A mesoporous niobium oxophosphate (NbOP) catalyst was successfully synthesized and for the first time applied to the catalytic pyrolysis of wood-plastic composite (WPC) waste. The synergistic interaction between biomass and plastic fractions in WPCs resulted in a significant reduction in oxygenated compounds while facilitating the formation of light aliphatic hydrocarbons. In the catalytic pyrolysis of wood-polyethylene composites (WPE) with H-ZSM-5 and Nb2O5 as reference catalysts, the NbOP catalyst demonstrated superior deoxygenation efficiency compared to both counterparts. Notably, only a trace amount of oxygenated compounds (0.2 %) was detected in the products catalyzed by NbOP, whereas the relative contents of oxygenated compounds in the volatile products generated by H-ZSM-5 and Nb2O5 stood at 9.1 % and 18.9 %, respectively. Furthermore, NbOP outperformed the reference catalysts in terms of monocyclic aromatic hydrocarbon (MAH) selectivity. At 650 degrees C, it achieved a MAH selectivity of 49.5 % from wood-polyethylene composites (WPE), which is substantially higher than the corresponding values obtained with H-ZSM-5 (37.7 %) and Nb2O5 (4.5 %) under comparative experimental conditions. A similar phenomenon was observed in the catalytic pyrolysis of wood-polypropylene composites (WPP). The superior performance of NbOP was attributed to its unique mesoporous structure (4.44 nm) and dual acid sites (Br & Oslash;nsted/Lewis acid ratio of 0.54), which synergistically promoted efficient deoxygenation and aromatization. Mechanistic studies revealed that NbOP accelerated both C-O bond cleavage in lignin-derived phenolics and cyclization-dehydrogenation of polyolefins. Notably, the regenerated NbOP catalyst retained excellent deoxygenation efficiency and aromatic hydrocarbon selectivity, demonstrating its potential for industrial application. This study provides a sustainable strategy for valorizing WPC waste into high-value aromatics, simultaneously addressing challenges related to environmental pollution and resource recovery.
Effectively capturing carbon dioxide (CO2) is crucial for environmental protection. In this research, we synthesized a composite aerogel (CSA-n) by integrating a bimetallic metal-organic framework (Mg/Co-MOF-74) with biomass materials (cellulose/chitosan) using an in situ mineralization approach. This composite aerogel exhibited enhanced CO2 adsorption capabilities than pure biomass aerogel. At 298 K and 100 KPa, the CO2 adsorption capacity of CSA-3 reached 6.4 mmol/g, an increase of 16.4% compared to pure MOF. The significant improvement of CO2 uptakes could be attributed to the more complex pore structure of the composite aerogel compared to pure MOF. Additionally, simulations based on the ideal adsorption solution theory (IAST) showed that the separation factors of CSA-3 for CO2/N2 and CO2/CH4 gas mixtures were 594.3 and 43.4, respectively. Furthermore, the composite aerogel exhibited excellent cyclic stability. After 10 cycles, the CO2 adsorption capacity of CSA-3 remained at 96.8%. The results suggest that this bimetallic metal-organic framework @biomass hybrid aerogel holds great potential for CO2 adsorption and separation applications.
In recent years polysorbate (PS) degradation in biotherapeutic protein formulations has become one of the most challenging topics for residual host cell protein control. With such focus, various assays have been showcased to help inform on enzymatically driven PS degradation risk assessment and control. Access to multiple, orthogonal data sets can improve understanding but also increases complexity in data interpretation. To highlight how multiple assays can work together to provide an aligned enzymatically driven PS degradation risk assessment and control, three cases studies are discussed. The case studies are diverse in the driver for performing these experiments along with if they are proactively or reactively addressing PS degradation. From these three case studies it becomes apparent that assays are consistent in their use and alignment regarding enzymatically driven PS degradation risk assessment and control. In general, an assay will fall into one of three categories: risk informing, characterization, and extended characterization. With this information future work focused on enzymatically driven PS degradation risk assessment and control has a blueprint for what assays can be used and what the data informs on.
