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Back Cover: Lysine aggregates-based nanostructured antimicrobial peptides for cariogenic biofilm microenvironment-activated caries treatment 封底:基于赖氨酸聚合体的纳米结构抗菌肽用于致龋生物膜微环境激活型龋病治疗
IF 13.9 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-20 DOI: 10.1002/agt2.684
Siyuan Li, Feng Wang, Yang Chen, Wanrui Shi, Dashuai Liu, Mingyang Lv, Bin Zhao, Yi Liu, Hao Zhang

Aggregated lysine mimics antimicrobial peptides (AMPs) by disrupting bacterial membranes, interfering with metabolism, and inhibiting protein synthesis. With Fe3+ hydrolysis, lysine coordination, and ultrasmall Au nanoparticle deposition, FeOOH@Fe-Lysine@Au shows AMP-like antibacterial activity and reactive oxygen species generation, providing an effective approach for cariogenic biofilm microenvironment-activated caries treatment (e578).

聚合赖氨酸通过破坏细菌膜、干扰新陈代谢和抑制蛋白质合成来模拟抗菌肽(AMPs)。通过 Fe3+ 水解、赖氨酸配位和超小金纳米粒子沉积,FeOOH@Fe-赖氨酸@金显示出类似于 AMP 的抗菌活性和活性氧生成,为龋病生物膜微环境激活型龋病治疗提供了一种有效的方法 (e578)。
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引用次数: 0
Inside Front Cover: Stimuli-responsive photoluminescent copper(I) halides for scintillation, anticounterfeiting, and light-emitting diode applications 封面内页:用于闪烁、防伪和发光二极管的刺激响应型光致发光铜(I)卤化物
IF 13.9 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-20 DOI: 10.1002/agt2.682
Dilruba A. Popy, Yashpal Singh, Yauhen Tratsiak, Abby M. Cardoza, John M. Lane, Luis Stand, Mariya Zhuravleva, Neeraj Rai, Bayram Saparov

Near unity photoluminescence efficiency has been achieved in green emitting (TEP)2Cu2Br4 and orange emitting (TEP)2Cu4Br6. In both cases, emission originates from self-trapped excitons localized on the copper(I) halide structural units. The sensitivity of these compounds to the external stimuli coupled with their ultrabright emission allows their consideration for applications such as solid-state lighting, scintillation, sensing, information storage, and anticounterfeiting (e602).

绿色发光的 (TEP)2Cu2Br4 和橙色发光的 (TEP)2Cu4Br6 的光致发光效率已接近统一。在这两种情况下,发射都源于卤化铜(I)结构单元上定位的自俘获激子。这些化合物对外部刺激的敏感性及其超亮的发射使它们可以被考虑用于固态照明、闪烁、传感、信息存储和防伪等领域 (e602)。
{"title":"Inside Front Cover: Stimuli-responsive photoluminescent copper(I) halides for scintillation, anticounterfeiting, and light-emitting diode applications","authors":"Dilruba A. Popy,&nbsp;Yashpal Singh,&nbsp;Yauhen Tratsiak,&nbsp;Abby M. Cardoza,&nbsp;John M. Lane,&nbsp;Luis Stand,&nbsp;Mariya Zhuravleva,&nbsp;Neeraj Rai,&nbsp;Bayram Saparov","doi":"10.1002/agt2.682","DOIUrl":"https://doi.org/10.1002/agt2.682","url":null,"abstract":"<p>Near unity photoluminescence efficiency has been achieved in green emitting (TEP)<sub>2</sub>Cu<sub>2</sub>Br<sub>4</sub> and orange emitting (TEP)<sub>2</sub>Cu<sub>4</sub>Br<sub>6</sub>. In both cases, emission originates from self-trapped excitons localized on the copper(I) halide structural units. The sensitivity of these compounds to the external stimuli coupled with their ultrabright emission allows their consideration for applications such as solid-state lighting, scintillation, sensing, information storage, and anticounterfeiting (e602).\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":"5 5","pages":""},"PeriodicalIF":13.9,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.682","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142540834","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Inside Back Cover: Supramolecular self-assembled nanoparticles for targeted therapy of myocardial infarction by enhancing cardiomyocyte mitophagy 封底内页超分子自组装纳米粒子通过增强心肌细胞有丝分裂靶向治疗心肌梗死
IF 13.9 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-20 DOI: 10.1002/agt2.683
Yang Jiao, Haimang Wang, Xiechuan Weng, Jihang Wang, Ying Li, Jian Shen, Weiwei Zhao, Qing Xi, Hongyu Zhang, Zhenhong Fu

