Khursand E Yorov, Saidkhodzha Nematulloev, Bedil M Saidzhonov, Maxim S Skorotetcky, Azimet A Karluk, Bashir E Hasanov, Wasim J Mir, Tariq Sheikh, Luis Gutiérrez-Arzaluz, Maximilian Emanuel Maria Phielepeit, Nawal Ashraf, Robert H Blick, Omar F Mohammed, Mehmet Bayindir, Osman M Bakr
Terbium-doped gadolinium oxysulfide (Gd2O2S:Tb3+), commonly referred to as Gadox, is a widely used scintillator material due to its exceptional X-ray attenuation efficiency and high light yield. However, Gadox-based scintillators suffer from low X-ray spatial resolution due to their large particle size, which causes significant light scattering. To address this limitation, we report the synthesis of terbium-doped colloidal Gadox nanoplatelets (NPLs) with near-unity photoluminescence quantum yield (PLQY) and high radioluminescence light yield (LY). In particular, our investigation reveals a strong correlation between PLQY, LY, particle size, and Tb3+concentration. Our synthetic approach allows precise control over the lateral size and thickness of the Gadox NPLs, resulting in a LY of 50,000 photons/MeV. Flexible scintillating screens fabricated with the solution-processable Gadox NPLs exhibited a 20 lp/mm X-ray spatial resolution, surpassing commercial Gadox scintillators. These high-performance and flexible Gadox NPL-based scintillators enable enhanced X-ray imaging capabilities in medicine and security. Our work provides a framework for designing nanomaterial scintillators with superior spatial resolution and efficiency through precise control of dimensions and dopant concentration.
掺铽的氧化钆硫化物(Gd2O2S:Tb3+)通常被称为 Gadox,因其出色的 X 射线衰减效率和高光产率而成为一种广泛使用的闪烁体材料。然而,基于 Gadox 的闪烁体由于粒径较大,会产生明显的光散射,因此 X 射线空间分辨率较低。为了解决这一局限性,我们报告了掺铽胶体 Gadox 纳米颗粒(NPLs)的合成过程,其光致发光量子产率(PLQY)接近统一,辐射发光光产率(LY)也很高。我们的研究尤其揭示了 PLQY、LY、粒度和 Tb3+ 浓度之间的密切联系。我们的合成方法可以精确控制 Gadox NPLs 的横向尺寸和厚度,从而使 LY 达到 50,000 光子/MeV。用溶液可加工 Gadox NPL 制造的柔性闪烁屏显示出 20 lp/mm 的 X 射线空间分辨率,超过了商用 Gadox 闪烁器。这些基于 Gadox NPL 的高性能柔性闪烁体可增强医学和安全领域的 X 射线成像能力。我们的工作为通过精确控制尺寸和掺杂浓度来设计具有卓越空间分辨率和效率的纳米材料闪烁体提供了一个框架。
{"title":"Controlled Synthesis of Terbium-Doped Colloidal Gd<sub>2</sub>O<sub>2</sub>S Nanoplatelets Enables High-Performance X-ray Scintillators.","authors":"Khursand E Yorov, Saidkhodzha Nematulloev, Bedil M Saidzhonov, Maxim S Skorotetcky, Azimet A Karluk, Bashir E Hasanov, Wasim J Mir, Tariq Sheikh, Luis Gutiérrez-Arzaluz, Maximilian Emanuel Maria Phielepeit, Nawal Ashraf, Robert H Blick, Omar F Mohammed, Mehmet Bayindir, Osman M Bakr","doi":"10.1021/acsnano.4c01652","DOIUrl":"https://doi.org/10.1021/acsnano.4c01652","url":null,"abstract":"<p><p>Terbium-doped gadolinium oxysulfide (Gd<sub>2</sub>O<sub>2</sub>S:Tb<sup>3+</sup>), commonly referred to as Gadox, is a widely used scintillator material due to its exceptional X-ray attenuation efficiency and high light yield. However, Gadox-based scintillators suffer from low X-ray spatial resolution due to their large particle size, which causes significant light scattering. To address this limitation, we report the synthesis of terbium-doped colloidal Gadox nanoplatelets (NPLs) with near-unity photoluminescence quantum yield (PLQY) and high radioluminescence light yield (LY). In particular, our investigation reveals a strong correlation between PLQY, LY, particle size, and Tb<sup>3+</sup>concentration. Our synthetic approach allows precise control over the lateral size and thickness of the Gadox NPLs, resulting in a LY of 50,000 photons/MeV. Flexible scintillating screens fabricated with the solution-processable Gadox NPLs exhibited a 20 lp/mm X-ray spatial resolution, surpassing commercial Gadox scintillators. These high-performance and flexible Gadox NPL-based scintillators enable enhanced X-ray imaging capabilities in medicine and security. Our work provides a framework for designing nanomaterial scintillators with superior spatial resolution and efficiency through precise control of dimensions and dopant concentration.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475363","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Evan Lafalce, Rikard Bodin, Bryon W Larson, Ji Hao, Md Azimul Haque, Uyen Huynh, Jeffrey L Blackburn, Zeev Valy Vardeny
