{"title":"Advances in anode interfacial materials for organic solar cells","authors":"Menglan Lv, Junhua Huang, Xuanyan Luo, Shan Yu, Xu Wang, Zhuo Wang, Fei Pan, Bin Zhang, Liming Ding","doi":"10.1002/agt2.544","DOIUrl":"10.1002/agt2.544","url":null,"abstract":"<p>Organic solar cells (OSCs) have attracted much interest in the past few decades because of their advantages, such as being lightweight, low cost, simple preparation process, and environmental friendliness. While researchers have made significant progress on the active layer materials of OSCs, the interface engineering is another entry point for upgrading the photovoltaic performance of OSCs. Significantly, the interface modification materials, including anode interfacial materials and cathode interfacial materials, are two essential parts of interfacial layers for OSCs, in which the excellent interfacial materials can realize the very high-performance photovoltaic cells. Among these interfacial materials, the anode interfacial layers (AILs) play a crucial role in improving photovoltaic performance. This review expresses a detailed conclusion of the development of anode interfacial materials and an outlook on future trends for OSCs.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":null,"pages":null},"PeriodicalIF":13.9,"publicationDate":"2024-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.544","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140165560","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}
Chen Chao, Shiqing Huang, Cuiping Wang, Rong Sun, Jinglin Yu, Les Copeland, Shujun Wang
{"title":"Interaction between amylose, fatty acid, and β-lactoglobulin to study multiple biomacromolecules self-assembly and application","authors":"Chen Chao, Shiqing Huang, Cuiping Wang, Rong Sun, Jinglin Yu, Les Copeland, Shujun Wang","doi":"10.1002/agt2.536","DOIUrl":"10.1002/agt2.536","url":null,"abstract":"<p>New concept for the development of supramolecular assemblies from intricate interactions between different classes of biomacromolecules (polysaccharides, proteins and lipids) is yet to come, due to their intrinsic chemical and structural complexity and incompatibility. Herein, we report an interaction mechanism among multiple biomacromolecules, and the structural and digestive properties of their assemblies using amylose (AM), lauric acid (LA), and β-lactoglobulin (βLG) as exemplars. AM, LA, and βLG interact to form a water-soluble ternary complex through van der Waals forces between AM and LA and high affinity binding between AM and βLG, which can further assemble into uniform-sized, semi-crystalline nanospheres under certain thermodynamic conditions. These nanospheres are substantially resistant to amylolysis, thus can be well utilized by gut microbiota, including increasing short-chain fatty acid levels and shaping bacterial communities. Illustrating the complexation of AM, LA, and βLG and their assemblies from disorder to order, this work offers potential rationale of assemblies for multiple biomacromolecules driven by non-covalent interactions and substantial potentials for supramolecular biomaterials development.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":null,"pages":null},"PeriodicalIF":13.9,"publicationDate":"2024-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.536","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140116515","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}
{"title":"Hybrid anionic block copolymerization: From organocatalysis-streamlined crossover to internally microphase-separated aggregates","authors":"Lijun Liu, Heng Li, Pengfei Zhang, Yubo Zhou, Junpeng Zhao, Guangzhao Zhang","doi":"10.1002/agt2.541","DOIUrl":"10.1002/agt2.541","url":null,"abstract":"<p>Polyolefin-<i>b</i>-poly(ethylene oxide) (PEO) represents the most widely investigated amphiphilic block copolymers. So far, one-pot continuous synthesis of such hybrid block copolymers has only been fulfilled by anionic polymerization through sequential addition of vinyl monomers and ethylene oxide (EO). It still remains challenging to achieve altogether high block efficiency, high polymerization efficiency, and high molar mass for PEO. Here, we report a one-pot hybrid block copolymerization approach to polyisoprene/polystyrene(PI/PS)-<i>b</i>-PEO, in which PI/PS are formed by <i><sup>s</sup></i>BuLi-initiated anionic vinyl-addition polymerization, then in situ employed as macroinitiators for the anionic ring-opening polymerization (ROP) of EO aided by an organic Lewis pair. The cooperative (dual-ion-complexing) catalytic effect of organobase and triethylborane is proven, for the first time, effective for lithium alkoxide initiator system, allowing to achieve at room temperature high ROP activity (complete EO conversion and PEO of 3–64 kg/mol reached in 1–6 h), narrow molar mass distribution, controlled block lengths and composition. Density functional theory calculation shows that phosphazene bases are particularly effective, compared with <i>N</i>-heterocyclic bases, for complexing with Li<sup>+</sup> and enhancing the nucleophilicity of oxyanion. The rate of ROP is also affected by Li<sup>+</sup>-induced aggregation of the chain-end ion pairs, which though can be offset by adequate catalyst loadings. The versatility of this approach is further demonstrated in the one-pot synthesis of tri-/tetrablock ter-/quaterpolymers constituted by PI, PS, PEO, and poly(propylene oxide). Of great interest, PS-<i>b</i>-PI-<i>b</i>-PEO triblock terpolymer with a specific composition is found to form internally microphase-separated micellar aggregates when dispersed in water.