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Cell Death Pathways: The Variable Mechanisms Underlying Fine Particulate Matter-Induced Cytotoxicity 细胞死亡途径:细颗粒物诱导的细胞毒性的可变机制
Q2 NANOSCIENCE & NANOTECHNOLOGY Pub Date : 2023-01-25 DOI: 10.1021/acsnanoscienceau.2c00059
Yucai Chen, Yue Wu, Yu Qi* and Sijin Liu, 

Recently, the advent of health risks due to the cytotoxicity of fine particulate matter (FPM) is concerning. Numerous studies have reported abundant data elucidating the FPM-induced cell death pathways. However, several challenges and knowledge gaps are still confronted nowadays. On one hand, the undefined components of FPM (such as heavy metals, polycyclic aromatic hydrocarbons, and pathogens) are all responsible for detrimental effects, thus rendering it difficult to delineate the specific roles of these copollutants. On the other hand, owing to the crosstalk and interplay among different cell death signaling pathways, precisely determining the threats and risks posed by FPM is difficult. Herein, we recapitulate the current knowledge gaps present in the recent studies regarding FPM-induced cell death, and propose future research directions for policy-making to prevent FPM-induced diseases and improve knowledge concerning the adverse outcome pathways and public health risks of FPM.

最近,细颗粒物(FPM)的细胞毒性导致的健康风险的出现令人担忧。大量研究报道了大量阐明FPM诱导的细胞死亡途径的数据。然而,今天仍然面临着一些挑战和知识差距。一方面,FPM的未定义成分(如重金属、多环芳烃和病原体)都是造成有害影响的原因,因此很难确定这些污染物的具体作用。另一方面,由于不同细胞死亡信号通路之间的串扰和相互作用,很难准确确定FPM带来的威胁和风险。在此,我们总结了最近关于FPM诱导的细胞死亡的研究中存在的知识空白,并提出了未来的研究方向,以预防FPM诱导疾病,提高对FPM不良后果途径和公共健康风险的认识。
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引用次数: 4
Mechanistic Study of the Conductance and Enhanced Single-Molecule Detection in a Polymer–Electrolyte Nanopore 聚合物-电解质纳米孔中电导及增强单分子检测的机理研究
Q2 NANOSCIENCE & NANOTECHNOLOGY Pub Date : 2023-01-10 DOI: 10.1021/acsnanoscienceau.2c00050
Fabio Marcuccio, Dimitrios Soulias, Chalmers C. C. Chau, Sheena E. Radford, Eric Hewitt, Paolo Actis* and Martin Andrew Edwards*, 

Solid-state nanopores have been widely employed in the detection of biomolecules, but low signal-to-noise ratios still represent a major obstacle in the discrimination of nucleic acid and protein sequences substantially smaller than the nanopore diameter. The addition of 50% poly(ethylene) glycol (PEG) to the external solution is a simple way to enhance the detection of such biomolecules. Here, we demonstrate with finite-element modeling and experiments that the addition of PEG to the external solution introduces a strong imbalance in the transport properties of cations and anions, drastically affecting the current response of the nanopore. We further show that the strong asymmetric current response is due to a polarity-dependent ion distribution and transport at the nanopipette tip region, leading to either ion depletion or enrichment for few tens of nanometers across its aperture. We provide evidence that a combination of the decreased/increased diffusion coefficients of cations/anions in the bath outside the nanopore and the interaction between a translocating molecule and the nanopore–bath interface is responsible for the increase in the translocation signals. We expect this new mechanism to contribute to further developments in nanopore sensing by suggesting that tuning the diffusion coefficients of ions could enhance the sensitivity of the system.