In this study, supramolecular self-assembled nanoparticles were developed with multi-functional properties of macrophage escape, cardiac targeting, and drug release for the treatment of myocardial infarction. The nanoparticles reduced cardiomyocyte apoptosis, alleviated myocardial interstitial fibrosis, and enhanced cardiac function based on the mechanism of the enhancement in mitophagy and alleviation in mitochondrial damage (e563).

本研究开发了具有巨噬细胞逃逸、心脏靶向和药物释放等多功能特性的超分子自组装纳米粒子,用于治疗心肌梗死。该纳米粒子可减少心肌细胞凋亡,减轻心肌间质纤维化,并基于增强有丝分裂和减轻线粒体损伤的机制增强心脏功能(e563)。
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引用次数: 0
Constructing benzothiadiazole-based donor‒acceptor covalent organic frameworks for efficient photocatalytic H2 evolution
IF 13.9 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-03 DOI: 10.1002/agt2.669
Yanchang Huang, Bin Gao, Qihang Huang, De-Li Ma, Hongwei Wu, Cheng Qian

Donor‒acceptor covalent organic frameworks (D‒A COFs) have been regarded as promising materials for photocatalytic water splitting because of their tunable band gaps. However, their efficiency is hindered by fast charge recombination and low photostability. Herein, we proposed a donor structural engineering strategy for improving the photocatalytic activity of D‒A COFs to tackle these problems. Two benzothiadiazole-based D‒A COFs (DHU-COF-BB and DHU-COF-BP) with distinct donors were prepared for photocatalytic H2 evolution reaction (HER). As a comparison, DHU-COF-TB without benzothiadiazole moieties was also designed and synthesized. Impressively, the photocatalytic H2 production rate of DHU-COF-BB reaches 12.80 mmol g−1 h−1 under visible light irradiation (≥420 nm), which was nearly 2.0 and 3.1 times higher than that of DHU-COF-BP (6.47 mmol g−1 h−1) and DHU-COF-TB (4.06 mmol g−1 h−1), respectively. In addition, the apparent quantum efficiency (AQE) of DHU-COF-BB was up to 5.04% at 420 nm. Photocatalytic and electrochemical measurements indicate that the enhanced hydrogen evolution activity of DHU-COF-BB can be ascribed to the introduction of appropriate benzene moiety into the donors, which increases the charge separation efficiency and thereby suppresses the electron‒hole recombination. Density functional theory (DFT) calculations revealed that both triphenylamine and benzothiadiazole units are the main active sites for HER over the DHU-COF-BB. This work provides new insight into the photocatalytic hydrogen production activity of D‒A COFs by a donor structural engineering strategy.

