ACS Sustainable Chemistry & Engineering最新文献

{"title":"SNAr Reactions Using Continuous Plug Flow...in Aqueous Biphasic Media","authors":"Madison J. Wong, Kaitlyn M. Freiberg, Trevor Reynafarje Jones, Kylee B. Dismuke Rodriguez, Alex B. Wood, Bruce H. Lipshutz","doi":"10.1021/acssuschemeng.4c08612","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08612","url":null,"abstract":"New plug-flow opportunities for carrying out S_NAr reactions are disclosed using water mixed with the green and separable/recyclable cosolvent 2-MeTHF. This approach enables C–O, C–N, and C–S bond formations. Several features characteristic of this sustainable technology are highlighted, such as recycling of the aqueous reaction medium, applications to several intermediates en route to numerous active pharmaceutical ingredients, and a new “flow-to-batch-to-flow” sequence of reactions demonstrating the possibilities for both time and pot economies to be realized.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"30 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832659","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Injectable and Self-Healing MXene-Reinforced pH-Responsive Hydrogel: Realizing Low-Friction and Durable Lubrication","authors":"Yan Huang, Zhangpeng Li, Yaochen Wang, Qiulong Gao, Kaiming Hou, Shuwen Liu, Jinqing Wang, Shengrong Yang","doi":"10.1021/acssuschemeng.4c07993","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07993","url":null,"abstract":"Hydrogels are ideal lubricants due to their hydrophilicity and ability to mitigate issues such as creep and leakage. Based on the diversity of application environments, it is crucial to develop hydrogels with adjustable lubrication that can adjust their lubrication properties by changing in the external environment. However, they still face challenges in balancing responsiveness, lubrication efficacy, and safety. This study presents a pH-responsive hydrogel prepared from polyvinylpyrrolidone and phytic acid, with the addition of MXene and glycerol to enhance its tribological performance. The optimal contents of MXene and glycerol for peak lubrication efficiency are found to be 5 mg/mL and 5 wt %, respectively. This hydrogel lubricant can maintain a low-friction state without failure in long-term testing for 3 h, achieving a coefficient of friction (COF) of 0.01. The synergistic lubrication effect of MXene and glycerol reached a friction reduction of 69% and a wear resistance improvement of up to 96%. Moreover, the COF can be regulated by adjusting the pH value. This hydrogel also stands out with its robust self-healing, injectability, and biocompatibility, making it an excellent candidate for advanced lubrication in biomedical applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"47 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832718","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modification of Condensed Lignin by Deep Eutectic Solvents: Insight into the Mechanism of Improving the Enzymatic Saccharification","authors":"Tingjun Chen, Xuelian Zhou, Yunni Zhan, Jinyuan Cheng, Caoxing Huang, Chang Geun Yoo, Guigan Fang, Arthur J. Ragauskas, Xianzhi Meng, Chen Huang","doi":"10.1021/acssuschemeng.4c05937","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05937","url":null,"abstract":"Liquid hot water pretreatment (LHWP) can convert hemicellulose in biomass into valuable xylooligosaccharides, but the utilization of glucan in the solid residue after hemicellulose extraction is usually constrained due to the significant lignin condensation during the LHWP. To alleviate lignin’s inhibition on glucan saccharification, this study established a variety of functional deep eutectic solvents (DESs) for the pretreatment of the solid residues after LHWP. The applied DES pretreatments resulted in different glucan saccharification yields. Under the premise of similar lignin removal, the ChCl/ethylene glycol (EG) system obtained near complete glucan digestibility, while the acid or alkali DESs had much lower enzymatic saccharification yields (35.7% and 20.6%). The mechanism of boosting the glucan saccharification by ChCl/EG was comprehensively analyzed by 2D-HSQC NMR, hydrophobicity, GPC and Langmuir adsorption isotherm of enzymes onto the cellulolytic enzyme lignin. Results indicated that lignin remaining in the ChCl/EG pretreated substrates had a lower hydrophobicity (2.8 L/g) and enzyme adsorption (4.6 mg/g), resulting from the EG grafting onto the α-position of the lignin side chain (as high as 5.0/100 Ar). The LHWP-DES pretreatment in this study unveiled the mechanism for cellulose digestibility enhancement using three common DESs and maximized the enzymatic hydrolysis yield, which provided a new scheme for the high-value utilization of biomass.