Two-dimensional (2D) hybrid organic/inorganic perovskites are an emerging materials class for optoelectronic and spintronic applications due to strong excitonic absorption and emission, large spin-orbit coupling, and Rashba spin-splitting effects. For many of the envisioned applications, tuning the majority charge carrier (electron or hole) concentration is desirable, but electronic doping of metal-halide perovskites has proven to be challenging. Here, we demonstrate electron injection into the lower-energy branch of the Rashba-split conduction band of 2D phenethylammonium lead iodide by means of n-type molecular doping at room temperature. The molecular dopant, benzyl viologen (BV), is shown to compensate adventitious p-type impurities and can lead to a tunable Fermi level above the conduction band minimum and increased conductivity in intrinsic samples. The doping-induced carrier concentration is monitored by the observation of free-carrier absorption and intraband optical transitions in the infrared spectral range. These optical measurements allow for an estimation of the Rashba splitting energy ER ≈38 ± 4 meV. Photoinduced quantum beating measurements demonstrate that the excess electron density reduces the electron spin g-factor by ca. 6%. This work demonstrates controllable carrier concentrations in hybrid organic/inorganic perovskites and yields potential for room temperature spin control through the Rashba effect.
二维(2D)混合有机/无机包晶由于具有强激子吸收和发射、大自旋轨道耦合和拉什巴自旋分裂效应,成为光电和自旋电子应用的新兴材料类别。对于许多设想中的应用来说,调整多数电荷载流子(电子或空穴)浓度是理想的,但事实证明,金属卤化物包晶的电子掺杂具有挑战性。在这里,我们展示了通过在室温下进行 n 型分子掺杂,将电子注入二维苯乙基铵碘化铅的 Rashba 分裂导带低能分支的方法。研究表明,分子掺杂剂苄基紫精(BV)可以补偿偶然出现的 p 型杂质,从而使费米级高于导带最小值并提高本征样品的电导率。通过观察红外光谱范围内的自由载流子吸收和带内光学转变,可以监测掺杂诱导的载流子浓度。通过这些光学测量,可以估算出拉什巴分裂能量 ER ≈38 ± 4 meV。光诱导量子跳动测量结果表明,过量电子密度使电子自旋 g 因子降低了约 6%。这项工作证明了有机/无机混合包晶石中载流子浓度的可控性,以及通过拉什巴效应实现室温自旋控制的潜力。
{"title":"Optical Studies of Doped Two-Dimensional Lead Halide Perovskites: Evidence for Rashba-Split Branches in the Conduction Band.","authors":"Evan Lafalce, Rikard Bodin, Bryon W Larson, Ji Hao, Md Azimul Haque, Uyen Huynh, Jeffrey L Blackburn, Zeev Valy Vardeny","doi":"10.1021/acsnano.4c01525","DOIUrl":"https://doi.org/10.1021/acsnano.4c01525","url":null,"abstract":"<p><p>Two-dimensional (2D) hybrid organic/inorganic perovskites are an emerging materials class for optoelectronic and spintronic applications due to strong excitonic absorption and emission, large spin-orbit coupling, and Rashba spin-splitting effects. For many of the envisioned applications, tuning the majority charge carrier (electron or hole) concentration is desirable, but electronic doping of metal-halide perovskites has proven to be challenging. Here, we demonstrate electron injection into the lower-energy branch of the Rashba-split conduction band of 2D phenethylammonium lead iodide by means of n-type molecular doping at room temperature. The molecular dopant, benzyl viologen (BV), is shown to compensate adventitious p-type impurities and can lead to a tunable Fermi level above the conduction band minimum and increased conductivity in intrinsic samples. The doping-induced carrier concentration is monitored by the observation of free-carrier absorption and intraband optical transitions in the infrared spectral range. These optical measurements allow for an estimation of the Rashba splitting energy <i>E</i><sub>R</sub> ≈38 ± 4 meV. Photoinduced quantum beating measurements demonstrate that the excess electron density reduces the electron spin <i>g</i>-factor by ca. 6%. This work demonstrates controllable carrier concentrations in hybrid organic/inorganic perovskites and yields potential for room temperature spin control through the Rashba effect.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475373","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Antonio Rossi, Jonas Zipfel, Indrajit Maity, Monica Lorenzon, Medha Dandu, Elyse Barré, Luca Francaviglia, Emma C Regan, Zuocheng Zhang, Jacob H Nie, Edward S Barnard, Kenji Watanabe, Takashi Taniguchi, Eli Rotenberg, Feng Wang, Johannes Lischner, Archana Raja, Alexander Weber-Bargioni