Lignin is the most abundant aromatic biopolymer. Thus, preparation of BTX (benzene, toluene and xylenes) by catalytic fast pyrolysis (CFP) of lignin is attractive. Ni-Al mixed metal oxide (MMO) catalysts, derived from pyrolyzing Ni-Al layered double hydroxides (LDH), were prepared for the catalytic fast pyrolysis of lignin. The effects of catalyst Ni/Al ratio, catalyst dosage and pyrolysis temperature on the liquid products were investigated by Py-GC/MS. The Ni3Al3-MMO produced the best liquid product distribution from lignin at 700 celcius. The selectivity of Ni3Al3-MMO for aliphatic hydrocarbons and monocyclic aromatic hydrocarbons (MAHs) was 18.0% and 78.2%, respectively. The selectivity to polyaromatic hydrocarbons (PAHs) was 3.8%. No phenols and phenolic derivatives were produced. This is related to the mesoporous catalytic structure (pore size of 14.37 nm), large external surface area (134.74 m2/g) and strong acidity (4.92 mmolNH3/g) of Ni3Al3-MMO. In addition, a mechanistic study was performed with the lignin model compound (guaiacol) showing that Ni3Al3-MMO exhibits strong deoxygenation activity for aromatic C-O bond cleavage of lignin.
In this study, researchers aimed to enhance the properties of wood flour/high-density polyethylene (HDPE) biocomposites by incorporating polycarbonate (PC). To improve the thermal stability of wood flour, boric acid treatment was employed. The treated wood flour was then blended with PC and HDPE to create hybrid polymer biocomposites. The resulting materials were characterized for their chemical structure, microstructure, and properties. The findings revealed that PC was uniformly distributed within the polyethylene matrix as micro- or nanoparticles. By adding PC, the thermal stability of the composites increased, with a 6.7% increase in char residue rate at a PC content of 28%. PC particles acted as nucleating agents for the crystallization behavior of the biocomposites, similar to other nanoparticles. Consequently, the crystallization temperature of the composites increased with increasing PC content. However, the addition of PC did not alter the crystallinity of the composites. Furthermore, the addition of PC reduced the heat release rate during combustion. The tensile strength and modulus of elasticity of the composites increased by 27.7% and 91.1%, respectively. In addition, the flexural strength and elasticity increased by 22.7% and 53.8%, respectively. The creep strain of the composites decreased gradually with increasing PC content, indicating improved anti-creep properties due to the presence of PC. In conclusion, through hybridization and fire retardancy enhancement, the strength, thermal stability, and fire resistance of wood fibers were improved in the resulting biocomposites.
A novel transparent flame retardant coating was prepared using aqueous melamine formaldehyde resin (MF) as the film-forming resin and gas source, phosphoric acid-tannic acid (H3PO4-TA) as the acid and carbon source, and nano zinc oxide (nano-ZnO) as the flame retardant synergist. These coatings were applied to the surface of poplar wood panels to enhance the flame retardancy of wood. After complete drying and curing, the surface of the flame retardant coating was smooth and flat, with an overall light transmission rate exceeding 80 %, and the surface pattern of the wood was clear and visible. The large-plate combustion test showed that the maximum flame retardant time of the sample with 5 % ZnO reached 32 min. The cone calorimeter test showed that the ignition time of the 5 % nano zinc oxide sample increased from 8 s for the coated sample to 310 s, an increase of 3775 %. At the same time, the flame retardant coating, particularly with the addition of nano-ZnO, significantly reduced the heat release rate (HRR) and total heat release (THR) of the wood, demonstrating excellent flame retardant properties. After combustion, the carbon layer showed that the addition of nano zinc oxide increased the graphitization degree of the carbon layer, increased the expansion height of the carbon layer, and formed a denser carbon layer. In summary, this coating has a simple preparation method, low cost, outstanding flame retardant effect, and good transparency, making it a promising application prospects in the flame retardant field of wood products.
The bio-based flame-retardant treatment for lyocell fabrics is often characterized by low flame-retardant efficiency and deterioration of wearing property. In this study, the modified lyocell fabrics (APDP/Lyocell) with excellent fire safety and wearing property were designed and obtained via hydrogen bonding. The well-coordinated bio-based APDP was evenly distributed on the surface of lyocell fibers. In addition, water solvent was used in the preparation of APDP and the whole treatment process of the resulting lyocell fabrics. The self-extinguishing property of APDP/Lyocell was obtained using the vertical burning test with the APDP loading of 13.0
The severe negative effects of impurities adhering to the external surface of wearable devices can significantly influence the signal transmission, performance, and lifespan of hydrogel sensors. Herein, we developed an ion-conducting hydrogel sensor with a strong adhesive side and a non-adhesive side, similar to a "semi-releasing material." This hydrogel, formulated using deep eutectic solvents obtained from choline chloride and acrylic acid, contained lignin. This versatile material, exhibiting properties similar to semi-releasing materials, was treated with an AlCl3 solution on one side. Additionally, the hydrogel was successfully used as a highly adhesive strain sensor for real-time monitoring of various human activity signals. Moreover, the hydrogel demonstrated excellent environmental tolerance and conductivity. Lignin extracted from wood flour endowed the hydrogel sensor with excellent adhesion energy (up to 427.1 J/m2) and UV resistance. Treatment of hydrogels with AlCl3 completely eliminated their adhesiveness, thereby enhancing fracture elongation and tensile strength. This improvement can be attributed to the absence of carboxyl groups and the formation of a metal-phenolic network. The implementation of this convenient and efficient strategy provides a more feasible approach to address challenges related to impurity adhesion and signal transmission in flexible wearable devices.
