Marina Corbella, Joe Bravo, Andrey O. Demkiv, Ana Rita Calixto, Kitty Sompiyachoke, Celine Bergonzi, Alfie-Louise R. Brownless, Mikael H. Elias, Shina Caroline Lynn Kamerlin
Several enzymes from the metallo-β-lactamase-like family of lactonases (MLLs) degrade N-acyl L-homoserine lactones (AHLs). They play a role in a microbial communication system known as quorum sensing, which contributes to pathogenicity and biofilm formation. Designing quorum quenching (QQ) enzymes that can interfere with this communication allows them to be used in a range of industrial and biomedical applications. However, tailoring these enzymes for specific communication signals requires a thorough understanding of their mechanisms and the physicochemical properties that determine their substrate specificities. We present here a detailed biochemical, computational, and structural study of GcL, which is a highly proficient and thermostable MLL with broad substrate specificity. We show that GcL not only accepts a broad range of substrates but also hydrolyzes these substrates through at least two different mechanisms. Further, the preferred mechanism appears to depend on both the substrate structure and/or the nature of the residues lining the active site. We demonstrate that other lactonases, such as AiiA and AaL, show similar mechanistic promiscuity, suggesting that this is a shared feature among MLLs. Mechanistic promiscuity has been seen previously in the lactonase/paraoxonase PON1, as well as with protein tyrosine phosphatases that operate via a dual general acid mechanism. The apparent prevalence of this phenomenon is significant from both a biochemical and protein engineering perspective: in addition to optimizing for specific substrates, it may be possible to optimize for specific mechanisms, opening new doors not just for the design of novel quorum quenching enzymes but also of other mechanistically promiscuous enzymes.
{"title":"Catalytic Redundancies and Conformational Plasticity Drives Selectivity and Promiscuity in Quorum Quenching Lactonases","authors":"Marina Corbella, Joe Bravo, Andrey O. Demkiv, Ana Rita Calixto, Kitty Sompiyachoke, Celine Bergonzi, Alfie-Louise R. Brownless, Mikael H. Elias, Shina Caroline Lynn Kamerlin","doi":"10.1021/jacsau.4c00404","DOIUrl":"https://doi.org/10.1021/jacsau.4c00404","url":null,"abstract":"Several enzymes from the metallo-β-lactamase-like family of lactonases (MLLs) degrade <i>N-</i>acyl L-homoserine lactones (AHLs). They play a role in a microbial communication system known as quorum sensing, which contributes to pathogenicity and biofilm formation. Designing quorum quenching (<i>QQ</i>) enzymes that can interfere with this communication allows them to be used in a range of industrial and biomedical applications. However, tailoring these enzymes for specific communication signals requires a thorough understanding of their mechanisms and the physicochemical properties that determine their substrate specificities. We present here a detailed biochemical, computational, and structural study of GcL, which is a highly proficient and thermostable MLL with broad substrate specificity. We show that GcL not only accepts a broad range of substrates but also hydrolyzes these substrates through at least two different mechanisms. Further, the preferred mechanism appears to depend on both the substrate structure and/or the nature of the residues lining the active site. We demonstrate that other lactonases, such as AiiA and AaL, show similar mechanistic promiscuity, suggesting that this is a shared feature among MLLs. Mechanistic promiscuity has been seen previously in the lactonase/paraoxonase PON1, as well as with protein tyrosine phosphatases that operate via a dual general acid mechanism. The apparent prevalence of this phenomenon is significant from both a biochemical and protein engineering perspective: in addition to optimizing for specific substrates, it may be possible to optimize for specific mechanisms, opening new doors not just for the design of novel quorum quenching enzymes but also of other mechanistically promiscuous enzymes.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"2 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The utilization of structure distortion to modulate the electronic structure and alter catalytic properties of metallic nanomaterials is a well-established practice, but accurately identifying and comprehensively understanding these distortions present significant challenges. Ligand-stabilized metal nanoclusters with well-defined structures serve as exemplary model systems to illustrate the structure chemistry of nanomaterials, among which few studies have investigated nanocluster models that incorporate structural distortions. In this work, a novel copper hydride nanocluster, Cu42(PPh3)8(RS)4(CF3COO)10(CH3O)4H10 (Cu42; PPh3 is triphenylphosphine and RSH is 2,4-dichlorophenylthiol), with a highly twisted structure has been synthesized in a simple way. Structural analysis reveals Cu42 comprises two Cu25 units that are conjoined in a nearly orthogonal manner. The dramatic distortion in the metal framework, which is driven by multiple interactions from the surface ligands, endows the cluster with a rich array of uncoordinated metal sites on the surface. The resulting cluster, as envisioned, exhibits remarkable activity in catalyzing carbonylation of anilines. The findings from this study not only provides atomically precise insights into the structural distortions that are pertinent to nanoparticle catalysts but also underscores the potential of structurally distorted NCs as a burgeoning generation of catalysts with precise structures and outstanding performances that can be tailored for specific functions.