Stacking van der Waals crystals allows for the on-demand creation of a periodic potential landscape to tailor the transport of quasiparticle excitations. We investigate the diffusion of photoexcited electron-hole pairs, or excitons, at the interface of WS2/WSe2 van der Waals heterostructure over a wide range of temperatures. We observe the appearance of distinct interlayer excitons for parallel and antiparallel stacking and track their diffusion through spatially and temporally resolved photoluminescence spectroscopy from 30 to 250 K. While the measured exciton diffusivity decreases with temperature, it surprisingly plateaus below 90 K. Our observations cannot be explained by classical models like hopping in the moiré potential. A combination of ab initio theory and molecular dynamics simulations suggests that low-energy phonons arising from the mismatched lattices of moiré heterostructures, also known as phasons, play a key role in describing and understanding this anomalous behavior of exciton diffusion. Our observations indicate that the moiré potential landscape is dynamic down to very low temperatures and that the phason modes can enable efficient transport of energy in the form of excitons.
通过堆叠范德瓦耳斯晶体,可以按需创建周期性电势图,从而调整准粒子激发的传输。我们研究了 WS2/WSe2 范德瓦尔斯异质结构界面上光激发电子-空穴对或激子在宽温度范围内的扩散情况。我们观察到平行堆叠和反平行堆叠出现了不同的层间激子,并通过空间和时间分辨光致发光光谱跟踪它们在 30 至 250 K 范围内的扩散情况。结合 ab initio 理论和分子动力学模拟表明,摩尔异质结构的不匹配晶格(也称为 phasons)产生的低能声子在描述和理解这种异常的激子扩散行为中起着关键作用。我们的观察结果表明,摩尔势图在极低温度下也是动态的,而声子模式可以实现激子形式的能量高效传输。
{"title":"Anomalous Interlayer Exciton Diffusion in WS<sub>2</sub>/WSe<sub>2</sub> Moiré Heterostructure.","authors":"Antonio Rossi, Jonas Zipfel, Indrajit Maity, Monica Lorenzon, Medha Dandu, Elyse Barré, Luca Francaviglia, Emma C Regan, Zuocheng Zhang, Jacob H Nie, Edward S Barnard, Kenji Watanabe, Takashi Taniguchi, Eli Rotenberg, Feng Wang, Johannes Lischner, Archana Raja, Alexander Weber-Bargioni","doi":"10.1021/acsnano.4c00015","DOIUrl":"10.1021/acsnano.4c00015","url":null,"abstract":"<p><p>Stacking van der Waals crystals allows for the on-demand creation of a periodic potential landscape to tailor the transport of quasiparticle excitations. We investigate the diffusion of photoexcited electron-hole pairs, or excitons, at the interface of WS<sub>2</sub>/WSe<sub>2</sub> van der Waals heterostructure over a wide range of temperatures. We observe the appearance of distinct interlayer excitons for parallel and antiparallel stacking and track their diffusion through spatially and temporally resolved photoluminescence spectroscopy from 30 to 250 K. While the measured exciton diffusivity decreases with temperature, it surprisingly plateaus below 90 K. Our observations cannot be explained by classical models like hopping in the moiré potential. A combination of ab initio theory and molecular dynamics simulations suggests that low-energy phonons arising from the mismatched lattices of moiré heterostructures, also known as phasons, play a key role in describing and understanding this anomalous behavior of exciton diffusion. Our observations indicate that the moiré potential landscape is dynamic down to very low temperatures and that the phason modes can enable efficient transport of energy in the form of excitons.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475359","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chemo-immunotherapy has become a promising strategy for cancer treatment. However, the inability of the drugs to penetrate deeply into the tumor and form potent tumor vaccines in vivo severely restricts the antitumor effect of chemo-immunotherapy. In this work, an injectable sodium alginate platform is reported to promote penetration of the chemotherapeutic doxorubicin (DOX) and delivery of personalized tumor vaccines. The injectable multifunctional sodium alginate platform cross-links rapidly in the presence of physiological concentrations of Ca2+, forming a hydrogel that acts as a drug depot and releases loaded hyaluronidase (HAase), DOX, and micelles (IP-NPs) slowly and sustainedly. By degrading hyaluronic acid (HA) overexpressed in tumor tissue, HAase can make tumor tissue "loose" and favor other components to penetrate deeply. DOX induces potent immunogenic cell death (ICD) and produces tumor-associated antigens (TAAs), which could be effectively captured by polyethylenimine (PEI) coated IP-NPs micelles and form personalized tumor vaccines. The vaccines efficaciously facilitate the maturation of dendritic cells (DCs) and activation of T lymphocytes, thus producing long-term immune memory. Imiquimod (IMQ) loaded in the core could further activate the immune system and trigger a more robust antitumor immune effect. Hence, the research proposes a multifunctional drug delivery platform for the effective treatment of colorectal cancer.