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"22 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832662","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selective Compatibility of High-Entropy Electrolytes for Low-Temperature Aqueous Zinc–Iodine Batteries","authors":"Mengdan Tian, Chuanzheng Zhu, Kun Luo","doi":"10.1021/acssuschemeng.4c06557","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06557","url":null,"abstract":"Aqueous zinc-ion batteries (AZIBs) have attracted massive interest on account of their environmental friendliness, low price, and high security. Nevertheless, the application of AZIBs is seriously constrained by the high liquid–solid transition temperature of aqueous electrolytes, which is strongly related to the water network connected through hydrogen bonds (HBs). Another critical technical issue is to explore the appropriate electrode material compatible with a low-temperature aqueous electrolyte. In order to ensure the battery works properly at low-temperature conditions, a high-entropy electrolyte (HEE) with multicomponent perchlorate salts, (Zn, Ca, Mg, Li)ClO₄, is developed. The calorimetric analysis indicates that the HEE exhibits an extremely low liquid–glass transition temperature (−114 °C). Structural characterizations using Raman, FTIR, and NMR spectroscopy indicate that the introduction of multicomponent perchlorate salts into the aqueous electrolyte breaks the initial water network by the formation of M···(H₂O)_<i>n</i>···ClO₄^– (M is Zn²⁺, Ca²⁺, Mg²⁺ or Li⁺) configurations, and the HEE therefore remains unfrozen even at −70 °C. The in situ viscosity measurement indicates the HEE has a viscosity of 13.8 mPa S at −70 °C. The electrochemical measurements indicate that the ionic conductivity of the HEE is 22.6 mS cm^–1 at 25 °C and 2.7 mS cm^–1 at −70 °C, and it has excellent electrochemical compatibility with Zn metal upon cycling Zn||Zn symmetric cells. The compatibility of the HEE and different electrode materials, particularly vanadate oxide with preinserted cations (KVO) and a carbon composite material with iodine (CCM/I₂) in this study, is systematically investigated, and the results of electrochemical measurements indicate the HEE shows the selectivity of battery systems. The KVO|HEE|Zn battery exhibits poor cycling stability at room temperature (only 33 mA h g^–1 after 5,000 cycles at 5.0 A g^–1), while the CCM-I₂|HEE|Zn battery displays a capacity of 182 mA h g^–1 at 100 mA g^–1 in the first cycle and superior cycling performances (102 mA h g^–1 after 5,000 cycles at 5.0 A g^–1). Low-temperature electrochemical measurements demonstrate that the battery system with the HEE exhibits enhanced electrochemical performances at −70 °C when compared with the binary electrolyte system (Zn, 3Ca)ClO₄. This work reveals the significance of electrode/electrolyte adaptability on the electrochemical performances of AZIBs and provides valuable insights for constructing low-temperature electrolytes using a multicomponent high-entropy strategy.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"39 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electronic Regulation of Pt for Low-Temperature Hydrogen Generation from Methanol and Water","authors":"Qiankang Liao, You Wang, Chen Chen, Sai Zhang","doi":"10.1021/acssuschemeng.4c07671","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07671","url":null,"abstract":"The aqueous-phase reforming of the methanol (APRM) reaction provides a potential approach for hydrogen (H₂) storage and transportation. However, the limited capacity of Pt nanocatalysts for H₂O activation leads to the drawback of requiring high reaction temperatures (&gt;200 °C) to achieve efficient H₂ generation through the APRM reaction. Herein, the electronic density of Pt nanocatalysts has been regulated by the phase of the Al₂O₃ supports. Mechanism analysis revealed that the α-Al₂O₃ supports with larger lattice fringe spacing resulted in an enhanced electronic density of Pt nanocatalysts, thereby enabling the effective adsorption and activation of H₂O. Consequently, the Pt/α-Al₂O₃ catalysts exhibited a TOF value of 69.8 h^–1 at 30 °C for H₂ generation via APRM reaction. Notably, this H₂ generation rate even suppressed that achieved by previous state-of-the-art homogeneous catalysts. This finding presents a promising avenue toward flexible hydrogen utilization.