{"title":"Structure Distortion Endows Copper Nanoclusters with Surface-Active Uncoordinated Sites for Boosting Catalysis","authors":"Jing Sun, Qingyuan Wu, Xiaodan Yan, Lei Li, Xiongkai Tang, Xuekun Gong, Bingzheng Yan, Qinghua Xu, Qingxiang Guo, Jinlu He, Hui Shen","doi":"10.1021/jacsau.4c00574","DOIUrl":"https://doi.org/10.1021/jacsau.4c00574","url":null,"abstract":"The utilization of structure distortion to modulate the electronic structure and alter catalytic properties of metallic nanomaterials is a well-established practice, but accurately identifying and comprehensively understanding these distortions present significant challenges. Ligand-stabilized metal nanoclusters with well-defined structures serve as exemplary model systems to illustrate the structure chemistry of nanomaterials, among which few studies have investigated nanocluster models that incorporate structural distortions. In this work, a novel copper hydride nanocluster, Cu<sub>42</sub>(PPh<sub>3</sub>)<sub>8</sub>(RS)<sub>4</sub>(CF<sub>3</sub>COO)<sub>10</sub>(CH<sub>3</sub>O)<sub>4</sub>H<sub>10</sub> (Cu<sub>42</sub>; PPh<sub>3</sub> is triphenylphosphine and RSH is 2,4-dichlorophenylthiol), with a highly twisted structure has been synthesized in a simple way. Structural analysis reveals Cu<sub>42</sub> comprises two Cu<sub>25</sub> units that are conjoined in a nearly orthogonal manner. The dramatic distortion in the metal framework, which is driven by multiple interactions from the surface ligands, endows the cluster with a rich array of uncoordinated metal sites on the surface. The resulting cluster, as envisioned, exhibits remarkable activity in catalyzing carbonylation of anilines. The findings from this study not only provides atomically precise insights into the structural distortions that are pertinent to nanoparticle catalysts but also underscores the potential of structurally distorted NCs as a burgeoning generation of catalysts with precise structures and outstanding performances that can be tailored for specific functions.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"10 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226852","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An electrochemically mediated enzyme process for nicotinamide adenine dinucleotide (NADH) oxidation and biosensing has been developed in which the oxygen-dependent activities of wild-type NADH oxidase are replaced by electrochemical regeneration of the flavin adenine dinucleotide (FAD) cofactor in the active site. Consequently, the present bioelectrocatalysis does not rely on a continuous oxygen supply through bubbling air or pure oxygen in biosynthetic applications, which reduces enzyme stability. The coupled electrochemical and enzymatic catalysis is achieved through a combination of enzyme immobilization on the electrode and electrochemical oxidation of FADH2 in the active site mediated by the electron transfer mediator ferrocene carboxylic acid (FcCA). Furthermore, to minimize the effect of dissolved oxygen when the electrocatalytic process is exposed to air, we successfully designed mutations at the Leu40 and Cys42 sites of Leuconostoc mesenteroides (LmNOx) to block the oxygen passage into the active site and to eliminate the native FAD cofactor regeneration half-reaction. The engineered enzymes, whose activities are significantly reduced or inactive in solution, are electrocatalytically active toward conversion of NADH to NAD+, demonstrating successful FAD cofactor regeneration in the active site via electrochemistry. Finally, we developed two highly responsive electrochemical biosensors for NADH detection which has a superior substrate specific to standard detectors using metal electrodes, and comparable detection range and detection limit (1–3 μM).