化学免疫疗法已成为一种前景广阔的癌症治疗策略。然而,药物无法深入肿瘤内部,无法在体内形成有效的肿瘤疫苗,这严重制约了化学免疫疗法的抗肿瘤效果。这项研究报告了一种可注射的海藻酸钠平台,它能促进化疗药物多柔比星(DOX)的渗透和个性化肿瘤疫苗的递送。这种可注射的多功能海藻酸钠平台在生理浓度的 Ca2+ 存在下迅速交联,形成一种水凝胶,作为药物储存库,缓慢而持续地释放负载的透明质酸酶(HAase)、DOX 和胶束(IP-NPs)。通过降解肿瘤组织中过度表达的透明质酸(HA),透明质酸酶可使肿瘤组织变得 "松散",有利于其他成分深入渗透。DOX 可诱导强效免疫原性细胞死亡(ICD),并产生肿瘤相关抗原(TAAs),聚乙烯亚胺(PEI)包被的 IP-NPs 胶束可有效捕获这些抗原,形成个性化的肿瘤疫苗。这种疫苗能有效促进树突状细胞(DC)的成熟和 T 淋巴细胞的活化,从而产生长期免疫记忆。核心中的咪喹莫特(IMQ)可进一步激活免疫系统,引发更强大的抗肿瘤免疫效应。因此,该研究提出了一种有效治疗结直肠癌的多功能给药平台。
{"title":"Multifunctional Nanoparticle-Loaded Injectable Alginate Hydrogels with Deep Tumor Penetration for Enhanced Chemo-Immunotherapy of Cancer.","authors":"Xinyu Yang, Chenlu Huang, Hanyong Wang, Kaiyue Yang, Mingyang Huang, Weijia Zhang, Qingyu Yu, Hai Wang, Linhua Zhang, Yanli Zhao, Dunwan Zhu","doi":"10.1021/acsnano.4c04766","DOIUrl":"https://doi.org/10.1021/acsnano.4c04766","url":null,"abstract":"<p><p>Chemo-immunotherapy has become a promising strategy for cancer treatment. However, the inability of the drugs to penetrate deeply into the tumor and form potent tumor vaccines in vivo severely restricts the antitumor effect of chemo-immunotherapy. In this work, an injectable sodium alginate platform is reported to promote penetration of the chemotherapeutic doxorubicin (DOX) and delivery of personalized tumor vaccines. The injectable multifunctional sodium alginate platform cross-links rapidly in the presence of physiological concentrations of Ca<sup>2+</sup>, forming a hydrogel that acts as a drug depot and releases loaded hyaluronidase (HAase), DOX, and micelles (IP-NPs) slowly and sustainedly. By degrading hyaluronic acid (HA) overexpressed in tumor tissue, HAase can make tumor tissue \"loose\" and favor other components to penetrate deeply. DOX induces potent immunogenic cell death (ICD) and produces tumor-associated antigens (TAAs), which could be effectively captured by polyethylenimine (PEI) coated IP-NPs micelles and form personalized tumor vaccines. The vaccines efficaciously facilitate the maturation of dendritic cells (DCs) and activation of T lymphocytes, thus producing long-term immune memory. Imiquimod (IMQ) loaded in the core could further activate the immune system and trigger a more robust antitumor immune effect. Hence, the research proposes a multifunctional drug delivery platform for the effective treatment of colorectal cancer.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475372","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Adrian Sanchez-Fernandez, Jia-Fei Poon, Anna Elizabeth Leung, Sylvain François Prévost, Cedric Dicko
Proteins are adjustable units from which biomaterials with designed properties can be developed. However, non-native folded states with controlled topologies are hardly accessible in aqueous environments, limiting their prospects as building blocks. Here, we demonstrate the ability of a series of anhydrous deep eutectic solvents (DESs) to precisely control the conformational landscape of proteins. We reveal that systematic variations in the chemical composition of binary and ternary DESs dictate the stabilization of a wide range of conformations, that is, compact globular folds, intermediate folding states, or unfolded chains, as well as controlling their collective behavior. Besides, different conformational states can be visited by simply adjusting the composition of ternary DESs, allowing for the refolding of unfolded states and vice versa. Notably, we show that these intermediates can trigger the formation of supramolecular gels, also known as eutectogels, where their mechanical properties correlate to the folding state of the protein. Given the inherent vulnerability of proteins outside the native fold in aqueous environments, our findings highlight DESs as tailorable solvents capable of stabilizing various non-native conformations on demand through solvent design.