{"title":"Constructing benzothiadiazole-based donor‒acceptor covalent organic frameworks for efficient photocatalytic H2 evolution","authors":"Yanchang Huang,&nbsp;Bin Gao,&nbsp;Qihang Huang,&nbsp;De-Li Ma,&nbsp;Hongwei Wu,&nbsp;Cheng Qian","doi":"10.1002/agt2.669","DOIUrl":"https://doi.org/10.1002/agt2.669","url":null,"abstract":"<p>Donor‒acceptor covalent organic frameworks (D‒A COFs) have been regarded as promising materials for photocatalytic water splitting because of their tunable band gaps. However, their efficiency is hindered by fast charge recombination and low photostability. Herein, we proposed a donor structural engineering strategy for improving the photocatalytic activity of D‒A COFs to tackle these problems. Two benzothiadiazole-based D‒A COFs (DHU-COF-BB and DHU-COF-BP) with distinct donors were prepared for photocatalytic H<sub>2</sub> evolution reaction (HER). As a comparison, DHU-COF-TB without benzothiadiazole moieties was also designed and synthesized. Impressively, the photocatalytic H<sub>2</sub> production rate of DHU-COF-BB reaches 12.80 mmol g<sup>−1</sup> h<sup>−1</sup> under visible light irradiation (≥420 nm), which was nearly 2.0 and 3.1 times higher than that of DHU-COF-BP (6.47 mmol g<sup>−1</sup> h<sup>−1</sup>) and DHU-COF-TB (4.06 mmol g<sup>−1</sup> h<sup>−1</sup>), respectively. In addition, the apparent quantum efficiency (AQE) of DHU-COF-BB was up to 5.04% at 420 nm. Photocatalytic and electrochemical measurements indicate that the enhanced hydrogen evolution activity of DHU-COF-BB can be ascribed to the introduction of appropriate benzene moiety into the donors, which increases the charge separation efficiency and thereby suppresses the electron‒hole recombination. Density functional theory (DFT) calculations revealed that both triphenylamine and benzothiadiazole units are the main active sites for HER over the DHU-COF-BB. This work provides new insight into the photocatalytic hydrogen production activity of D‒A COFs by a donor structural engineering strategy.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":"6 1","pages":""},"PeriodicalIF":13.9,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.669","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143111553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Metal-coordinated amino acid/peptide/protein-based supramolecular self-assembled nanomaterials for anticancer applications
IF 13.9 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-03 DOI: 10.1002/agt2.672
Maryam Shabbir, Atia Atiq, Jiahua Wang, Maria Atiq, Nyla Saeed, Ibrahim Yildiz, Xuehai Yan, Ruirui Xing, Manzar Abbas

Biomolecules with metals can form supramolecular nanomaterials through coordination assembly, opening new avenues for cancer theranostics and bringing unique insights into personalized nanomedicine. These biomaterials have been considered versatile and innovative nanoagents due to their structure‒function control, biological nature, and simple preparation methods. This review article summarized the recent developments in multicomponent nanomaterials formed from metal coordination interactions with amino acids, peptides, and proteins, together with anticancer drugs, for cancer theranostics. We discussed the role of functional groups anchored in building blocks for coordination interactions, and subsequently, the types of interactions were examined from a structure‒function perspective. Amino acids with different metals and anticancer drugs forming supramolecular nanomaterials and their anticancer mechanisms were highlighted. Peptides with different metals and anticancer drugs, proteins with metals and anticancer drugs used for material formations, and anticancer activity have been discussed. Ultimately, the conclusion and future outlook for multicomponent supramolecular nanomaterials offer fundamental insights into fabrication design and precision medicine.

{"title":"Metal-coordinated amino acid/peptide/protein-based supramolecular self-assembled nanomaterials for anticancer applications","authors":"Maryam Shabbir,&nbsp;Atia Atiq,&nbsp;Jiahua Wang,&nbsp;Maria Atiq,&nbsp;Nyla Saeed,&nbsp;Ibrahim Yildiz,&nbsp;Xuehai Yan,&nbsp;Ruirui Xing,&nbsp;Manzar Abbas","doi":"10.1002/agt2.672","DOIUrl":"https://doi.org/10.1002/agt2.672","url":null,"abstract":"<p>Biomolecules with metals can form supramolecular nanomaterials through coordination assembly, opening new avenues for cancer theranostics and bringing unique insights into personalized nanomedicine. These biomaterials have been considered versatile and innovative nanoagents due to their structure‒function control, biological nature, and simple preparation methods. This review article summarized the recent developments in multicomponent nanomaterials formed from metal coordination interactions with amino acids, peptides, and proteins, together with anticancer drugs, for cancer theranostics. We discussed the role of functional groups anchored in building blocks for coordination interactions, and subsequently, the types of interactions were examined from a structure‒function perspective. Amino acids with different metals and anticancer drugs forming supramolecular nanomaterials and their anticancer mechanisms were highlighted. Peptides with different metals and anticancer drugs, proteins with metals and anticancer drugs used for material formations, and anticancer activity have been discussed. Ultimately, the conclusion and future outlook for multicomponent supramolecular nanomaterials offer fundamental insights into fabrication design and precision medicine.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":"6 1","pages":""},"PeriodicalIF":13.9,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.672","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143111554","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Programmable light-driven soft actuator enabled by structurally anisotropic liquid crystalline network
IF 13.9 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-02 DOI: 10.1002/agt2.633
Zhaoping Deng, Xinyu Chen, Xinrui Deng, Jiangmin Yang, Shuai Zhou, Jingyu Chen, Peixiang Wang, Huai Yang, Ruochen Lan