{"title":"Engineering Oxygen-Independent NADH Oxidase Integrated with Electrocatalytic FAD Cofactor Regeneration","authors":"Mengjie Hou, Jing Yuan, Xinyu Dong, Yingjie Wang, Shihe Yang, Jiali Gao","doi":"10.1021/jacsau.4c00528","DOIUrl":"https://doi.org/10.1021/jacsau.4c00528","url":null,"abstract":"An electrochemically mediated enzyme process for nicotinamide adenine dinucleotide (NADH) oxidation and biosensing has been developed in which the oxygen-dependent activities of wild-type NADH oxidase are replaced by electrochemical regeneration of the flavin adenine dinucleotide (FAD) cofactor in the active site. Consequently, the present bioelectrocatalysis does not rely on a continuous oxygen supply through bubbling air or pure oxygen in biosynthetic applications, which reduces enzyme stability. The coupled electrochemical and enzymatic catalysis is achieved through a combination of enzyme immobilization on the electrode and electrochemical oxidation of FADH<sub>2</sub> in the active site mediated by the electron transfer mediator ferrocene carboxylic acid (FcCA). Furthermore, to minimize the effect of dissolved oxygen when the electrocatalytic process is exposed to air, we successfully designed mutations at the Leu40 and Cys42 sites of <i>Leuconostoc mesenteroides</i> (<i>Lm</i>NOx) to block the oxygen passage into the active site and to eliminate the native FAD cofactor regeneration half-reaction. The engineered enzymes, whose activities are significantly reduced or inactive in solution, are electrocatalytically active toward conversion of NADH to NAD<sup>+</sup>, demonstrating successful FAD cofactor regeneration in the active site via electrochemistry. Finally, we developed two highly responsive electrochemical biosensors for NADH detection which has a superior substrate specific to standard detectors using metal electrodes, and comparable detection range and detection limit (1–3 μM).","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"6 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Saidbakhrom Saidjalolov, Xiao-Xiao Chen, Julia Moreno, Michael Cognet, Luis Wong-Dilworth, Francesca Bottanelli, Naomi Sakai, Stefan Matile
Thiol-mediated uptake (TMU) is thought to occur through dynamic covalent cascade exchange networks. Here we show that the cascade accounting for TMU of asparagusic acid derivatives (AspA) ends in the Golgi apparatus (G) and shifts from disulfide to thioester exchange with palmitoyl transferases as the final exchange partner. As a result, AspA combined with pH-sensitive fluoresceins, red-shifted silicon-rhodamines, or mechanosensitive flipper probes selectively labels the Golgi apparatus in fluorescence microscopy images in living and fixed cells. AspA Golgi trackers work without cellular engineering and excel with speed, simplicity, generality, and compatibility with G/ER and cis/trans discrimination, morphological changes, anterograde vesicular trafficking, and superresolution imaging by stimulated emission depletion microscopy. Golgi flippers in particular can image membrane order and tension in the Golgi and, if desired, at the plasma membrane during TMU.
{"title":"Asparagusic Golgi Trackers","authors":"Saidbakhrom Saidjalolov, Xiao-Xiao Chen, Julia Moreno, Michael Cognet, Luis Wong-Dilworth, Francesca Bottanelli, Naomi Sakai, Stefan Matile","doi":"10.1021/jacsau.4c00487","DOIUrl":"https://doi.org/10.1021/jacsau.4c00487","url":null,"abstract":"Thiol-mediated uptake (TMU) is thought to occur through dynamic covalent cascade exchange networks. Here we show that the cascade accounting for TMU of asparagusic acid derivatives (AspA) ends in the Golgi apparatus (G) and shifts from disulfide to thioester exchange with palmitoyl transferases as the final exchange partner. As a result, AspA combined with pH-sensitive fluoresceins, red-shifted silicon-rhodamines, or mechanosensitive flipper probes selectively labels the Golgi apparatus in fluorescence microscopy images in living and fixed cells. AspA Golgi trackers work without cellular engineering and excel with speed, simplicity, generality, and compatibility with G/ER and cis/trans discrimination, morphological changes, anterograde vesicular trafficking, and superresolution imaging by stimulated emission depletion microscopy. Golgi flippers in particular can image membrane order and tension in the Golgi and, if desired, at the plasma membrane during TMU.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"5 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Waygen Thor, Hei-Yui Kai, Yik-Hoi Yeung, Yue Wu, Tsz-Lam Cheung, Leo K. B. Tam, Yonghong Zhang, Loïc J. Charbonnière, Peter A. Tanner, Ka-Leung Wong
The conventional energy transfer pathway in organic lanthanide complexes is purported to be from the excited singlet state of the chromophore to the triplet state and subsequently directly to the emitting state of the trivalent lanthanide ion. In this work, we found that the energy transfer occurs from the triplet state to the nearest energy level, instead of directly to the emitting state of the lanthanide ion. The triplet decay rate for different lanthanide ions follows an energy gap law from the triplet level to the receiving level of the lanthanide ion. Three different categories of complexes were synthesized and inspected using different techniques, demonstrating the universality of our findings. This work renews the insights to conventional findings, highlighting the importance of the energy gap between the triplet state and the nearest lanthanide energy level in optimization of light harvesting. The rationale of ligand design of chromophores should be reconsidered, leading to various applications of lanthanide complexes with enhanced quantum yield and brightness.