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":null,"pages":null},"PeriodicalIF":13.9,"publicationDate":"2024-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.541","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140106127","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}
{"title":"The aggregation behaviors of organic radicals in polar fluorinated arenes","authors":"Shan Liu, Yin Yang, Tianfei Liu","doi":"10.1002/agt2.543","DOIUrl":"10.1002/agt2.543","url":null,"abstract":"<p>Polar fluorinated arenes can promote organic free radical reactions, which have attracted scientists’ interest in recent years. However, it is still unknown how these solvents interact weakly with organic radical molecules to influence their reactivity. In this study, we investigated how organic free radicals aggregate in five polar fluorocarbon solvents, and demonstrated that different substituents can influence their aggregation behaviors. In these solvents, small organic radicals with simple substituents maintain a homogeneous solution; however, radicals with substituents that form intermolecular hydrogen bonds or with long-chain aliphatic hydrocarbons tend to aggregate in them, whereas substituents of long-chain aliphatic hydrocarbons tend to promote aggregation better. The critical aggregation concentrations of these aggregates are measured by concentration-dependent UV–visible spectroscopy. Their topological morphologies are all spherical based on TEM. The compactness and rotational motivation speed of radical molecules within these aggregates are determined by EPR spectroscopy. The particle sizes of these aggregates are determined by analyzing their cyclic voltammograms. Most excitingly, electrochemical experiments reveal that the aggregation behaviors of free radical molecules with intermolecular hydrogen bonds can significantly increase their catalytic rate for electro-oxidizing benzyl alcohol in such a solvent. The results of this study indicate that in polar fluorinated arenes organic radical molecules’ aggregation behaviors are related to their structures. This may provide guidelines for regulating organic radical reactivity in these solvents in the future.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":null,"pages":null},"PeriodicalIF":13.9,"publicationDate":"2024-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.543","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140074176","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}
{"title":"Exploring and leveraging aggregation effects on reactive oxygen species generation in photodynamic therapy","authors":"Zeyan Zhuang, Jianqing Li, Pingchuan Shen, Zujin Zhao, Ben Zhong Tang","doi":"10.1002/agt2.540","DOIUrl":"10.1002/agt2.540","url":null,"abstract":"<p>Aggregate-level photodynamic therapy (PDT) has attracted significant interest and driven substantial advances in multifunction phototheranostic platforms. As exemplified by two typical instances of aggregation-caused quenching of reactive oxygen species (ROS) and aggregation-induced generation of ROS, the aggregation effect plays a significant role on the ROS generation of photosensitizers (PSs), which is worthy of in-depth exploration and full utilization. However, in contrast to the well-developed researches on the aggregation effect on luminescence, the studies concerning the aggregation effect on ROS generation are currently in a relatively nascent and disjointed stage, lacking guidance from a firmly established research paradigm. To advance this regard, this review aims at providing a consolidated overview of the fundamental principles and research status of aggregation effects on the ROS generation. Here, the research status can be organized into two main facets. One involves the comparison between isolated state and aggregated state, which is mainly conducted by two methods of changing solvent environments and adding adjuvants into a given solvent. The other underscores the distinctions between different aggregate states, consisting of three parts, namely comparison within the same or between different categories based on the classification of single-component and multicomponent aggregates. In this endeavor, we will present our views on current research methodologies that explore how aggregation affects ROS generation and highlight the design strategies to leverage the aggregation effect to optimize PS regiments. We aspire this review to propel the advancement of phototheranostic platforms and accelerate the clinical implementation of precision medicine, and inspire more contributions to aggregate-level photophysics and photochemistry, pushing the aggregate science and materials forward.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":null,"pages":null},"PeriodicalIF":13.9,"publicationDate":"2024-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.540","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140106271","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}