The synthesis of a novel flame retardant that can enhance fire-safety while maintaining or even improving the mechanical properties is crucial for the application of wood flour/polyvinyl chloride composites (WF/PVC). Here, the alginate-derived tactic was utilized to produce zinc oxide (ZnO) in situ on the surface of montmorillonite (MMT) nanosheet, and an original type of MMT@ZnO nanosheet was synthesized. Then, MMT@ZnO nanosheet was incorporated into the WF/PVC. The experimental results confirmed that the incorporation of MMT@ZnO nanosheet in WF/PVC simultaneously improves the flame retardancy and mechanical properties. Comparing with the WF/PVC, WF/PVC containing 6 wt% MMT@ZnO nanosheets (WF/PVCMZ-6) reduced the total heat release rate, and total smoke production by 30.1% and 32.2%, respectively. Encouragingly, the WF/ PVCMZ-6 exhibited a significant increase of 24.6% in tensile strength and 36.8% in flexural strength. This work develops a biomass alginate-derived strategy to combine ZnO and two-dimensional MMT nanosheets that simultaneously enhance the mechanical performance and flame retardancy of WF/PVC for the construction field.
Clearance of residual Host Cell Proteins (HCPs) is critical for the manufacturing processes of biotherapeutics. HCPs have the potential to impact product efficacy and quality, posing a risk to patient safety. It is therefore essential to be able to both identify and quantitate HCPs throughout drug development, even if the proteins are present in low concentrations. Traditional Enzyme-Linked Immunosorbent Assays (ELISAs) have historically served as the gold standard for monitoring HCPs; however, ELISA methods are labor-intensive and costly. With an increase of HCPs being identified below detectable quantification levels, there is a need for simultaneous detection of selectively targeted HCPs. Here, we develop a Luminex multiplexing method that is able to accurately quantify two “high-risk” lipases Lipoprotein Lipase (LPL) and Phospholipase B-Like 2 (PLBL2) within the same assay. This study outlines the method development for optimizing parameters such as antibody constructs, conjugation ratios, signal enhancement, and more in order to create the most efficient multiplexing method. As a result, a Luminex multiplexing method can provide a similar result to a monoplexing ELISA method but in a faster and more cost-effective manner. This method can be expanded to include other “high-risk” HCPs and used for future HCP applications.
A transparent intumescent flame retardant coating was prepared using melamine formaldehyde resin (MF) as the film-forming resin, phosphoric acid-pentaerythritol (H3PO4-PER) as the intumescent flame retardant system, and graphene oxide-ammonium borate (GO-ABT) as the flame retardant synergists, and applied to the surface of wood-plastic composite (WPC). The transparency, flame retardancy, and thermal stability of the flame retardant coatings were investigated and the flame retardant mechanisms of GO and ABT were analyzed. The results showed that the addition of 0.4 (wt%) GO and 4.0 (wt%) ABT coating had the best overall performance. After curing, the surface of the coating was smooth and flat, no whitening and cracking and other undesirable phenomena. Its overall light transmittance was greater than 80 %, and the surface pattern of the substrate was clearly visible. The addition of flame retardant synergists of GO and ABT significantly improve the flame retardant performance of the coating, with a maximum flame resistance time of 37 min. Meanwhile, the total heat release and total smoke release of the coating with 0.4 % GO and 4.0 % ABT decreased by 33.23 % and 39.43 % respectively compared with the control sample, and the carbon residue increased by 94.97 %, demonstrating good flame retardant and smoke suppression effects.
Catalytic fast pyrolysis (CFP) of lignin aiming monocyclic aromatic hydrocarbons (MAHs) is attractive. Five metal oxide catalysts (named c-Nb3Alx) with different Nb/Al ratios, c-Nb, c-Al, c-Nb3Al1, c-Nb3Al2 and c-Nb3Al3 were synthesized and applied to CFP of lignin. Among these catalysts, c-Nb3Al2 exhibits excellent deoxygenation ability and the highest selectivity for MAHs (77.0%). The selectivity and deoxygenation capacity of c-Nb3Al2 for MAHs were higher than H-ZSM-5 (25) as a control. It was attributed to the large external surface area (90 m2g-1), mesoporous structure (16.15 nm) and high acid amount (2.00 mmolNH3/gcat) of c-Nb3Al2. The c-Nb3Al2 has good stability and can be regenerated by simple calcination. The selectivity of the regenerated c-Nb3Al2 for MAHs was still high at 70.1%. Guaiacol was used to compare the difference in the deoxygenation capacity of c-Nb3Al2 and H-ZSM-5.