{"title":"Unearthing the Real-Time Excited State Dynamics from Antenna to Rare Earth Ions Using Ultrafast Transient Absorption","authors":"Waygen Thor, Hei-Yui Kai, Yik-Hoi Yeung, Yue Wu, Tsz-Lam Cheung, Leo K. B. Tam, Yonghong Zhang, Loïc J. Charbonnière, Peter A. Tanner, Ka-Leung Wong","doi":"10.1021/jacsau.4c00468","DOIUrl":"https://doi.org/10.1021/jacsau.4c00468","url":null,"abstract":"The conventional energy transfer pathway in organic lanthanide complexes is purported to be from the excited singlet state of the chromophore to the triplet state and subsequently directly to the emitting state of the trivalent lanthanide ion. In this work, we found that the energy transfer occurs from the triplet state to the nearest energy level, instead of directly to the emitting state of the lanthanide ion. The triplet decay rate for different lanthanide ions follows an energy gap law from the triplet level to the receiving level of the lanthanide ion. Three different categories of complexes were synthesized and inspected using different techniques, demonstrating the universality of our findings. This work renews the insights to conventional findings, highlighting the importance of the energy gap between the triplet state and the nearest lanthanide energy level in optimization of light harvesting. The rationale of ligand design of chromophores should be reconsidered, leading to various applications of lanthanide complexes with enhanced quantum yield and brightness.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"59 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214400","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Iakovos Saridakis, Immo Klose, Benjamin T. Jones, Nuno Maulide
Hydride shuttle catalysis has emerged as a powerful synthetic platform, enabling the selective formation of C–C bonds to yield sp3-rich structures. By virtue of the compelling reactivity of sterically encumbered Lewis acids from the frustrated Lewis pair regime, hydride shuttle catalysis enables the regioselective functionalization of alkyl amines at either the α- or β-position. In contrast to classical Lewis acid reactivity, the increased steric hindrance prevents interaction with the Lewis basic amine itself, instead leading to reversible abstraction of a hydride from the amine α-carbon. The created positive charge facilitates the occurrence of transformations before hydride rebound or a similar capture event happen. In this Perspective, we outline a broad selection of transformations featuring hydride shuttle catalysis, as well as the recently developed approach of inverse hydride shuttle catalysis. Both strategies give rise to a wide array of functionalized amines and offer elegant approaches to otherwise elusive bond formations.