固态纳米孔已被广泛用于生物分子的检测,但低信噪比仍然是区分明显小于纳米孔径的核酸和蛋白质序列的主要障碍。向外部溶液中添加50%的聚乙二醇(PEG)是增强对此类生物分子检测的简单方法。在这里,我们通过有限元建模和实验证明,在外部溶液中添加PEG会导致阳离子和阴离子的传输特性严重失衡,从而极大地影响纳米孔的电流响应。我们进一步表明,强烈的不对称电流响应是由于纳米移液管尖端区域的极性依赖性离子分布和传输,导致离子耗尽或富集几十纳米。我们提供的证据表明,阳离子/阴离子在纳米孔外的浴中的扩散系数降低/增加,以及易位分子和纳米孔-浴界面之间的相互作用,是易位信号增加的原因。我们预计,这一新机制将有助于纳米孔传感的进一步发展,因为它表明调整离子的扩散系数可以提高系统的灵敏度。
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引用次数: 4
Back to the Basics: Developing Advanced Metal–Organic Frameworks Using Fundamental Chemistry Concepts 回到基础:开发先进的金属有机框架使用基本化学概念
Q2 NANOSCIENCE & NANOTECHNOLOGY Pub Date : 2022-12-27 DOI: 10.1021/acsnanoscienceau.2c00046
Kent O. Kirlikovali, Sylvia L. Hanna, Florencia A. Son and Omar K. Farha*, 

Over the past 25 years, metal–organic frameworks (MOFs) have developed into an increasingly intricate class of crystalline porous materials in which the choice of building blocks offers significant control over the physical properties of the resulting material. Despite this complexity, fundamental coordination chemistry design principles provided a strategic basis to design highly stable MOF structures. In this Perspective, we provide an overview of these design strategies and discuss how researchers leverage fundamental chemistry concepts to tune reaction parameters and synthesize highly crystalline MOFs. We then discuss these design principles in the context of several literature examples, highlighting both relevant fundamental chemistry principles and additional design principles required to access stable MOF structures. Finally, we envision how these fundamental concepts may offer access to even more advanced structures with tailored properties as the MOF field looks toward the future.

在过去的25年里,金属-有机框架(MOFs)已经发展成为一类越来越复杂的结晶多孔材料,其中构建块的选择对所得材料的物理性能提供了重要的控制。尽管存在这种复杂性,但基本的配位化学设计原则为设计高度稳定的MOF结构提供了战略基础。从这个角度来看,我们概述了这些设计策略,并讨论了研究人员如何利用基本化学概念来调整反应参数和合成高度结晶的MOFs。然后,我们在几个文献例子的背景下讨论了这些设计原则,强调了相关的基本化学原则和获得稳定MOF结构所需的额外设计原则。最后,我们设想,随着MOF领域展望未来,这些基本概念将如何提供具有定制性能的更先进结构。
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引用次数: 8
Plasmonic Sensing Assay for Long-Term Monitoring (PSALM) of Neurotransmitters in Urine 尿中神经递质长期监测的等离子体传感试验
Q2 NANOSCIENCE & NANOTECHNOLOGY Pub Date : 2022-12-24 DOI: 10.1021/acsnanoscienceau.2c00048
Wei-Hsin Chen, Wenting Wang, Qianqi Lin, David-Benjamin Grys, Marika Niihori, Junyang Huang, Shu Hu, Bart de Nijs, Oren A. Scherman and Jeremy J. Baumberg*, 

A liquid-based surface-enhanced Raman spectroscopy assay termed PSALM is developed for the selective sensing of neurotransmitters (NTs) with a limit of detection below the physiological range of NT concentrations in urine. This assay is formed by quick and simple nanoparticle (NP) “mix-and-measure” protocols, in which FeIII bridges NTs and gold NPs inside the sensing hotspots. Detection limits of NTs from PreNP PSALM are significantly lower than those of PostNP PSALM, when urine is pretreated by affinity separation. Optimized PSALM enables the long-term monitoring of NT variation in urine in conventional settings for the first time, allowing the development of NTs as predictive or correlative biomarkers for clinical diagnosis.