蛋白质是一种可调节的单元,可据此开发出具有设计特性的生物材料。然而,具有可控拓扑结构的非原生折叠态在水性环境中很难获得,这限制了它们作为构件的前景。在这里,我们展示了一系列无水深共晶溶剂(DES)精确控制蛋白质构象格局的能力。我们发现,二元和三元 DES 化学成分的系统性变化决定了多种构象的稳定性,即紧凑的球状折叠、中间折叠状态或未折叠链,以及控制它们的集体行为。此外,只需调整三元DES的组成,就能造访不同的构象状态,从而实现未折叠状态的再折叠,反之亦然。值得注意的是,我们发现这些中间体可以引发超分子凝胶(也称为共晶凝胶)的形成,其机械性能与蛋白质的折叠状态相关。鉴于蛋白质在水性环境中的原生折叠之外的固有脆弱性,我们的研究结果强调了DES是一种可定制的溶剂,能够通过溶剂设计按需稳定各种非原生构象。
{"title":"Stabilization of Non-Native Folds and Programmable Protein Gelation in Compositionally Designed Deep Eutectic Solvents.","authors":"Adrian Sanchez-Fernandez, Jia-Fei Poon, Anna Elizabeth Leung, Sylvain François Prévost, Cedric Dicko","doi":"10.1021/acsnano.4c01950","DOIUrl":"https://doi.org/10.1021/acsnano.4c01950","url":null,"abstract":"<p><p>Proteins are adjustable units from which biomaterials with designed properties can be developed. However, non-native folded states with controlled topologies are hardly accessible in aqueous environments, limiting their prospects as building blocks. Here, we demonstrate the ability of a series of anhydrous deep eutectic solvents (DESs) to precisely control the conformational landscape of proteins. We reveal that systematic variations in the chemical composition of binary and ternary DESs dictate the stabilization of a wide range of conformations, that is, compact globular folds, intermediate folding states, or unfolded chains, as well as controlling their collective behavior. Besides, different conformational states can be visited by simply adjusting the composition of ternary DESs, allowing for the refolding of unfolded states and vice versa. Notably, we show that these intermediates can trigger the formation of supramolecular gels, also known as eutectogels, where their mechanical properties correlate to the folding state of the protein. Given the inherent vulnerability of proteins outside the native fold in aqueous environments, our findings highlight DESs as tailorable solvents capable of stabilizing various non-native conformations on demand through solvent design.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yirui Zhang, Kai Chang, Babatunde Ogunlade, Liam Herndon, Loza F Tadesse, Amanda R Kirane, Jennifer A Dionne
Raman spectroscopy has made significant progress in biosensing and clinical research. Here, we describe how surface-enhanced Raman spectroscopy (SERS) assisted with machine learning (ML) can expand its capabilities to enable interpretable insights into the transcriptome, proteome, and metabolome at the single-cell level. We first review how advances in nanophotonics-including plasmonics, metamaterials, and metasurfaces-enhance Raman scattering for rapid, strong label-free spectroscopy. We then discuss ML approaches for precise and interpretable spectral analysis, including neural networks, perturbation and gradient algorithms, and transfer learning. We provide illustrative examples of single-cell Raman phenotyping using nanophotonics and ML, including bacterial antibiotic susceptibility predictions, stem cell expression profiles, cancer diagnostics, and immunotherapy efficacy and toxicity predictions. Lastly, we discuss exciting prospects for the future of single-cell Raman spectroscopy, including Raman instrumentation, self-driving laboratories, Raman data banks, and machine learning for uncovering biological insights.