The design and fabrication of advanced soft actuators with programmable actuation are highly desirable in constructing intelligent soft robots. In this work, a programmable light-driven liquid crystalline network (LCN)-based soft actuator was judiciously designed and prepared by constructing structural anisotropy across the thickness of the film. A three-dimensional (3D) deformable LCN actuator was realized by polymerization-induced phase separation of small-molar-weight monomers and polymer networks. The resultant anisotropic LCN displays anisotropic microscale nanoporous architecture across the thickness in addition to uniform alignment at the molecular scale. The actuation behaviors of LCN film are tunable by adjusting the size and distribution of nanopores in LCN bulk via changing polymerization conditions and monomer components. More importantly, the nanoporous LCN film can be harnessed as a promising template to achieve diverse light responsiveness by changing the photothermal dyes via a feasible washing and refilling process, demonstrating a reprogrammable light-driven soft actuator.

{"title":"Programmable light-driven soft actuator enabled by structurally anisotropic liquid crystalline network","authors":"Zhaoping Deng,&nbsp;Xinyu Chen,&nbsp;Xinrui Deng,&nbsp;Jiangmin Yang,&nbsp;Shuai Zhou,&nbsp;Jingyu Chen,&nbsp;Peixiang Wang,&nbsp;Huai Yang,&nbsp;Ruochen Lan","doi":"10.1002/agt2.633","DOIUrl":"https://doi.org/10.1002/agt2.633","url":null,"abstract":"<p>The design and fabrication of advanced soft actuators with programmable actuation are highly desirable in constructing intelligent soft robots. In this work, a programmable light-driven liquid crystalline network (LCN)-based soft actuator was judiciously designed and prepared by constructing structural anisotropy across the thickness of the film. A three-dimensional (3D) deformable LCN actuator was realized by polymerization-induced phase separation of small-molar-weight monomers and polymer networks. The resultant anisotropic LCN displays anisotropic microscale nanoporous architecture across the thickness in addition to uniform alignment at the molecular scale. The actuation behaviors of LCN film are tunable by adjusting the size and distribution of nanopores in LCN bulk via changing polymerization conditions and monomer components. More importantly, the nanoporous LCN film can be harnessed as a promising template to achieve diverse light responsiveness by changing the photothermal dyes via a feasible washing and refilling process, demonstrating a reprogrammable light-driven soft actuator.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":"6 1","pages":""},"PeriodicalIF":13.9,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.633","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143111016","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Fluorescence imaging-guided lipid droplets-localized photodynamic therapy
IF 13.9 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 DOI: 10.1002/agt2.665
Shan Wang, Qiang Wang, Yang Lv, Zhe Liu, Kippeum Lee, Dongeun Kim, Miae Won, Jianliang Shen, Jong Seung Kim

Photodynamic therapy (PDT) has emerged as a promising strategy for cancer treatment due to its non-invasive nature and high specificity toward malignant tissues. In recent years, a variety of protocols have been proposed to improve the PDT efficacy, of which organelle-targeted PDT strategy is supposed to be quite promising. Particularly, lipid droplets (LDs)-localized PDT attracts a lot of interest due to the inherent advantages such as abundant LDs in cancer cells and their close relation with ferroptosis. This review provides a comprehensive summary of the advancements of LDs-localized photosensitizers (PSs) according to their chemical structures and functions. Especially, these PSs are featured with fluorescence emission, thereby facilitating an imaging-guided phototherapy. The review highlights the cytocidal actions of these PSs, such as the cell death pathway and their cytotoxicity. Finally, some unresolved issues and challenges in this domain will be discussed.