{"title":"Hydride Shuttle Catalysis: From Conventional to Inverse Mode","authors":"Iakovos Saridakis, Immo Klose, Benjamin T. Jones, Nuno Maulide","doi":"10.1021/jacsau.4c00532","DOIUrl":"https://doi.org/10.1021/jacsau.4c00532","url":null,"abstract":"Hydride shuttle catalysis has emerged as a powerful synthetic platform, enabling the selective formation of C–C bonds to yield sp<sup>3</sup>-rich structures. By virtue of the compelling reactivity of sterically encumbered Lewis acids from the frustrated Lewis pair regime, hydride shuttle catalysis enables the regioselective functionalization of alkyl amines at either the α- or β-position. In contrast to classical Lewis acid reactivity, the increased steric hindrance prevents interaction with the Lewis basic amine itself, instead leading to reversible abstraction of a hydride from the amine α-carbon. The created positive charge facilitates the occurrence of transformations before hydride rebound or a similar capture event happen. In this Perspective, we outline a broad selection of transformations featuring hydride shuttle catalysis, as well as the recently developed approach of <i>inverse</i> hydride shuttle catalysis. Both strategies give rise to a wide array of functionalized amines and offer elegant approaches to otherwise elusive bond formations.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"180 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214401","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mohamed Gamal Mohamed, Chia-Chi Chen, Mervat Ibrahim, Aya Osama Mousa, Mohamed Hammad Elsayed, Yunsheng Ye, Shiao-Wei Kuo
Conjugated microporous polymers (CMPs) feature extended excellent porosity properties and fully conjugated electronic systems, making them highly effective for several uses, including photocatalysis, dye adsorption, CO2 capture, supercapacitors, and so on. These polymers are known for their high specific surface area and adjustable porosity. To synthesize DHTP-CMPs (specifically TPE-DHTP CMP and Anthra-DHTP CMP) with abundant nitrogen (N) and oxygen (O) adsorption sites and spherical structures, we employed a straightforward Schiff-base [4 + 2] condensation reaction. This involved using 2,5-dihydroxyterephthalaldehyde (DHTP-2CHO) as the primary building block and phenolic OH group source, along with two distinct structures: 4,4′,4″,4”’-(ethene-1,1,2,2-tetrayl)tetraaniline (TPE-4NH2) and 4,4′,4″,4”’-(anthracene-9,10-diylidenebis(methanediylylidene))tetraaniline (Anthra-4Ph-4NH2). The synthesized Anthra-DHTP CMP had a remarkable BET surface area (BETSA) of 431 m2 g–1. Additionally, it exhibited outstanding thermal stability, as shown by a Td10 of 505 °C. Furthermore, for practical implementation, the Anthra-DHTP CMP demonstrates a significant capacity for capturing CO2, measuring 1.85 mmol g–1 at a temperature of 273 K and 1 bar. In a three-electrode test, the Anthra-DHTP CMP has a remarkable specific capacitance of 121 F g–1 at 0.5 A g–1. Furthermore, even after undergoing 5000 cycles, it maintains a capacitance retention rate of 79%. Due to their outstanding pore characteristics, abundant N and O, and conjugation properties, this Anthtra-DHTP CMP holds significant potential for CO2 capture and supercapacitor applications. This work will pave the way for the development of materials based on DHTP-CMPs and their postmodification with additional groups, facilitating their use in photocatalysis, photodegradation, lithium battery applications, and so on.
共轭微孔聚合物（CMPs）具有扩展的优异孔隙率特性和完全共轭的电子系统，因此在光催化、染料吸附、二氧化碳捕获、超级电容器等多种用途上都非常有效。这些聚合物以高比表面积和可调孔隙率著称。为了合成具有大量氮（N）和氧（O）吸附位点和球形结构的 DHTP-CMP（特别是 TPE-DHTP CMP 和 Anthra-DHTP CMP），我们采用了一种简单的席夫碱 [4 + 2] 缩合反应。该反应以 2,5-二羟基对苯二甲醛（DHTP-2CHO）为主要结构单元和酚羟基来源，并具有两种不同的结构：4,4′,4″,4"'-(ethene-1,1,2,2-tetrayl)tetraaniline (TPE-4NH2) 和 4,4′,4″,4"'-(anthracene-9,10-diylidenebis(methanediylylidene))tetraaniline (Anthra-4Ph-4NH2) 两种不同的结构。合成的 Anthra-DHTP CMP 具有显著的 BET 表面积（BETSA），达到 431 m2 g-1。此外，它还具有出色的热稳定性，Td10 为 505 ℃。此外，在实际应用中，Anthra-DHTP CMP 还具有显著的二氧化碳捕获能力，在温度为 273 K、压力为 1 bar 时，捕获量为 1.85 mmol g-1。在三电极测试中，Anthra-DHTP CMP 在 0.5 A g-1 时的比电容高达 121 F g-1。此外，即使在经历 5000 次循环后，其电容保持率仍高达 79%。由于其出色的孔隙特征、丰富的 N 和 O 以及共轭特性，这种 Anthtra-DHTP CMP 在二氧化碳捕获和超级电容器应用方面具有巨大潜力。这项工作将为开发基于 DHTP-CMP 的材料及其与其他基团的后修饰铺平道路，从而促进其在光催化、光降解、锂电池应用等方面的应用。