A niobium-doped HZSM-5 (H[Nb]ZSM-5) was prepared by a hydrothermal synthesis method. The morphology, phase structure, composition, pore structure, and acid content of the catalyst were characterized using a series of analysis techniques such as scanning electron microscope (SEM), energy-dispersive X-ray (EDX), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption, and temperature programmed desorption measurements (NH3-TPD). The H[Nb]ZSM-5 catalyst fully remained within the crystal framework and pore structure of HZSM-5. Meanwhile, introduction of niobium (V) endowed the catalyst with both Lewis acid and Bronsted acid sites. Catalytic fast pyrolysis (CFP) of alkali lignin was carried out through a pyrolysis and gas chromatography-mass spectrometry (Py-GC/MS) at 650 °C and atmospheric pressure. The results indicated that H[Nb]ZSM-5 can efficiently and selectively convert lignin into monoaromatic hydrocarbons (MAHs), compared to the control HZSM-5. Catalyzed by H[Nb]ZSM-5, the content of MAHs and aliphatic hydrocarbons reached 43.4% and 20.8%, respectively; while under the catalysis of HZSM-5, these values were 35.5% and 3.2%, respectively. H[Nb]ZSM-5 remarkably lowered the phenol content to approximately 2.8%, which is far lower than the content (24.9%) obtained under HZSM-5 catalysis.
Series wood-based MOF composites were fabricated by in situ growth of metal–organic frameworks in nano-wood aerogel, achieving a sustainable and efficient capture and separation of CO 2 .
以三聚氰胺甲醛树脂(Melamine-Formaldehyde,MF)为成膜树脂,以磷酸-季戊四醇(H3 PO4-PER)为膨胀阻燃体系,以氧化石墨烯(Graphene oxide,GO)为阻燃协效助剂制备透明膨胀型阻燃涂料,从而提高木塑复合材料(wood-plastic com-posites,WPC)的阻燃抑烟性能.结果表明,涂层的透明度高,物理性能良好,阻燃抑烟性能优异.GO的加入,未改变涂层物理性能,但显著提高复合材料的热稳定性和阻燃抑烟性能.加入 0.2%的GO,热重分析(Thermogravimetric analysis,TG)测试表明,涂层的残炭量增加了 11.0%;模拟大板燃烧法显示,涂层的耐燃时间较对照组提升了 75.0%;锥形量热仪(Cone calorim-eter,CONE)燃烧测试表明,可以有效抑制涂层的热释放和烟释放,涂层的总热释放量和总烟释放量最大分别下降 35.6%和 43.5%.片状结构的GO在涂料受热膨胀后成为交联点,提高炭层整体的力学强度和稳定性,进而达到阻燃抑烟的作用.
Given the increased reliance on multienzymatic cascades to synthesize biologically inspired small molecule drug candidates, the pharmaceutical industry requires efficient strategies to control immunogenic protein impurities in active pharmaceutical ingredients. Despite advances in directed enzyme evolution and biocatalysis, it is still economical to use unpurified enzymes overexpressed in host cell lysates in manufacturing processes. Due to similar solubility profiles between protein impurities and the pharmaceutical, separation strategies relying on solubility differences (direct crystallization from water or extraction) often fail. Leveraging the rapid generation of modular acid-base pairs, we describe a pH-responsive extraction strategy using tertiary ammonium phase-transfer agents for efficient purification and isolation of hydrophilic immuno-oncology drug candidate MK-1454 from an aqueous biocatalytic cascade containing crude E. coli cell lysates. We demonstrate this technique to isolate several hundred grams of MK-1454 with undetectable protein impurities for human administration in clinical trials. We further show that this extraction technique is driven by reverse micellization, and may be generally applied to the purification of other hydrophilic small molecules.