{"title":"Fluorescence imaging-guided lipid droplets-localized photodynamic therapy","authors":"Shan Wang,&nbsp;Qiang Wang,&nbsp;Yang Lv,&nbsp;Zhe Liu,&nbsp;Kippeum Lee,&nbsp;Dongeun Kim,&nbsp;Miae Won,&nbsp;Jianliang Shen,&nbsp;Jong Seung Kim","doi":"10.1002/agt2.665","DOIUrl":"https://doi.org/10.1002/agt2.665","url":null,"abstract":"<p>Photodynamic therapy (PDT) has emerged as a promising strategy for cancer treatment due to its non-invasive nature and high specificity toward malignant tissues. In recent years, a variety of protocols have been proposed to improve the PDT efficacy, of which organelle-targeted PDT strategy is supposed to be quite promising. Particularly, lipid droplets (LDs)-localized PDT attracts a lot of interest due to the inherent advantages such as abundant LDs in cancer cells and their close relation with ferroptosis. This review provides a comprehensive summary of the advancements of LDs-localized photosensitizers (PSs) according to their chemical structures and functions. Especially, these PSs are featured with fluorescence emission, thereby facilitating an imaging-guided phototherapy. The review highlights the cytocidal actions of these PSs, such as the cell death pathway and their cytotoxicity. Finally, some unresolved issues and challenges in this domain will be discussed.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":"6 1","pages":""},"PeriodicalIF":13.9,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.665","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143110326","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A new class of organic nanoparticles through hyperbranching and crosslinking 一类通过超支化和交联的新型有机纳米颗粒
IF 13.9 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 DOI: 10.1002/agt2.668
Haoran Wang, Junyi Gong, Ben Zhong Tang
<p>Brush-modified nanoparticles, created by grafting functional polymers from nanoparticle surfaces, have demonstrated their versatility in various applications.<sup>[</sup><span><sup>1</sup></span><sup>]</sup> Traditionally, these nanoparticle brushes are formed by tethering polymer chains onto surface-modified “inorganic” particles. However, customizing the internal molecular structure of these nanoparticles is quite limited. In contrast, “organic” nanoparticles (oNPs) offer significant potential for incorporating small functional molecules, enabling applications in areas such as luminescence, sensing, and drug delivery.<sup>[</sup><span><sup>2</sup></span><sup>]</sup> Additionally, materials composed of oNPs are less dense, making them suitable for lightweight equipment, for example, for soft robotics. Despite these advantages, realizing oNPs remains a challenge. Most synthetic approaches rely on “bottom-up” methods such as self-assembly. However, in these systems labile interactions can undermine performance and long-term stability under harsh conditions.</p><p>In a recent breakthrough, Matyjaszewski, Bockstaller, and their teams have developed a new class of oNPs by leveraging macromolecular architecture through concurrent hyperbranching and crosslinking, utilizing atom transfer radical polymerization (ATRP) in microemulsion (Figure 1A).<sup>[</sup><span><sup>3</sup></span><sup>]</sup> Unlike previous work on hyperbranched homopolymers such as poly[2-(2-bromoisobutyryloxy)ethyl methacrylate] (PBiBEM),<sup>[</sup><span><sup>4</sup></span><sup>]</sup> the new method introduces copolymerization with ethylene glycol dimethacrylate (EGDMA) to enhance internal rigidity. Within a confined space, these inimer-based oNPs had tunable sizes and mechanical properties through varying crosslinking densities. With BiBEM composition varying from 60 to 90 mol%, the resulting oNPs are spherical macromolecules (<i>M</i><sub>n,MALS</sub> ranged from 2 to 6 million Daltons), with nanometer-scale diameters, uniform distribution, and minimal aggregation after purification. Also, the increasing crosslinker content yielded smaller oNPs (diameters from 17 to 36 nm) with lower dispersity (<i>M</i><sub>w</sub>/<i>M</i><sub>n</sub>), and greater rigidity (Figure 1B). Furthermore, the addition of sodium dodecyl sulfate (SDS) as an anionic cosurfactant improved uniformity, achieving size dispersity below 3% (Figure 1C).</p><p>Due to the high concentration of alkyl bromide ATRP functionality from the inimer BiBEM and the retention of polymer chain-end functionality via ATRP, these oNPs are well suited as effective macroinitiators for surface-initiated ATRP (Figure 1D). Surface grafting of poly(methyl methacrylate) brushes from oNPs demonstrated high grafting density (<i>σ</i> ∼ 0.5 chains nm<sup>−2</sup>), indicating the potential for direct assembly of brush-modified oNPs or their integration into matrix materials. As crosslinking density increased, each oNP was densely d
电刷修饰的纳米颗粒是通过从纳米颗粒表面接枝功能聚合物而产生的,已经证明了它们在各种应用中的多功能性传统上,这些纳米颗粒刷是通过将聚合物链系在表面修饰的“无机”颗粒上形成的。然而,定制这些纳米颗粒的内部分子结构是相当有限的。相比之下,“有机”纳米颗粒(oNPs)在整合小功能分子方面提供了巨大的潜力,使其在发光、传感和药物输送等领域的应用成为可能此外,由onp组成的材料密度较低,适用于轻型设备,例如软机器人。尽管有这些优势,实现onp仍然是一个挑战。大多数合成方法依赖于自组装等“自下而上”的方法。然而,在这些系统中,在恶劣条件下,不稳定的相互作用会破坏性能和长期稳定性。在最近的一项突破中,Matyjaszewski、Bockstaller和他们的团队利用微乳液中的原子转移自由基聚合(ATRP),通过并发超分支和交联,利用大分子结构开发了一类新的oNPs(图1A)与之前的超支化均聚物(如聚[2-(2-溴异丁基氧基)甲基丙烯酸乙酯](PBiBEM)不同,[4]新方法引入了与乙二醇二甲基丙烯酸酯(EGDMA)的共聚,以提高内部刚性。在有限的空间内,通过不同的交联密度,这些微基oNPs具有可调的尺寸和机械性能。当BiBEM的组成在60 ~ 90 mol%之间变化时,得到的oNPs是球形大分子(Mn,MALS在200 ~ 600万道尔顿之间),其直径为纳米级,分布均匀,纯化后聚集最小。此外,增加交联剂含量产生更小的onp(直径从17到36 nm),更低的分散性(Mw/Mn)和更大的刚性(图1B)。此外,添加十二烷基硫酸钠(SDS)作为阴离子助表面活性剂改善了均匀性,使粒径分散度低于3%(图1C)。由于来自于BiBEM的高浓度的烷基溴ATRP官能,以及通过ATRP保留的聚合物链端官能,这些oNPs非常适合作为表面启动ATRP的有效宏观引发剂(图1D)。聚甲基丙烯酸甲酯刷表面接枝oNPs的接枝密度高(σ ~ 0.5链nm - 2),表明刷修饰的oNPs可以直接组装或集成到基体材料中。随着交联密度的增加,每个oNP被密集地装饰了大约2000个接近均匀Mn ~ 40 kDa的链,产生了总分子量约为30 - 1亿道尔顿的单个oNP刷大分子。原子力显微镜显示,在室温下,最刚性的oNPs接枝相对较软的聚丙烯酸甲酯(Tg约为10°C)刷中存在明显的“核壳”结构(图1E)。本研究为这类新型oNPs的合成和性质提供了一个基础的认识。相应的电刷系留onp有望在各种纳米技术和聚合科学领域实现创新应用未来的研究应侧重于探索功能化机会,如荧光,并在本研究建立的坚实基础上评估这些onp在实际应用中的性能。作者声明无利益冲突。
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引用次数: 0
Enhancing antibacterial photodynamic therapy with NIR-activated gold nanoclusters: Atomic-precision size effect on reducing bacterial biofilm formation and virulence
IF 13.9 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-28 DOI: 10.1002/agt2.666
Chengyu Liu, Tenghui Tian, Yujia Shi, Meiqi Li, Le Hong, Jing Zhou, Jia Liu, Yuan Zhong, Xue Wang, Zhenyu Wang, Xue Bai, Lin Wang, Chunyan Li, Zhennan Wu