开发了一种称为PSALM的基于液体的表面增强拉曼光谱测定法,用于选择性传感神经递质(NT),其检测极限低于尿液中NT浓度的生理范围。该测定是通过快速简单的纳米颗粒(NP)“混合和测量”方案形成的,其中FeIII在传感热点内桥接纳米颗粒和金纳米颗粒。当尿液通过亲和分离进行预处理时,来自PreNP-PSLM的NT的检测限显著低于PostNP-PSLm的检测限。优化的PSALM首次能够在常规环境中长期监测尿液中的NT变化,从而将NT开发为临床诊断的预测或相关生物标志物。
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引用次数: 1
One Year of ACS Nanoscience Au ACS纳米科学Au一年
Q2 NANOSCIENCE & NANOTECHNOLOGY Pub Date : 2022-12-21 DOI: 10.1021/acsnanoscienceau.2c00056
Raymond E. Schaak*, 
I is hard to believe that a year has passed already since the first issue of ACS Nanoscience Au was published in December of 2021. In the six issues in Volume 2, which constitute the first full year, ACS Nanoscience Au has published 44 contributions, including 3 Editorials, 1 Perspective, 11 Reviews, and 29 Articles/Letters. In total, all of the content published thus far in ACS Nanoscience Au has been viewed more than 88,000 times! This large number of views is a testament to the journal’s outstanding content, as well as its visibility and reach, which are maximized by its open access status. The published papers have been authored and accessed by researchers from around the world, highlighting the global impact and visibility of ACS Nanoscience Au. These papers also span the breadth of topics that define the field of nanoscience. To highlight the topical diversity and impact of the first year of ACS Nanoscience Au, the papers highlighted below are among the most accessed and cited so far. They represent a collection of Reviews and Perspectives in nanomedicine, nanoelectronics, active matter, environmental remediation, 1-D and 2-D materials, and energy, as well as Articles and Letters in nanoclusters, nanomedicine, nanoagriculture, nanowires, halide perovskites, SERS imaging, nanophotonics, DNA nanotechnology, and MXenes. Luciferase-Based Biosensors in the Era of the COVID-19 Pandemic (ACS Nanosci. Au 2021, 1, 15−37). Our very first published Review, by Taha Azad, Carolina Ilkow, John Bell, and co-workers, holds the current record for the highest number of article views in the journal. Viruses and proteins are inherently nanoscopic systems, and this Review highlights the development and use of biosensors to study virus biology, including SARS-CoV-2. Design of Over-1000 nm Near-Infrared Fluorescent Polymeric Micellar Nanoparticles by Matching the Solubility Parameter of the Core Polymer and Dye (ACS Nanosci. Au 2021, 1, 61−68). This Article by Masakazu Umezawa, Kohei Soga, and co-workers demonstrated a strategy for designing polymeric nanoparticles for biological imaging. They showed how near-infrared fluorescent probes could be accessed by matching the solubility parameters of a core polymer and a dye molecule. Gold Nanoparticle Smartphone Platform for Diagnosing Urinary Tract Infections (ACS Nanosci. Au 2022, 2, 324− 332). The diagnosis of urinary tract infections is important in medicine. In this Article, Warren Chan and co-workers used a gold nanoparticle colorimetric approach to detect clinically relevant bacteria concentrations, finding it both inexpensive and fast. They then used this to develop a smartphone platform for detecting urinary tract infections. Ligand Ratio Plays a Critical Role in the Design of Optimal Multifunctional Gold Nanoclusters for Targeted Gastric Cancer Therapy (ACS Nanosci. Au 2021, 1, 47−60). This Article by Mariá Francisca Matus, Sami Malola, and Hannu Hak̈kinen was the first to be accepted for publication in ACS
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引用次数: 0
Label-Free Digital Holotomography Reveals Ibuprofen-Induced Morphological Changes to Red Blood Cells 无标签数字全息断层扫描揭示布洛芬诱导红细胞形态学改变
Q2 NANOSCIENCE & NANOTECHNOLOGY Pub Date : 2022-12-14 DOI: 10.1101/2022.12.13.519447
Talia Bergaglio, Shayon Bhattacharya, Damien Thompson, P. Nirmalraj
Understanding the dose-dependent effect of over-the-counter drugs on red blood cells (RBCs) is crucial for hematology and digital pathology. Yet, it is challenging to continuously record the real-time, drug-induced nanoscopic shape changes of RBCs in a label-free manner. Here, we demonstrate digital holotomography (DHTM) enabled real-time, label-free concentration-dependent and time-dependent monitoring of ibuprofen on RBCs from a healthy donor. The RBCs are segmented based on 3D and 4D refractive index tomograms and their morphological and chemical parameters are retrieved with their shapes classified using machine learning. We directly observed the formation and motion of spicules on the RBC membranes when aqueous solutions of ibuprofen were drop cast on wet blood, creating rough-membraned echinocyte forms. At low concentrations of 0.25-0.50 mM, the ibuprofen-induced morphological change was transient but at high concentrations (1.5-3 mM) the spiculated RBC remained over a period of up to 1.5 hours. Molecular simulations confirmed that aggregates of ibuprofen molecules at high concentrations significantly disrupted the RBC membrane structural integrity and lipid order, but produced negligible effect at low ibuprofen concentrations. Control experiments on the effect of urea, hydrogen peroxide and aqueous solutions on RBCs showed zero spicule formation. Our work elucidates the dose-dependent chemical effects on RBCs using label-free microscopes that can be deployed for the rapid detection of overdosage of over-the-counter and prescribed drugs. Significance The interaction between drugs and blood cells is an important field of study in order to understand the risk for drug-induced haematological adverse effects. Using digital holo-tomographic microscopy (DHTM), we can resolve the real-time effect of medications on the morphological and chemical properties of red blood cells with high spatial and temporal resolution and in a label-free manner. We show that our approach can be used as a haematology platform for the diagnosis of blood disorders and for monitoring the dose-dependent effect of prescribed and over-the-counter medications in a cost-effective manner, with significant implications for its applicability in resource-limited settings and in the field of personalized medicine.
了解非处方药对红细胞(RBCs)的剂量依赖性作用对血液学和数字病理学至关重要。然而,以无标记的方式连续记录RBCs的实时、药物诱导的纳米级形状变化是一项挑战。在这里,我们展示了数字全息断层扫描(DHTM)能够实时、无标记、浓度依赖性和时间依赖性地监测布洛芬对健康供体红细胞的影响。基于3D和4D折射率断层图像对RBC进行分割,并利用机器学习对其形状进行分类来检索其形态和化学参数。当布洛芬水溶液滴注在湿血上时,我们直接观察到红细胞膜上针状物的形成和运动,产生粗糙的膜棘细胞形式。在0.25-0.50mM的低浓度下,布洛芬诱导的形态变化是短暂的,但在高浓度(1.5-3mM)下,加香料的RBC保持长达1.5小时。分子模拟证实,高浓度的布洛芬分子聚集体显著破坏了红细胞膜的结构完整性和脂质秩序,但在低浓度的布洛芬下产生的影响可以忽略不计。尿素、过氧化氢和水溶液对RBCs影响的对照实验显示,无毛刺形成。我们的工作使用无标记显微镜阐明了RBCs的剂量依赖性化学效应,该显微镜可用于快速检测非处方药和处方药的过量使用。意义药物和血细胞之间的相互作用是一个重要的研究领域,以了解药物引起的血液学不良反应的风险。使用数字全息断层显微镜(DHTM),我们可以以高空间和时间分辨率,以无标记的方式,实时解决药物对红细胞形态和化学性质的影响。我们表明,我们的方法可以作为血液学平台,以成本效益高的方式诊断血液疾病,并监测处方药和非处方药的剂量依赖性效果,这对其在资源有限的环境和个性化医学领域的适用性具有重要意义。
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引用次数: 2
Efficient Preparation of a Magnetic Helical Carbon Nanomotor for Targeted Anticancer Drug Delivery 用于靶向抗癌药物递送的磁性螺旋碳纳米马达的高效制备
Q2 NANOSCIENCE & NANOTECHNOLOGY Pub Date : 2022-11-25 DOI: 10.1021/acsnanoscienceau.2c00042
Yanming Sun, Renjie Pan, Yuduo Chen, Yong Wang, Lei Sun, Neng Wang, Xing Ma* and Guo Ping Wang*, 