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832665","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Surface-Functionalized PEDOT:PSS Interfaces for Improved Adhesion, Viability, and Extracellular Charge Transfer of Shewanella oneidensis MR-1","authors":"Abdullah, Sara Shakibania, Taral Patel, Divine Yufetar Shyntum, Katarzyna Krukiewicz","doi":"10.1021/acssuschemeng.4c05458","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05458","url":null,"abstract":"<i>Shewanella oneidensis</i> MR-1 is an electroactive bacterium commonly employed in the design of microbial fuel cells (MFCs) due to its ability to convert organic matter to electricity. Its applicability is limited by low adhesion to the surface of the electrode, which decreases the efficiency of charge transfer and reduces the available power outputs. In this study, we aimed to improve the adhesion, viability, and extracellular charge transfer ability of <i>S. oneidensis</i> on the surface of electrodes modified with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), which is a conducting polymer frequently used to enhance the performance of MFCs. PEDOT:PSS-coated glass surface was modified with organic moieties, namely, glucose, sucrose, maltose, cellulose, chitosan, poly(vinyl alcohol), poly-<span>l</span>-lysine, and laminin. The modified surfaces were then analyzed using Fourier-transform infrared spectroscopy, energy dispersive X-ray spectroscopy, electrochemical impedance spectroscopy, scanning electron microscopy, and fluorescence microscopy, and the results demonstrated an overall improvement in their chemical composition, substantial roughness, and moderate wettability. Biofilm formation was found to be significantly improved on PEDOT:PSS surface coated with glucose, resulting in 54.8 ± 1.2% increase in the amount of biomass. LIVE/DEAD analysis indicated a significantly higher percentage of live bacteria (97.5 ± 1.5%) on the PEDOT:PSS surface coated with glucose when compared to bare PEDOT:PSS (42.1 ± 2.1%). The improved adhesion of <i>S. oneidensis</i> on the glucose-functionalized PEDOT:PSS surface resulted in enhanced charge transfer characteristics, leading to significant decrease in charge transfer resistance at the electrode interface. Our approach shows promise in the further development of efficient renewable energy technology for bioelectricity generation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"82 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832660","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Not Cutting Corners: Bioderived Triggers Driving Oxidative Main Chain Scission of Poly(ethylene terephthalate)","authors":"Dhananjay Dileep, Michael J. Forrester, Jack Bonde, Valentina Camelo Vega, Lauren Burton, Ting-Han Lee, Aleksei Ananin, Baker Kuehl, George A. Kraus, Eric W. Cochran","doi":"10.1021/acssuschemeng.4c07021","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07021","url":null,"abstract":"About 20–34 billion poly(ethylene terephthalate) (PET) bottles from the beverage industry leak into aquatic ecosystems annually, necessitating the development of urgent strategies to treat waterborne plastic pollution. Inspired by the scalability of water disinfection infrastructure and protocols, we present a dual depolymerization approach relying on oxidation, followed by hydrolysis. Incorporating bioderived monounsaturated C18 diacid (C18:1-DA) counits at low dosages (2–5%) in the PET backbone overcomes the diffusional limitations of depolymerizing PET in the solid state by suppressing the glass transition temperature of the copolymer by 20 °C. Cryomilled C18:1-PET powder suspended in an oxidant-loaded alkaline slurry underwent bulk depolymerization to oligomers at 80–100 °C via oxidative scissions at the internally located unsaturations. In contrast, conventional PET undergoes only minor end-chain scission under mild alkaline conditions. These oligomers are suitable for low-energy repolymerization or facile solvolysis to monomers. A permanganate-periodate oxidant couple demonstrated successful oxidation through the bulk of the polymer, which subsequently was hydrolyzed to monomers. This model system serves as a proxy for ozonolysis, followed by mild hydrolysis to reduce the energetics of alkaline hydrolysis. This integrated oxidation–hydrolysis strategy paves the way for the industrial adoption of cleaner, advanced oxidation processes, such as ozonolysis for plastic pretreatment, further enabling commercialized chemical recycling of unsaturation-containing polyesters.