Persistent biofilm infections pose a critical health threat with their relentless presence and amplified antibiotic resistance. Traditional antibacterial photodynamic therapy can inhibit bacteria extracellularly but struggles to control biofilm formation and virulence. Thus, there is an urgent need to develop photosensitizers, such as ultra-small gold nanoclusters (AuNCs), that can penetrate biofilms and internalize into bacteria. However, AuNCs still face the challenge of insufficient reactive oxygen species (ROS) production and limited near-infrared light absorption. This study develops a model of indocyanine green (ICG)-sensitized AuNCs with atomic-precision size effect. This approach achieved near-infrared light absorption while inhibiting radiation transitions, thereby regulating the generation of ROS. Notably, different-sized AuNCs (Au10NCs, Au15NCs, Au25NCs) yielded varied ROS types, resulting from different energy level distributions and electron transfer rates. ICG-Au15NCs achieved a treatment efficacy of 99.94% against Staphylococcus aureus infections in vitro and significantly accelerated wound healing in vivo. Moreover, this study highlights the unique role of ICG-AuNCs in suppressing quorum sensing, virulence, and ABC transporters compared to their larger counterparts. This strategy demonstrates that atomic-precision size effect of AuNCs paves the way for innovative approaches in antibacterial photodynamic therapy for infection control.