拉曼光谱在生物传感和临床研究方面取得了重大进展。在此,我们将介绍表面增强拉曼光谱(SERS)如何在机器学习(ML)的辅助下扩展其功能,从而在单细胞水平上对转录组、蛋白质组和代谢组进行可解释的深入研究。我们首先回顾了纳米光子学的进步--包括等离子体、超材料和超表面--是如何增强拉曼散射以实现快速、强大的无标记光谱学的。然后,我们讨论了用于精确和可解释光谱分析的 ML 方法,包括神经网络、扰动和梯度算法以及迁移学习。我们提供了利用纳米光子学和 ML 进行单细胞拉曼表型分析的示例,包括细菌抗生素敏感性预测、干细胞表达谱、癌症诊断以及免疫疗法疗效和毒性预测。最后,我们讨论了单细胞拉曼光谱学令人兴奋的未来前景,包括拉曼仪器、自动驾驶实验室、拉曼数据库以及用于揭示生物学见解的机器学习。
{"title":"From Genotype to Phenotype: Raman Spectroscopy and Machine Learning for Label-Free Single-Cell Analysis.","authors":"Yirui Zhang, Kai Chang, Babatunde Ogunlade, Liam Herndon, Loza F Tadesse, Amanda R Kirane, Jennifer A Dionne","doi":"10.1021/acsnano.4c04282","DOIUrl":"https://doi.org/10.1021/acsnano.4c04282","url":null,"abstract":"<p><p>Raman spectroscopy has made significant progress in biosensing and clinical research. Here, we describe how surface-enhanced Raman spectroscopy (SERS) assisted with machine learning (ML) can expand its capabilities to enable interpretable insights into the transcriptome, proteome, and metabolome at the single-cell level. We first review how advances in nanophotonics-including plasmonics, metamaterials, and metasurfaces-enhance Raman scattering for rapid, strong label-free spectroscopy. We then discuss ML approaches for precise and interpretable spectral analysis, including neural networks, perturbation and gradient algorithms, and transfer learning. We provide illustrative examples of single-cell Raman phenotyping using nanophotonics and ML, including bacterial antibiotic susceptibility predictions, stem cell expression profiles, cancer diagnostics, and immunotherapy efficacy and toxicity predictions. Lastly, we discuss exciting prospects for the future of single-cell Raman spectroscopy, including Raman instrumentation, self-driving laboratories, Raman data banks, and machine learning for uncovering biological insights.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475370","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
As a noninvasive treatment modality, high-intensity focused ultrasound (HIFU)-induced antitumor immune responses play a vital role in surgery prognosis. However, limited response intensity largely hinders postoperative immunotherapy. Herein, a hypoxia-specific metal-organic framework (MOF) nanosystem, coordinated by Fe3+, hypoxic-activated prodrug AQ4N, and IDO-1 signaling pathway inhibitor NLG919, is developed for the potentiating immunotherapy of HIFU surgery. The loaded AQ4N enhances the photoacoustic imaging effects to achieve accurate intraoperative navigation. Within the HIFU-established severe hypoxic environment, AQ4N is activated sequentially, following which it cooperates with Fe3+ to effectively provoke immunogenic cell death. In addition, potent NLG919 suppresses IDO-1 activity and degrades the immunosuppressive tumor microenvironment aggravated by postoperative hypoxia. In vivo studies demonstrate that the MOF-mediated immunotherapy greatly inhibits the growth of primary/distant tumors and eliminates lung metastasis. This work establishes a robust delivery platform to improve immunotherapy and the overall prognosis of HIFU surgery with high specificity and potency.