{"title":"Tetraphenylanthraquinone and Dihydroxybenzene-Tethered Conjugated Microporous Polymer for Enhanced CO2 Uptake and Supercapacitive Energy Storage","authors":"Mohamed Gamal Mohamed, Chia-Chi Chen, Mervat Ibrahim, Aya Osama Mousa, Mohamed Hammad Elsayed, Yunsheng Ye, Shiao-Wei Kuo","doi":"10.1021/jacsau.4c00537","DOIUrl":"https://doi.org/10.1021/jacsau.4c00537","url":null,"abstract":"Conjugated microporous polymers (CMPs) feature extended excellent porosity properties and fully conjugated electronic systems, making them highly effective for several uses, including photocatalysis, dye adsorption, CO<sub>2</sub> capture, supercapacitors, and so on. These polymers are known for their high specific surface area and adjustable porosity. To synthesize DHTP-CMPs (specifically TPE-DHTP CMP and Anthra-DHTP CMP) with abundant nitrogen (N) and oxygen (O) adsorption sites and spherical structures, we employed a straightforward Schiff-base [4 + 2] condensation reaction. This involved using 2,5-dihydroxyterephthalaldehyde (DHTP-2CHO) as the primary building block and phenolic OH group source, along with two distinct structures: 4,4′,4″,4”’-(ethene-1,1,2,2-tetrayl)tetraaniline (TPE-4NH<sub>2</sub>) and 4,4′,4″,4”’-(anthracene-9,10-diylidenebis(methanediylylidene))tetraaniline (Anthra-4Ph-4NH<sub>2</sub>). The synthesized Anthra-DHTP CMP had a remarkable BET surface area (BET<sub>SA</sub>) of 431 m<sup>2</sup> g<sup>–1</sup>. Additionally, it exhibited outstanding thermal stability, as shown by a <i>T</i><sub>d10</sub> of 505 °C. Furthermore, for practical implementation, the Anthra-DHTP CMP demonstrates a significant capacity for capturing CO<sub>2</sub>, measuring 1.85 mmol g<sup>–1</sup> at a temperature of 273 K and 1 bar. In a three-electrode test, the Anthra-DHTP CMP has a remarkable specific capacitance of 121 F g<sup>–1</sup> at 0.5 A g<sup>–1</sup>. Furthermore, even after undergoing 5000 cycles, it maintains a capacitance retention rate of 79%. Due to their outstanding pore characteristics, abundant N and O, and conjugation properties, this Anthtra-DHTP CMP holds significant potential for CO<sub>2</sub> capture and supercapacitor applications. This work will pave the way for the development of materials based on DHTP-CMPs and their postmodification with additional groups, facilitating their use in photocatalysis, photodegradation, lithium battery applications, and so on.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"108 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214402","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Molecular doping plays a crucial role in modulating the performance of polymeric semiconductor (PSC) materials and devices. Despite the development of numerous molecular dopants and doping methods over the past few decades, achieving highly efficient doping of PSCs remains challenging, primarily because of the inadequate matching of frontier energy levels between the host polymers and the dopants, which is critical for facilitating charge transfer. In this work, we introduce a novel doping method termed photoexcitation-assisted molecular doping (PE-MD), capable of transcending limitations imposed by energy level disparities through the mediation of efficient photoinduced electron transfer between polymers and dopants. This approach significantly amplifies the electrical conductivity of the PDPP4T polymer, increasing it by more than 4 orders of magnitude to a maximum value of 349.67 S cm–1. Given that only the irradiated region experiences a substantial increase in doping level, the PE-MD process facilitates the photoresist-free and precise patterning of doped polymers at a resolution down to 1 μm. Furthermore, the enhanced electrical conductivity of the photoexcitation-assisted molecularly doped PDPP4T film promotes efficient thermoelectric conversion, yielding an impressive initial power factor of 226.1 μW m–1 K–2 and a figure-of-merit (ZT) of 0.18, accompanied by improved thermal and ambient stability. The PE-MD strategy not only remarkably elevates the doping level of PSCs toward efficient thermoelectric conversion but also preserves the easy processability of flexible and integrated devices.