{"title":"Enhancing antibacterial photodynamic therapy with NIR-activated gold nanoclusters: Atomic-precision size effect on reducing bacterial biofilm formation and virulence","authors":"Chengyu Liu,&nbsp;Tenghui Tian,&nbsp;Yujia Shi,&nbsp;Meiqi Li,&nbsp;Le Hong,&nbsp;Jing Zhou,&nbsp;Jia Liu,&nbsp;Yuan Zhong,&nbsp;Xue Wang,&nbsp;Zhenyu Wang,&nbsp;Xue Bai,&nbsp;Lin Wang,&nbsp;Chunyan Li,&nbsp;Zhennan Wu","doi":"10.1002/agt2.666","DOIUrl":"https://doi.org/10.1002/agt2.666","url":null,"abstract":"<p>Persistent biofilm infections pose a critical health threat with their relentless presence and amplified antibiotic resistance. Traditional antibacterial photodynamic therapy can inhibit bacteria extracellularly but struggles to control biofilm formation and virulence. Thus, there is an urgent need to develop photosensitizers, such as ultra-small gold nanoclusters (AuNCs), that can penetrate biofilms and internalize into bacteria. However, AuNCs still face the challenge of insufficient reactive oxygen species (ROS) production and limited near-infrared light absorption. This study develops a model of indocyanine green (ICG)-sensitized AuNCs with atomic-precision size effect. This approach achieved near-infrared light absorption while inhibiting radiation transitions, thereby regulating the generation of ROS. Notably, different-sized AuNCs (Au<sub>10</sub>NCs, Au<sub>15</sub>NCs, Au<sub>25</sub>NCs) yielded varied ROS types, resulting from different energy level distributions and electron transfer rates. ICG-Au<sub>15</sub>NCs achieved a treatment efficacy of 99.94% against <i>Staphylococcus aureus</i> infections in vitro and significantly accelerated wound healing in vivo. Moreover, this study highlights the unique role of ICG-AuNCs in suppressing quorum sensing, virulence, and ABC transporters compared to their larger counterparts. This strategy demonstrates that atomic-precision size effect of AuNCs paves the way for innovative approaches in antibacterial photodynamic therapy for infection control.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":"6 1","pages":""},"PeriodicalIF":13.9,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.666","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143120430","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Aggregation-induced circularly polarized luminescence and delayed fluorescence enabled by activating high-level reverse intersystem crossing
IF 13.9 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-25 DOI: 10.1002/agt2.667
Ke Wang, Xinwen Ou, Xiaofei Niu, Zhenghao Wang, Fengyan Song, Xiaobin Dong, Wu-jie Guo, Hui-Qing Peng, Zujin Zhao, Jacky W. Y. Lam, Jianwei Sun, Hongkai Wu, Shu-Yan Yu, Fei Li, Ben Zhong Tang