The applications of nanomotors in the biomedical field have been attracting extensive attention. However, it remains a challenge to fabricate nanomotors in a facile way and effectively load drugs for active targeted therapy. In this work, we combine the microwave heating method and chemical vapor deposition (CVD) to fabricate magnetic helical nanomotors efficiently. The microwave heating method can accelerate intermolecular movement, which converts kinetic energy into heat energy and shortens the preparation time of the catalyst used for carbon nanocoil (CNC) synthesis by 15 times. Fe3O4 nanoparticles are in situ nucleated on the CNC surface by the microwave heating method to fabricate magnetically driven CNC/Fe3O4 nanomotors. In addition, we achieved precise control of the magnetically driven CNC/Fe3O4 nanomotors through remote manipulation of magnetic fields. Anticancer drug doxorubicin (DOX) is then efficiently loaded onto the nanomotors via π–π stacking interactions. Finally, the drug-loaded CNC/Fe3O4@DOX nanomotor can accurately accomplish cell targeting under external magnetic field control. Under short-time irradiation of near-infrared light, DOX can be quickly released onto target cells to effectively kill the cells. More importantly, CNC/Fe3O4@DOX nanomotors allow for single-cell or cell-cluster-targeted anticancer drug delivery, providing a dexterous platform to potentially perform many medically relevant tasks in vivo. The efficient preparation method and application in drug delivery are beneficial for future industrial production and provide inspiration for advanced micro/nanorobotic systems using the CNC as a carrier for a wide range of biomedical applications.