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"115 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Use of Benzyl Alcohol as a Solvent for Kraft Lignin","authors":"Tejasvi Laxminarayan, Søren Kiil, Narayanan Rajagopalan","doi":"10.1021/acssuschemeng.4c07882","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07882","url":null,"abstract":"Lignin, an abundant and complex aromatic biopolymer, holds significant potential for producing value-added chemicals and materials. However, its utilization is limited by its solubility in common organic solvents. In this study, we investigated the solubility of softwood Kraft lignin in benzyl alcohol and compared it to other traditionally studied solvents. Methanol achieved a lignin solubility yield of 59%, while ethanol (18%) and acetone (34%), due to their longer alkyl chains and lower polarity, were less effective in solubilizing larger lignin fragments. Benzyl alcohol, on the other hand, exhibited a complete dissolution of lignin, thereby exceeding by far the capability of the standard solvents. Furthermore, benzyl alcohol resulted in a moderate molecular weight of 3621 g/mol for the lignin fragments and a narrow polydispersity index of 1.54. The complete solubility of lignin in benzyl alcohol suggests significant potential for high yield lignin fractionation and subsequent chemical modifications, which are essential for valorization. Despite the high boiling point of benzyl alcohol, the enhanced solubility could facilitate the production of homogeneous lignin fractions with increased reactive sites, thereby broadening the scope of lignin applications in coatings and industrial materials.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"77 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832717","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Efficient Cellobiose Hydrolysis over a Sulfonated Carbon Catalyst in a Spatially Separated Microwave Electric- and Magnetic-Field Flow Reactor","authors":"Shuntaro Tsubaki, Kazuaki Senda, Ayumu Onda, Satoshi Fujii","doi":"10.1021/acssuschemeng.4c07690","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07690","url":null,"abstract":"Enhanced polysaccharide hydrolysis is essential for converting polysaccharides into mono- and oligosaccharide sugars for use in food, pharmaceutical, and biobased chemical applications. In this study, we developed an efficient continuous-flow hydrolysis process by applying microwaves and sulfonated carbon catalyst (AC-SO₃H) using cellobiose as a model sugar substrate. We built a microwave flow reactor equipped with a rectangular waveguide and a solid-state microwave generator capable of applying microwaves to a fixed catalyst bed with spatially separated electric (<i>E</i>-) and magnetic (<i>H</i>-) fields and showed that the microwave flow reaction under the <i>E</i>-field improves the glucose formation rate up to 21.7 mmol/g per hour, which is 35.3 times higher than that achieved in the batch microwave reactor. AC-SO₃H showed 16–30 times higher activity than Amberlyst 70 because of the higher dielectric loss tangent (tan δ) value of AC-SO₃H (0.187) than Amberlyst 70 (0.040). <i>H</i>-field heating of AC-SO₃H also improved the glucose formation rate by 1.2–1.6 times. Notably, the <i>H</i>-field reduced the microwave power to 45% of that of the <i>E</i>-field. Therefore, a microwave <i>H</i>-field flow reactor equipped with an AC-SO₃H catalyst greatly improves both the glucose production rate and energy efficiency of cellobiose hydrolysis.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"22 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832716","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Acid/Iodide Cooperative Catalysis for Highly Chemoselective Esterification of Unactivated Tertiary Amides via Electrophilic N−C(O) Activation","authors":"Chenglong Li, Qun Wang, Qihang Tan, Lei Yang, Long Liu, Tianzeng Huang, Michal Szostak, Tieqiao Chen","doi":"10.1021/acssuschemeng.4c07052","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07052","url":null,"abstract":"Due to the n_N-to-π*_C═O conjugation, the direct functionalization of unactivated amides via C−N activation is a longstanding challenge in functional group interconversion involving ubiquitous amide linkages. Herein, we report highly chemoselective esterification of unactivated tertiary amides with various equivalent oxygen nucleophiles, including both aliphatic alcohols and weakly nucleophilic phenols, for the first time. In this reaction, amide C−N bonds are electrophilically activated through cooperative acid/iodide catalysis via the selective formation of a highly reactive acyl iodide species. This powerful strategy enables the use of a stoichiometric quantity of O−H nucleophiles and provides the first general method for converting unactivated <i>N,N</i>-dialkyl amides into the corresponding esters with exquisite chemoselectivity. An exceptionally wide substrate scope of both amides and oxygen nucleophiles is demonstrated with high functional group tolerance, including the late-stage modification of some drugs’ amide derivatives and bioactive O−H nucleophiles (&gt;100 examples). We anticipate that this powerful esterification of amides will find wide application in synthetic organic chemistry.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832664","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}