{"title":"Photoexcitation-Assisted Molecular Doping for High-Performance Polymeric Thermoelectric Materials","authors":"Zhen Ji, Zhiyi Li, Xiaojuan Dai, Lanyi Xiang, Yue Zhao, Dongyang Wang, Xiao Zhang, Liyao Liu, Zhiyuan Han, Lixin Niu, Yuqiu Di, Ye Zou, Chong-an Di, Daoben Zhu","doi":"10.1021/jacsau.4c00567","DOIUrl":"https://doi.org/10.1021/jacsau.4c00567","url":null,"abstract":"Molecular doping plays a crucial role in modulating the performance of polymeric semiconductor (PSC) materials and devices. Despite the development of numerous molecular dopants and doping methods over the past few decades, achieving highly efficient doping of PSCs remains challenging, primarily because of the inadequate matching of frontier energy levels between the host polymers and the dopants, which is critical for facilitating charge transfer. In this work, we introduce a novel doping method termed photoexcitation-assisted molecular doping (PE-MD), capable of transcending limitations imposed by energy level disparities through the mediation of efficient photoinduced electron transfer between polymers and dopants. This approach significantly amplifies the electrical conductivity of the PDPP4T polymer, increasing it by more than 4 orders of magnitude to a maximum value of 349.67 S cm<sup>–1</sup>. Given that only the irradiated region experiences a substantial increase in doping level, the PE-MD process facilitates the photoresist-free and precise patterning of doped polymers at a resolution down to 1 μm. Furthermore, the enhanced electrical conductivity of the photoexcitation-assisted molecularly doped PDPP4T film promotes efficient thermoelectric conversion, yielding an impressive initial power factor of 226.1 μW m<sup>–1</sup> K<sup>–2</sup> and a figure-of-merit (<i>ZT</i>) of 0.18, accompanied by improved thermal and ambient stability. The PE-MD strategy not only remarkably elevates the doping level of PSCs toward efficient thermoelectric conversion but also preserves the easy processability of flexible and integrated devices.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"78 1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142214419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yizhen Wang, Zihan Lin, Runhai Ouyang, Bin Jiang, Igor Ying Zhang, Xin Xu
Accurate description of the static correlation poses a persistent challenge in electronic structure theory, particularly when it has to be concurrently considered with the dynamic correlation. We develop here a method in the generalized Kohn–Sham density functional theory (DFT) framework, named R-xDH7-SCC15, which achieves an unprecedented accuracy in capturing the static correlation, while maintaining a good description of the dynamic correlation on par with the state-of-the-art DFT and wave function theory methods, all grounded in the same single-reference black-box methodology. Central to R-xDH7-SCC15 is a general-purpose static correlation correction (SCC) model applied to the renormalized XYG3-type doubly hybrid method (R-xDH7). The SCC model development involves a hybrid machine learning strategy that integrates symbolic regression with nonlinear parameter optimization, aiming to achieve a balance between generalization capability, numerical accuracy, and interpretability. Extensive benchmark studies confirm the robustness and broad applicability of R-xDH7-SCC15 across a diverse array of main-group chemical scenarios. Notably, it displays exceptional aptitude in accurately characterizing intricate reaction kinetics and dynamic processes in regions distant from equilibrium, where the influence of static correlation is most profound. Its capability to consistently and efficiently predict the whole energy profiles, activation barriers, and reaction pathways within a user-friendly “black-box” framework represents an important advance in the field of electronic structure theory.
{"title":"Toward Efficient and Unified Treatment of Static and Dynamic Correlations in Generalized Kohn–Sham Density Functional Theory","authors":"Yizhen Wang, Zihan Lin, Runhai Ouyang, Bin Jiang, Igor Ying Zhang, Xin Xu","doi":"10.1021/jacsau.4c00488","DOIUrl":"https://doi.org/10.1021/jacsau.4c00488","url":null,"abstract":"Accurate description of the static correlation poses a persistent challenge in electronic structure theory, particularly when it has to be concurrently considered with the dynamic correlation. We develop here a method in the generalized Kohn–Sham density functional theory (DFT) framework, named R-xDH7-SCC15, which achieves an unprecedented accuracy in capturing the static correlation, while maintaining a good description of the dynamic correlation on par with the state-of-the-art DFT and wave function theory methods, all grounded in the same single-reference black-box methodology. Central to