纳米电机在生物医学领域的应用引起了人们的广泛关注。然而,以一种简单的方式制造纳米马达并有效地装载用于主动靶向治疗的药物仍然是一个挑战。在这项工作中,我们将微波加热方法和化学气相沉积(CVD)相结合,有效地制备了磁性螺旋纳米电机。微波加热方法可以加速分子间运动,将动能转化为热能,并将用于碳纳米线圈(CNC)合成的催化剂的制备时间缩短15倍。采用微波加热的方法在CNC表面原位成核Fe3O4纳米颗粒,制备了磁驱动的CNC/Fe3O4纳米粒子电机。此外,我们还通过磁场的远程操作实现了对磁驱动CNC/Fe3O4纳米电机的精确控制。抗癌药物阿霉素(DOX)通过π–π堆叠相互作用有效地负载到纳米马达上。最后,装有药物的CNC/Fe3O4@DOX纳米电机可以在外部磁场控制下准确地实现细胞靶向。在近红外光的短时间照射下,DOX可以快速释放到靶细胞上,有效杀死细胞。更重要的是,CNC/Fe3O4@DOX纳米马达允许单细胞或细胞簇靶向抗癌药物递送,为在体内执行许多医学相关任务提供了一个灵活的平台。高效的制备方法和在药物递送中的应用有利于未来的工业生产,并为使用CNC作为载体的先进微/纳米机器人系统提供了灵感,用于广泛的生物医学应用。
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引用次数: 3
Intermetallic Nanoarchitectures for Efficient Electrocatalysis 高效电催化的金属间纳米结构
Q2 NANOSCIENCE & NANOTECHNOLOGY Pub Date : 2022-11-02 DOI: 10.1021/acsnanoscienceau.2c00045
Ho Young Kim, Minki Jun, Sang Hoon Joo* and Kwangyeol Lee*, 

Intermetallic structures whose regular atomic arrays of constituent elements present unique catalytic properties have attracted considerable attention as efficient electrocatalysts for energy conversion reactions. Further performance enhancement in intermetallic catalysts hinges on constructing catalytic surfaces possessing high activity, durability, and selectivity. In this Perspective, we introduce recent endeavors to boost the performance of intermetallic catalysts by generating nanoarchitectures, which have well-defined size, shape, and dimension. We discuss the beneficial effects of nanoarchitectures compared with simple nanoparticles in catalysis. We highlight that the nanoarchitectures have high intrinsic activity owing to their inherent structural factors, including controlled facets, surface defects, strained surfaces, nanoscale confinement effects, and a high density of active sites. We next present notable examples of intermetallic nanoarchitectures, namely, facet-controlled intermetallic nanocrystals and multidimensional nanomaterials. Finally, we suggest the future research directions of intermetallic nanoarchitectures.