Famin Yu, Rui Li, Xinrui Yang, Yulei Shi, Zhigang Wang
{"title":"Superatomic-based chirality: Asymmetric structures constructed by superatoms","authors":"Famin Yu, Rui Li, Xinrui Yang, Yulei Shi, Zhigang Wang","doi":"10.1002/agt2.539","DOIUrl":"10.1002/agt2.539","url":null,"abstract":"<p>Chirality is one of the fundamental properties of molecules traditionally constructed from atoms. Here, we report for the first time the successful construction of asymmetric chiral structures utilizing highly symmetric endohedral metallofullerene superatoms based on their own bonding properties. Specifically, stable mirror-symmetric sinister and rectus structures are obtained by selecting a superatom capable of forming four chemical bonds as the chiral center. Further analysis shows that the chiral vibration frequency of superatomic assemblies can be as low as a few wavenumbers, which greatly expands the range of chiral spectra compared to atom-based molecules. We term this type of chirality based on superatoms as “superatomic-based chirality”. It is anticipated that this work will significantly expand the variety of chiral structures at the atomic level.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":null,"pages":null},"PeriodicalIF":13.9,"publicationDate":"2024-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.539","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140074177","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}
Wei Liu, Yuwei Zhu, Hang Jiang, Lidan Zhou, Yinan Li, Jiahao Wu, Jie Han, Cheng Yang, Jianzhong Jiang, To Ngai
{"title":"Aggregation and aging of nanoparticle–protein complexes at interfaces studied by evanescent-light scattering microscopy","authors":"Wei Liu, Yuwei Zhu, Hang Jiang, Lidan Zhou, Yinan Li, Jiahao Wu, Jie Han, Cheng Yang, Jianzhong Jiang, To Ngai","doi":"10.1002/agt2.538","DOIUrl":"10.1002/agt2.538","url":null,"abstract":"<p>Plasma protein-induced aggregation of nanoparticles (NPs) is a crucial issue in many applications, such as drug delivery. Although great efforts have been made to investigate the protein adsorption kinetics or protein-induced NPs coalescence in bulk solutions, limited evidence has been uncovered for interfacial circumstances. Diet, disease, medicine, or senility could thoroughly change interfacial physicochemical properties of the inner lining of blood vessels. Implants including stents and artificial heart valves also have varied and evolutionary interfaces. Hence, there is an urgent need to understand the mechanism behind the non-specific protein adsorption and NP-protein aggregation in such interfacial cases. Here, we use evanescent light scattering to observe polystyrene NPs‒fibrinogen aggregation at substrates with varying surface properties. A density-fluctuation correlation function is utilized to reveal the relaxation dynamics of the aggregates. Both time-resolved and spatial-correlated evidence shows that the aging process of such soft materials is out-of-equilibrium, where the dynamics faster and slower than exponential can coexist in one single relaxation process. Besides, corona formation, inner stress, and interconnection together determine the microstructure, local adhesion, and structural relaxation of the aggregates, which can further correspond to the protein-to-NP ratio as well as the surface chemistry of NPs and substrates.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":null,"pages":null},"PeriodicalIF":13.9,"publicationDate":"2024-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.538","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140074184","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}
{"title":"Multifunctional inverse opal microcarriers-based cytokines delivery system with stem cell homing capability for osteoarthritis treatment","authors":"Lingyu Sun, Jingjing Gan, Lijun Cai, Feika Bian, Wei Xu, Yuanjin Zhao","doi":"10.1002/agt2.537","DOIUrl":"10.1002/agt2.537","url":null,"abstract":"<p>Osteoarthritis has been regarded as a complex and serious degenerative disease. Attempts in this area are focused on improving the curative effect of stem cell-based therapies. In this work, we present a novel inverse opal microcarriers-based cytokines delivery system to induce autologous stem cell homing for osteoarthritis treatment. Considering their important role in stem cell recruitment and chondrogenic differentiation respectively, platelet-derived growth factor BB (PDGF-BB) and transforming growth factor β3 (TGF-β3) are loaded into inverse opal microcarriers as model cytokines. Since cytokine release induces the corresponding variations in characteristic reflection spectra and structural colors, the inverse opal microcarriers possess the optical self-reporting capacity to monitor the release process. In vitro cell experiments reveal that inverse opal microcarriers could successfully recruit the gathering of mesenchymal stem cells through the release of loaded cytokines. Based on these features, we have demonstrated the enhanced therapeutic effect of PDGF-BB and TGF-β3 loaded inverse opal microcarriers in the treatment of rat osteoarthritis models. These results indicate that the multifunctional inverse opal microcarriers-based cytokines delivery system would find broad prospects in osteoarthritis treatment and other biomedical fields.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":null,"pages":null},"PeriodicalIF":13.9,"publicationDate":"2024-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.537","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140056344","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}
Mei Yang, Honglan Shen, Suting Zhong, Zongpu Xu, Xiangyu Liu, Weicheng Wu, Chuanbin Mao, Mingying Yang
{"title":"Payload-free protein nanoparticles target inflamed colons to restore intestinal barrier integrity for effectively treating inflammatory bowel diseases","authors":"Mei Yang, Honglan Shen, Suting Zhong, Zongpu Xu, Xiangyu Liu, Weicheng Wu, Chuanbin Mao, Mingying Yang","doi":"10.1002/agt2.515","DOIUrl":"10.1002/agt2.515","url":null,"abstract":"<p>Anti-inflammatory compounds, delivered as a payload to the gastrointestinal tract (GIT) by carriers, still cannot treat inflammatory bowel diseases without avoiding side effects. Here, we developed payload-free protein nanoparticles (PNPs) that crossed GIT to retain in the colon and treat colitis by restoring intestinal barrier integrity by modulating gut microbiome and metabolome. Specifically, PNPs, orally administered to mice with acute colitis, reached the colon within three hours. Consequently, PNPs improve gut microbiota dysbiosis to reverse metabolism balance, suppressing the expression of tumor-necrosis factor α and toll-like receptor 4 that restores the intestinal barrier integrity. PNPs then ameliorated colon inflammation and attenuated gut microbiota dysbiosis by exerting probiotic effects on gut microbiota, treating colitis in a week more effectively than the clinically often used 5-aminosalicylic acid without causing undesired side effects. Such PNPs represent safe, sustainable, and cost-effective therapeutics for treating inflammatory and metabolic diseases by eliminating microbial and metabolomic imbalance.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":null,"pages":null},"PeriodicalIF":13.9,"publicationDate":"2024-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.515","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140056340","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}
Matthew J. Margeson, Mark Atwood, Yashar Esfahani Monfared, Mita Dasog
{"title":"Plasmonic group 4 transition metal carbide interfaces for solar-driven desalination","authors":"Matthew J. Margeson, Mark Atwood, Yashar Esfahani Monfared, Mita Dasog","doi":"10.1002/agt2.531","DOIUrl":"10.1002/agt2.531","url":null,"abstract":"<p>To combat the dwindling supply of freshwater, solar-driven desalination using plasmonic nanomaterials has emerged as a promising and renewable solution. Refractory plasmonic carbide nanomaterials are exciting candidates that are inexpensive and chemically robust but have not been widely explored. Herein, plasmonic carbide interfaces made of TiC, ZrC, and HfC nanoparticle aggregates loaded onto to a mixed cellulose ester (MCE) membrane were explored to gain insight into their solar-vapor generation and desalination potential. Desalination using Atlantic Ocean water under 1 sun intensity yielded rates of 1.26 ± 0.01, 1.18 ± 0.02, and 1.40 ± 0.01 kg m<sup>−2</sup> h<sup>−1</sup>, with efficiencies of 86%, 80%, and 96% for TiC, ZrC, and HfC, respectively. Carbide interfaces showed good stability and effectively removed heavy metal ions and salt from solutions with concentrations up to 35%. PVA hydrogel based TMC evaporators afforded rates of 3.31 ± 0.03 and 3.22 ± 0.03 kg m<sup>−2</sup> h<sup>−1</sup> for TiC and ZrC, respectively. The HfC-PVA interface afforded a high solar desalination rate of 3.69 ± 0.04 kg m<sup>−2</sup> h<sup>−1</sup>, corresponding to an efficiency of 97% under 1-sun illumination. The hydrogel evaporators also retained their strong salt rejection action over time.</p>","PeriodicalId":72127,"journal":{"name":"Aggregate (Hoboken, N.J.)","volume":null,"pages":null},"PeriodicalIF":13.9,"publicationDate":"2024-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/agt2.531","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140045662","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}