantage of the hydrotropic feature. This hydrotrope solvent system features selective, rapid, and room temperature dissolution polysaccharides, which will shed new light in technological applications of the industrial spinning or biorefining processes.

Top-Down Production of Sustainable and Scalable Hemicellulose Nanocrystals.

Polysaccharide nanocrystals have led to the development of multifunctional and sustainable materials, but most are glucose-based carbohydrates derived from valuable natural sources. Here, we present a top-down strategy that enables one, for the first time, to isolate xylose-based hemicellulose nanocrystals from available industrial biowastes. By leveraging the selective oxidation of alkaline periodate, as high as 34 wt % solid yield is accessible. The hemicellulose nanocrystals exhibit platelet-like shapes (10-20 nm thickness, 30-80 nm wide), crystalline features, and superior dispersibility in water. We also showcase their successful interface applications for one-dimensional (1D) carbon nanotube (CNT) nanoinks and two-dimensional (2D) transition-metal dichalcogenide (TMD) nanozymes, which are comparable to the traditional cellulose nanocrystals. The scalable, low-cost, and sustainable hemicellulose nanocrystals can be envisioned to provide an alternative for glucose-based polysaccharide nanocrystals, as well as hold promise for the high-value utilization of biowastes.

CoSn3 Intermetallic Nanoparticles for Electronic Packaging.

At present, composite solder pastes are getting a lot of attention, especially composite Sn based solders reinforced by nanoparticles. Indeed, CoSn3 is a strong nucleating agent of Sn crystal, which has potential application value in the field of electronic packaging. However, there is no reliable synthetic path for CoSn3 nanoparticles at present. In this article, a chemical synthesis method for CoSn3 nanoparticles is developed. Here, CoCl2 and SnCl2 are reduced by NaHB4 in triethylene glycol (TEG), dispersed by ultrasonics, and heated to 350 °C in a tube furnace for growth. The CoSn3 nanoparticles with a diameter of about 150 nm are obtained by heating at 350 °C for 10 min. The CoSn3 nanoparticles undergo a step reaction in the process of synthesis and go through different stages of merging and annexation during their growth. The crystal growth behavior and the process of orientation change during the nucleation and growth of CoSn3 nanoparticles are studied, especially the two growth mechanisms, namely OU (orientation unified) and OA (orientation attached). By mixing CoSn3 nanoparticles with SAC305, we obtain a kind of strengthened composite soldering paste. There are obvious six-fold cyclic twins in the joints made by this soldering paste.

Effects of hydrothermal pretreatment on the dissolution and structural evolution of hemicelluloses and lignin: A review.

Exploration of lignocellulosic biomass provides a sustainable and eco-friendly route for producing liquid fuels, materials, and chemicals. However, direct utilization of lignocelluloses is limited by the stable and complicated cross-linking structure of the plant cell wall. Hydrothermal pretreatment (HTP) is a green and cost-effective technology because it can disrupt lignin-carbohydrate complex (LCC) linkages, dissolve hemicelluloses and lignin, and redistribute lignin in the cell wall layers without utilization of any chemicals. Thus, HTP is expected to achieve industrial scale in second-generation biorefineries and circular bioeconomies. This review analyzed the deconstruction of lignocelluloses by HTP, with particular emphasis on the formation mechanism of hemicellulose degradation products and the structural evolution of hemicelluloses and lignin accompanying HTP. Meanwhile, the formation mechanism of pseudolignin and its effect on the enzymatic hydrolysis of cellulose as well as strategies for inhibiting lignin recondensation were discussed.

Constructing a Novel Xylan-Based Film with Flexibility, Transparency, and High Strength.

Xylan-based films have great potential to replace petroleum-based polymers used for packaging and coatings due to their excellent biocompatibility, biodegradability, and good gas barrier properties. However, fabricating a xylan-based film with flexible, transparent, water-proof, and excellent mechanical properties is an enormous challenge. Herein, we manufactured a series of degradable films with adjustable properties via solution-casting using a water-soluble xylan derivative. This is the first report of a pure xylan-based film with high performance, requiring no additives. The tensile strength of the xylan-based film could be controlled by adjusting the aldehyde content, which varied from 105.0 to 132.6 MPa. The smallest initial water contact angle of the xylan-based films is 93.26°, indicating that these films are hydrophobic. This work shows a simple and viable route toward manufacturing xylan-based films with high tensile strength, flexibility, and transparency, which can be used for packaging materials and coatings.

Fabrication of flexible composite film based on xylan from pulping process for packaging application.

To realize the application of xylan based film in food and drug packaging, the poor mechanical property and film-forming property of xylan based film must be overcome. Herein, a good oxygen barrier composite film with desired mechanical properties was prepared based on carboxymethly xylan (CMX), chitosan (CS), and graphene oxide (GO). The results of scanning electron microscope revealed the composite film had a dense and continuous structure, which will endow the composite film with excellent mechanical property. As expected, the composite film with the 0.5% mass fraction of GO exhibited best mechanical property, among which the tensile stress, tensile strain, and Young's modulus of the composite film reached 50.81 MPa, 47.61%, and 1.39 GPa, respectively. The oxygen barrier properties of the composite films significantly increased with the addition of graphene oxide due to the dense, stacked multilayer structure. In addition, these composite films exhibited good antibacterial properties. Therefore, these films show great promise in the field of food packaging and wound dressing due to their excellent mechanical, oxygen barrier and antibacterial properties.