其组成元素的规则原子阵列具有独特催化性能的金属间结构作为用于能量转换反应的有效电催化剂已经引起了相当大的关注。金属间催化剂性能的进一步提高取决于构建具有高活性、耐久性和选择性的催化表面。从这个角度来看,我们介绍了最近通过生成具有明确尺寸、形状和尺寸的纳米结构来提高金属间催化剂性能的努力。我们讨论了纳米结构与简单纳米颗粒相比在催化方面的有益效果。我们强调,由于其固有的结构因素,包括可控的晶面、表面缺陷、应变表面、纳米级限制效应和高密度的活性位点,纳米结构具有高的固有活性。接下来,我们将介绍金属间纳米结构的显著例子,即面控金属间纳米晶体和多维纳米材料。最后,提出了金属间纳米结构的研究方向。
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引用次数: 4
Significance of an Electrochemical Sensor and Nanocomposites: Toward the Electrocatalytic Detection of Neurotransmitters and Their Importance within the Physiological System 电化学传感器和纳米复合材料的意义:神经递质电催化检测及其在生理系统中的重要性
Q2 NANOSCIENCE & NANOTECHNOLOGY Pub Date : 2022-10-28 DOI: 10.1021/acsnanoscienceau.2c00039
Harjot Kaur, Samarjeet Singh Siwal*, Reena V. Saini, Nirankar Singh and Vijay Kumar Thakur*, 

A prominent neurotransmitter (NT), dopamine (DA), is a chemical messenger that transmits signals between one neuron to the next to pass on a signal to and from the central nervous system (CNS). The imbalanced concentration of DA may cause numerous neurological sicknesses and syndromes, for example, Parkinson’s disease (PD) and schizophrenia. There are many types of NTs in the brain, including epinephrine, norepinephrine (NE), serotonin, and glutamate. Electrochemical sensors have offered a creative direction to biomedical analysis and testing. Researches are in progress to improve the performance of sensors and develop new protocols for sensor design. This review article focuses on the area of sensor growth to discover the applicability of polymers and metallic particles and composite materials as tools in electrochemical sensor surface incorporation. Electrochemical sensors have attracted the attention of researchers as they possess high sensitivity, quick reaction rate, good controllability, and instantaneous detection. Efficient complex materials provide considerable benefits for biological detection as they have exclusive chemical and physical properties. Due to distinctive electrocatalytic characteristics, metallic nanoparticles add fascinating traits to materials that depend on the material’s morphology and size. Herein, we have collected much information on NTs and their importance within the physiological system. Furthermore, the electrochemical sensors and corresponding techniques (such as voltammetric, amperometry, impedance, and chronoamperometry) and the different types of electrodes’ roles in the analysis of NTs are discussed. Furthermore, other methods for detecting NTs include optical and microdialysis methods. Finally, we show the advantages and disadvantages of different techniques and conclude remarks with future perspectives.

一种重要的神经递质(NT),多巴胺(DA),是一种化学信使,在一个神经元与另一个神经元之间传递信号,将信号传递给中枢神经系统(CNS)。DA浓度不平衡可能导致许多神经系统疾病和综合征,例如帕金森病(PD)和精神分裂症。大脑中有许多类型的NT,包括肾上腺素、去甲肾上腺素(NE)、血清素和谷氨酸。电化学传感器为生物医学分析和测试提供了一个创造性的方向。提高传感器性能和开发新的传感器设计协议的研究正在进行中。这篇综述文章聚焦于传感器生长领域,以发现聚合物、金属颗粒和复合材料作为电化学传感器表面结合工具的适用性。电化学传感器具有灵敏度高、反应速度快、可控性好、检测速度快等特点,引起了研究人员的关注。高效的复杂材料具有独特的化学和物理特性,为生物检测提供了相当大的好处。由于独特的电催化特性,金属纳米颗粒为材料添加了迷人的特性,这些特性取决于材料的形态和尺寸。在此,我们收集了许多关于NT及其在生理系统中的重要性的信息。此外,还讨论了电化学传感器和相应的技术(如伏安法、电流法、阻抗法和计时电流法)以及不同类型的电极在NTs分析中的作用。此外,检测NT的其他方法包括光学和微透析方法。最后,我们展示了不同技术的优缺点,并对未来的发展前景进行了总结。
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引用次数: 19
Self-Induced Core–Shell InAlN Nanorods: Formation and Stability Unraveled by Ab Initio Simulations 自诱导核壳纳米棒:由从头算模拟揭示的形成和稳定性
Q2 NANOSCIENCE & NANOTECHNOLOGY Pub Date : 2022-10-28 DOI: 10.1021/acsnanoscienceau.2c00041
Manoel Alves Machado Filho, Ching-Lien Hsiao, Renato Batista dos Santos, Lars Hultman, Jens Birch and Gueorgui K. Gueorguiev*, 