R-xDH7-SCC15 is a general-purpose static correlation correction (SCC) model applied to the renormalized XYG3-type doubly hybrid method (R-xDH7). The SCC model development involves a hybrid machine learning strategy that integrates symbolic regression with nonlinear parameter optimization, aiming to achieve a balance between generalization capability, numerical accuracy, and interpretability. Extensive benchmark studies confirm the robustness and broad applicability of R-xDH7-SCC15 across a diverse array of main-group chemical scenarios. Notably, it displays exceptional aptitude in accurately characterizing intricate reaction kinetics and dynamic processes in regions distant from equilibrium, where the influence of static correlation is most profound. Its capability to consistently and efficiently predict the whole energy profiles, activation barriers, and reaction pathways within a user-friendly “black-box” framework represents an important advance in the field of electronic structure theory.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"20 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141969510","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this study, we present the first example of using a machine learning (ML)-assisted design strategy to optimize the synthesis formulation of enzyme/ZIFs (zeolitic imidazolate framework) for enhanced performance. Glucose oxidase (GOx) and horseradish peroxidase (HRP) were chosen as model enzymes, while Zn(eIM)2 (eIM = 2-ethylimidazolate) was selected as the model ZIF to test our ML-assisted workflow paradigm. Through an iterative ML-driven training-design-synthesis-measurement workflow, we efficiently discovered GOx/ZIF (G151) and HRP/ZIF (H150) with their overall performance index (OPI) values (OPI represents the product of encapsulation efficiency (E in %), retained enzymatic activity (A in %), and thermal stability (T in %)) at least 1.3 times higher than those in systematic seed data studies. Furthermore, advanced statistical methods derived from the trained random forest model qualitatively and quantitatively reveal the relationship among synthesis, structure, and performance in the enzyme/ZIF system, offering valuable guidance for future studies on enzyme/ZIFs. Overall, our proposed ML-assisted design strategy holds promise for accelerating the development of enzyme/ZIFs and other enzyme immobilization systems for biocatalysis applications and beyond, including drug delivery and sensing, among others.
在本研究中，我们首次举例说明了如何利用机器学习（ML）辅助设计策略来优化酶/ZIF（唑基咪唑酸框架）的合成配方，以提高其性能。葡萄糖氧化酶（GOx）和辣根过氧化物酶（HRP）被选为模型酶，而 Zn(eIM)2（eIM = 2-乙基咪唑酸盐）被选为模型 ZIF，以测试我们的 ML 辅助工作流程范例。通过迭代式 ML 驱动的 "训练-设计-合成-测量 "工作流程，我们高效地发现了 GOx/ZIF (G151) 和 HRP/ZIF (H150)，其总体性能指数（OPI）值（OPI 表示封装效率（E，单位 %）、保留酶活性（A，单位 %）和热稳定性（T，单位 %）的乘积）至少是系统种子数据研究的 1.3 倍。此外，从训练有素的随机森林模型中得出的先进统计方法定性和定量地揭示了酶/ZIF 系统中合成、结构和性能之间的关系，为今后的酶/ZIF 研究提供了宝贵的指导。总之，我们提出的 ML 辅助设计策略有望加速酶/ZIF 及其他酶固定化系统的开发，使其应用于生物催化及其他领域，包括药物输送和传感等。
{"title":"Machine Learning Optimizing Enzyme/ZIF Biocomposites for Enhanced Encapsulation Efficiency and Bioactivity","authors":"Weibin Liang, Sisi Zheng, Ying Shu, Jun Huang","doi":"10.1021/jacsau.4c00485","DOIUrl":"https://doi.org/10.1021/jacsau.4c00485","url":null,"abstract":"In this study, we present the first example of using a machine learning (ML)-assisted design strategy to optimize the synthesis formulation of enzyme/ZIFs (zeolitic imidazolate framework) for enhanced performance. Glucose oxidase (GOx) and horseradish peroxidase (HRP) were chosen as model enzymes, while Zn(eIM)<sub>2</sub> (eIM = 2-ethylimidazolate) was selected as the model ZIF to test our ML-assisted workflow paradigm. Through an iterative ML-driven training-design-synthesis-measurement workflow, we efficiently discovered GOx/ZIF (G151) and HRP/ZIF (H150) with their overall performance index (OPI) values (OPI represents the product of encapsulation efficiency (<i>E</i> in %), retained enzymatic activity (<i>A</i> in %), and thermal stability (<i>T</i> in %)) at least 1.3 times higher than those in systematic seed data studies. Furthermore, advanced statistical methods derived from the trained random forest model qualitatively and quantitatively reveal the relationship among synthesis, structure, and performance in the enzyme/ZIF system, offering valuable guidance for future studies on enzyme/ZIFs. Overall, our proposed ML-assisted design strategy holds promise for accelerating the development of enzyme/ZIFs and other enzyme immobilization systems for biocatalysis applications and beyond, including drug delivery and sensing, among others.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"31 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141946203","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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