{"title":"Hypoxia-Specific Metal-Organic Frameworks Augment Cancer Immunotherapy of High-Intensity Focused Ultrasound.","authors":"Jingnan Li, Chengyan Luo, Tingyu Sun, Yinglin Zhou, Xinchang Huang, Dezhou Wu, Xirui Luo, Chao Zeng, Huanan Li","doi":"10.1021/acsnano.4c02921","DOIUrl":"https://doi.org/10.1021/acsnano.4c02921","url":null,"abstract":"<p><p>As a noninvasive treatment modality, high-intensity focused ultrasound (HIFU)-induced antitumor immune responses play a vital role in surgery prognosis. However, limited response intensity largely hinders postoperative immunotherapy. Herein, a hypoxia-specific metal-organic framework (MOF) nanosystem, coordinated by Fe<sup>3+</sup>, hypoxic-activated prodrug AQ4N, and IDO-1 signaling pathway inhibitor NLG919, is developed for the potentiating immunotherapy of HIFU surgery. The loaded AQ4N enhances the photoacoustic imaging effects to achieve accurate intraoperative navigation. Within the HIFU-established severe hypoxic environment, AQ4N is activated sequentially, following which it cooperates with Fe<sup>3+</sup> to effectively provoke immunogenic cell death. In addition, potent NLG919 suppresses IDO-1 activity and degrades the immunosuppressive tumor microenvironment aggravated by postoperative hypoxia. <i>In vivo</i> studies demonstrate that the MOF-mediated immunotherapy greatly inhibits the growth of primary/distant tumors and eliminates lung metastasis. This work establishes a robust delivery platform to improve immunotherapy and the overall prognosis of HIFU surgery with high specificity and potency.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475371","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The cost of annual energy consumption in buildings in the United States exceeds 430 billion dollars ( Science 2019, 364 (6442), 760-763), of which about 48% is used for space thermal management (https://www.iea.org/reports/global-status-report-for-buildings-and-construction-2019), revealing the urgent need for efficient thermal management of buildings and dwellings. Radiative cooling technologies, combined with the booming photonic and microfabrication technologies ( Nature 2014, 515 (7528), 540-544), enable energy-free cooling by radiative heat transfer to outer space through the atmospheric transparent window ( Nat. Commun. 2024, 15 (1), 815). To pursue all-season energy savings in climates with large temperature variations, switchable and tunable radiative coolers (STRC) have emerged in recent years and quickly gained broad attention. This Perspective introduces the existing STRC technologies and analyzes their benefits and challenges in future large-scale applications, suggesting ways for the development of future STRCs.
{"title":"Switchable and Tunable Radiative Cooling: Mechanisms, Applications, and Perspectives.","authors":"Xuzhe Zhao, Jiachen Li, Kaichen Dong, Junqiao Wu","doi":"10.1021/acsnano.4c05929","DOIUrl":"https://doi.org/10.1021/acsnano.4c05929","url":null,"abstract":"<p><p>The cost of annual energy consumption in buildings in the United States exceeds 430 billion dollars ( <i>Science</i> 2019, 364 (6442), 760-763), of which about 48% is used for space thermal management (https://www.iea.org/reports/global-status-report-for-buildings-and-construction-2019), revealing the urgent need for efficient thermal management of buildings and dwellings. Radiative cooling technologies, combined with the booming photonic and microfabrication technologies ( <i>Nature</i> 2014, 515 (7528), 540-544), enable energy-free cooling by radiative heat transfer to outer space through the atmospheric transparent window ( <i>Nat. Commun.</i> 2024, 15 (1), 815). To pursue all-season energy savings in climates with large temperature variations, switchable and tunable radiative coolers (STRC) have emerged in recent years and quickly gained broad attention. This Perspective introduces the existing STRC technologies and analyzes their benefits and challenges in future large-scale applications, suggesting ways for the development of future STRCs.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475376","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Therapy-induced modulation of the tumor microenvironment (TME) to overcome the immunosuppressive TME is considered to be an opportunity for cancer treatment. However, monitoring of TME modulation during the therapeutic process to accurately determine immune responses and adjust treatment plans in a timely manner remains to be challenging. Herein, we report a carrier-free nanotheranostic system (CANPs) assembled by two boron dipyrromethene (BODIPY) dyes, a sonophotosensitizer C-BDP, and a nitric oxide (NO) probe amino-BODIPY (A-BDP). CANPs can exert combined sonophototherapeutic effects of C-BDP under ultrasound and light irradiation and simultaneously induce inflammatory TME, as well as emit bright fluorescence via A-BDP by monitoring tumor-associated macrophages (TAMs) repolarization through the released NO in vitro and in vivo. Of note, transforming growth factor-β (TGF-β) could be the key cytokine involved in the sonophototherapy-induced TME reprogramming. By virtue of high physiological stability, good biocompatibility, and effective tumor targetability, CANPs could be a potential nanotheranostic system for the simultaneous induction and detection of TME reprogramming triggered by sonophototherapy.