Cork materials have the property of elastic deformation under pressure due to their unique closed, porous, cell structure with thin cell wall; and they accordingly need a surface coating that matches their deformation during there being used as floor materials. However, traditional wood coatings are hard, brittle, and mostly suitable for stiff wood surfaces, which are difficult to be directly adapted to the requirements of flexible cork. Although waterborne polyurethane (WPU) has the advantage of property tailorability, its fully applicable to cork materials are still a challenge. Herein, this study utilized a simple physical blending of waterborne polyurethane and nanocellulose with high aspect ratio, to develop a high-strength coating that matches the elastic deformation requirements of cork materials. When both two kinds of nanocellulose, poplar wood nanocellulose (WCNF) with an aspect ratio of 800 and bacterial nanocellulose (BCNF) with an aspect ratio of 2000, was individually added into the WPU emulsion at 0.5 wt%, the tensile strength and elastic modulus of the nanocellulose-modified polyurethane coating increased by 48.58 % and 118.88 %, 54.50 % and 120.48 %, respectively, compared to those of the pure WPU coating (14.09 MPa and 312.74 MPa). It is notable that both the nanocellulose-modified coatings showed no signs of damage on the cork surface even they underwent continuous bending over 2000 cycles, which indicates their excellent flexural fatigue resistance. Interestingly, such nanocellulose-modified coatings maintain comparable transparency, gloss, adhesion, solvent resistance and even present slightly improved hardness and wear resistance than their pure WPU coatings. Overall, the two nanocelluloses are comparative to the modification of the coatings, both of which could match the elastic deformation requirements of cork materials. Therefore, the nanocellulose physically blended polyurethane technology provides a simple and effective solution for the design and property tailoring of flexible coatings for cork floor.
Abstract Nonionic surfactant polysorbates, including PS-80 and PS-20, are commonly used in the formulation of biotherapeutic products for both preventing surface adsorption and acting as stabilizer against protein aggregation. Trace levels of residual host cell proteins (HCPs) with lipase or esterase enzymatic activity have been shown to degrade polysorbates in biologics formulation. The measurement and control of these low abundance, high-risk HCPs for polysorbate degradation are an industry-wide challenge to achieve desired shelf life of biopharmaceuticals in liquid formulation, especially for high-concentration formulation product development. Here, we reviewed the challenges, recent advances, and future opportunities of analytical method development, risk assessment, and control strategies for polysorbate degradation during formulation development with a focus on enzymatic degradation. Continued efforts to advance our understanding of polysorbate degradation in biologics formulation will help develop high-quality medicines for patients.
The introduction of molecular complexity in an atom- and step-efficient manner remains an outstanding goal in modern synthetic chemistry. Artificial biosynthetic pathways are uniquely able to address this challenge by using enzymes to carry out multiple synthetic steps simultaneously or in a one-pot sequence1-3. Conducting biosynthesis ex vivo further broadens its applicability by avoiding cross-talk with cellular metabolism and enabling the redesign of key biosynthetic pathways through the use of non-natural cofactors and synthetic reagents4,5. Here we describe the discovery and construction of an enzymatic cascade to MK-1454, a highly potent stimulator of interferon genes (STING) activator under study as an immuno-oncology therapeutic6,7 (ClinicalTrials.gov study NCT04220866 ). From two non-natural nucleotide monothiophosphates, MK-1454 is assembled diastereoselectively in a one-pot cascade, in which two thiotriphosphate nucleotides are simultaneously generated biocatalytically, followed by coupling and cyclization catalysed by an engineered animal cyclic guanosine-adenosine synthase (cGAS). For the thiotriphosphate synthesis, three kinase enzymes were engineered to develop a non-natural cofactor recycling system in which one thiotriphosphate serves as a cofactor in its own synthesis. This study demonstrates the substantial capacity that currently exists to use biosynthetic approaches to discover and manufacture complex, non-natural molecules.
Host cell proteins (HCPs) are a significant class of process-related impurities commonly associated with the manufacturing of biopharmaceuticals. However, due to the increased use of crude enzymes as biocatalysts for modern organic synthesis, HCPs can also be introduced as a new class of impurities in chemical drugs. In both cases, residual HCPs need to be adequately controlled to ensure product purity, quality, and patient safety. Although a lot of attentions have been focused on defining a universally acceptable limit for such impurities, the risks associated with residual HCPs on product quality, safety, and efficacy often need to be determined on a case-by-case basis taking into consideration the residual HCP profile in the product, the dose, dosage form, administration route, and so forth. Here we describe the unique challenges for residual HCP control presented by the biocatalytic synthesis of an investigational stimulator of interferon genes protein agonist, MK-1454, which is a cyclic dinucleotide synthesized using Escherichia coli cell lysate overexpressing cyclic GMP-AMP synthase as a biocatalyst. In this study, a holistic characterization of residual protein impurities using a variety of analytical tools including nanoscale liquid chromatography coupled to tandem mass spectrometry, together with in silico immunogenicity prediction of identified proteins, facilitated risk assessment and guided process development to achieve adequate removal of residual protein impurities in MK-1454 active pharmaceutical ingredient.