By addressing precursor prevalence and energetics using the DFT-based synthetic growth concept (SGC), the formation mechanism of self-induced InAlN core–shell nanorods (NRs) synthesized by reactive magnetron sputter epitaxy (MSE) is explored. The characteristics of In- and Al-containing precursor species are evaluated considering the thermal conditions at a typical NR growth temperature of around 700 °C. The cohesive and dissociation energies of In-containing precursors are consistently lower than those of their Al-containing counterparts, indicating that In-containing precursors are more weakly bonded and more prone to dissociation. Therefore, In-containing species are expected to exhibit lower abundance in the NR growth environment. At increased growth temperatures, the depletion of In-based precursors is even more pronounced. A distinctive imbalance in the incorporation of Al- and In-containing precursor species (namely, AlN/AlN+, AlN2/AlN2+, Al2N2/Al2N2+, and Al2/Al2+ vs InN/InN+, InN2/InN2+, In2N2/In2N2+, and In2/In2+) is found at the growing edge of the NR side surfaces, which correlates well with the experimentally obtained core–shell structure as well as with the distinctive In-rich core and vice versa for the Al-rich shell. The performed modeling indicates that the formation of the core–shell structure is substantially driven by the precursors’ abundance and their preferential bonding onto the growing edge of the nanoclusters/islands initiated by phase separation from the beginning of the NR growth. The cohesive energies and the band gaps of the NRs show decreasing trends with an increment in the In concentration of the NRs’ core and with an increment in the overall thickness (diameter) of the NRs. These results reveal the energy and electronic reasons behind the limited growth (up to ∼25% of In atoms of all metal atoms, i.e., InxAl1–xN, x ∼ 0.25) in the NR core and may be qualitatively perceived as a limiting factor for the thickness of the grown NRs (typically <50 nm).

通过使用基于DFT的合成生长概念(SGC)解决前驱体的普遍性和能量学问题,探索了通过反应磁控溅射外延(MSE)合成的自诱导InAlN核壳纳米棒(NRs)的形成机制。考虑到在700°C左右的典型NR生长温度下的热条件,评估了含In和Al前体物种的特性。含In的前体的内聚能和离解能始终低于含Al的前体,这表明含In的前驱体结合更弱,更容易离解。因此,含In物种在NR生长环境中表现出较低的丰度。在生长温度升高的情况下,铟基前体的损耗更加明显。在NR侧表面的生长边缘处发现含Al和in的前体物种(即AlN/AlN+、AlN2/AlN2+、Al2N2/Al2N2+和Al2/Al2+与InN/InN+、InN2/InN2+、In2N2/In2N2+和In2/In2+)的掺入的明显不平衡,这与实验获得的核-壳结构以及独特的富In核密切相关,反之亦然。所进行的建模表明,核壳结构的形成基本上是由前体的丰度及其在纳米团簇/岛的生长边缘上的优先键合驱动的,这是由NR生长开始的相分离引发的。NRs的内聚能和带隙随着NRs核心in浓度的增加和NRs总厚度(直径)的增加而呈下降趋势。这些结果揭示了NR核中有限生长(所有金属原子的In原子高达~25%,即InxAl1–xN,x~0.25)背后的能量和电子原因,并且可以定性地视为生长的NR厚度的限制因素(通常<;50 nm)。
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引用次数: 14
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ACS Nanoscience Au
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