Circularly polarized luminescence (CPL) materials with delayed fluorescence have attracted much attention due to their ability to efficiently trap triplet state excitons, thereby improving the photoluminescence quantum yields of CPL materials. However, much effort has been normally focused on the utilization of T1 excitons but seldom on the utilization of higher excited triplet state Tn (n > 1) excitons. Rational manipulation of higher excited triplet state Tn (n > 1) excitons and suppression of Kasha's rule of CPL materials remains a major challenge. Herein, two gold complex enantiomers ((R/S)-BPAuBC) based on axially chiral binaphthyls and 3,6-Di-tert-butylcarbazole groups are synthesized and systematically investigated. These materials exhibit aggregation-induced circularly polarized delayed fluorescence. Circularly polarized delayed fluorescence was found to be enabled by activating high-level reverse intersystem crossing (hRISC). The anti-Kasha phosphorescence at 77 K proves that the exciton has a large population in the high-lying triplet state T2, which allows the effective hRISC process to cross back to the singlet state S1 and emit delayed fluorescence. In addition, CPL “on–off” switching is further achieved in nanoparticles by acid–base stimulus, showing its potential as an acid–base responsive material.

{"title":"Aggregation-induced circularly polarized luminescence and delayed fluorescence enabled by activating high-level reverse intersystem crossing","authors":"Ke Wang,&nbsp;Xinwen Ou,&nbsp;Xiaofei Niu,&nbsp;Zhenghao Wang,&nbsp;Fengyan Song,&nbsp;Xiaobin Dong,&nbsp;Wu-jie Guo,&nbsp;Hui-Qing Peng,&nbsp;Zujin Zhao,&nbsp;Jacky W. Y. Lam,&nbsp;Jianwei Sun,&nbsp;Hongkai Wu,&nbsp;Shu-Yan Yu,&nbsp;Fei Li,&nbsp;Ben Zhong Tang","doi":"10.1002/agt2.667","DOIUrl":"https://doi.org/10.1002/agt2.667","url":null,"abstract":"<p>Circularly polarized luminescence (CPL) materials with delayed fluorescence have attracted much attention due to their ability to efficiently trap triplet state excitons, thereby improving the photoluminescence quantum yields of CPL materials. However, much effort has been normally focused on the utilization of T<sub>1</sub> excitons but seldom on the utilization of higher excited triplet state T<i><sub>n</sub></i> (<i>n</i> &gt; 1) excitons. Rational manipulation of higher excited triplet state T<i><sub>n</sub></i> (<i>n</i> &gt; 1) excitons and suppression of Kasha's rule of CPL materials remains a major challenge. Herein, two gold complex enantiomers ((<i>R</i>/<i>S</i>)-BPAuBC) based on axially chiral binaphthyls and 3,6-Di-tert-butylcarbazole groups are synthesized and systematically investigated. These materials exhibit aggregation-induced circularly polarized delayed fluorescence. Circularly polarized delayed fluorescence was found to be enabled by activating high-level reverse intersystem crossing (hRISC). The anti-Kasha phosphorescence at 77 K proves that the exciton has a large population in the high-lying triplet state T<sub>2</sub>, which allows the effective hRISC process to cross back to the singlet state S<sub>1</sub> and emit delayed fluorescence. In addition, CPL “on–off” switching is further achieved in nanoparticles by acid–base stimulus, showing its potential as an acid–base responsive material.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":"6 1","pages":""},"PeriodicalIF":13.9,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.667","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143119451","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Aggregate (Hoboken, N.J.)
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