{"title":"Boron Dipyrromethene-Based Nanotheranostic System for Sonophotoassisted Therapy and Simultaneous Monitoring of Tumor Immune Microenvironment Reprogramming.","authors":"Xudong Li, Xianbin Sun, Hui Chen, Ya Wang, Haijun Chen, Yu Gao","doi":"10.1021/acsnano.4c00650","DOIUrl":"https://doi.org/10.1021/acsnano.4c00650","url":null,"abstract":"<p><p>Therapy-induced modulation of the tumor microenvironment (TME) to overcome the immunosuppressive TME is considered to be an opportunity for cancer treatment. However, monitoring of TME modulation during the therapeutic process to accurately determine immune responses and adjust treatment plans in a timely manner remains to be challenging. Herein, we report a carrier-free nanotheranostic system (CANPs) assembled by two boron dipyrromethene (BODIPY) dyes, a sonophotosensitizer C-BDP, and a nitric oxide (NO) probe amino-BODIPY (A-BDP). CANPs can exert combined sonophototherapeutic effects of C-BDP under ultrasound and light irradiation and simultaneously induce inflammatory TME, as well as emit bright fluorescence via A-BDP by monitoring tumor-associated macrophages (TAMs) repolarization through the released NO in vitro and in vivo. Of note, transforming growth factor-β (TGF-β) could be the key cytokine involved in the sonophototherapy-induced TME reprogramming. By virtue of high physiological stability, good biocompatibility, and effective tumor targetability, CANPs could be a potential nanotheranostic system for the simultaneous induction and detection of TME reprogramming triggered by sonophototherapy.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of lithium metal batteries (LMBs) is severely hindered owing to the limited temperature window of the electrolyte, which renders uncontrolled side reactions, unstable electrolyte/electrode interface (EEI) formation, and sluggish desolvation kinetics for wide temperature operation condition. Herein, we developed an all-fluorinated electrolyte composed of lithium bis(trifluoromethane sulfonyl)imide, hexafluorobenzene (HFB), and fluoroethylene carbonate, which effectively regulates solvation structure toward a wide temperature of 160 °C (-50 to 110 °C). The introduction of thermostable HFB induces the generation of EEI with a high LiF ratio of 93%, which results in an inhibited side reaction and gas generation on EEI and enhanced interfacial ion transfer at extreme temperatures. Therefore, an unparalleled capacity retention of 88.3% after 400 cycles at 90 °C and an improved cycling performance at -50 °C can be achieved. Meanwhile, the practical 1.3 Ah-level pouch cell delivers high energy density of 307.13 Wh kg-1 at 60 °C and 277.99 Wh kg-1 at -30 °C after 50 cycles under lean E/C ratio of 2.7 g/Ah and low N/P ratio of 1.2. This work not only offers a viable strategy for wide-temperature-range electrolyte design but also promotes the practicalization of LMBs.
{"title":"All-Fluorinated Electrolyte Engineering Enables Practical Wide-Temperature-Range Lithium Metal Batteries.","authors":"Liwei Dong, Dan Luo, Bowen Zhang, Yaqiang Li, Tingzhou Yang, Zuotao Lei, Xinghong Zhang, Yuanpeng Liu, Chunhui Yang, Zhongwei Chen","doi":"10.1021/acsnano.4c06231","DOIUrl":"https://doi.org/10.1021/acsnano.4c06231","url":null,"abstract":"<p><p>The development of lithium metal batteries (LMBs) is severely hindered owing to the limited temperature window of the electrolyte, which renders uncontrolled side reactions, unstable electrolyte/electrode interface (EEI) formation, and sluggish desolvation kinetics for wide temperature operation condition. Herein, we developed an all-fluorinated electrolyte composed of lithium bis(trifluoromethane sulfonyl)imide, hexafluorobenzene (HFB), and fluoroethylene carbonate, which effectively regulates solvation structure toward a wide temperature of 160 °C (-50 to 110 °C). The introduction of thermostable HFB induces the generation of EEI with a high LiF ratio of 93%, which results in an inhibited side reaction and gas generation on EEI and enhanced interfacial ion transfer at extreme temperatures. Therefore, an unparalleled capacity retention of 88.3% after 400 cycles at 90 °C and an improved cycling performance at -50 °C can be achieved. Meanwhile, the practical 1.3 Ah-level pouch cell delivers high energy density of 307.13 Wh kg<sup>-1</sup> at 60 °C and 277.99 Wh kg<sup>-1</sup> at -30 °C after 50 cycles under lean E/C ratio of 2.7 g/Ah and low N/P ratio of 1.2. This work not only offers a viable strategy for wide-temperature-range electrolyte design but also promotes the practicalization of LMBs.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475358","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}