Single-walled carbon nanotubes

单壁碳纳米管
  • 文章类型: Journal Article
    光谱指纹已经成为一种强大的工具,它擅长识别化合物并破译细胞和工程纳米材料内的复杂相互作用。使用近红外(NIR)荧光光谱指纹结合机器学习技术,我们揭示了DNA功能化的单壁碳纳米管(DNA-SWCNT)和活的巨噬细胞之间的复杂相互作用,实现原位表型区分。利用拉曼显微镜,与M2和幼稚表型相比,我们在M1巨噬细胞中显示了统计学上更高的DNA-SWCNT摄取和显着更低的缺陷比。NIR荧光数据还表明,这些细胞类型的独特内体环境导致许多光学特征的显着差异。如发射峰强度,中心波长,和峰强度比。这些特征用作鉴定不同巨噬细胞表型的独特标记。我们进一步使用在SWCNT荧光数据上训练的支持向量机(SVM)模型来识别M1和M2巨噬细胞,实现了>95%的令人印象深刻的精度。最后,我们观察到DNA-SWCNT复合物的稳定性,受DNA序列长度的影响,是应用程序的关键考虑因素,例如使用AI技术进行细胞表型分析或映射内体内微环境。我们的发现表明,由于SWCNT在内体微环境中与生物分子的活性相互作用增加,例如GT6的较短DNA序列可提高模型准确性(>87%)。这项研究的意义扩展到基于纳米材料的细胞识别平台的开发,在实时监测体内细胞分化方面具有潜在的应用前景。
    Spectral fingerprinting has emerged as a powerful tool that is adept at identifying chemical compounds and deciphering complex interactions within cells and engineered nanomaterials. Using near-infrared (NIR) fluorescence spectral fingerprinting coupled with machine learning techniques, we uncover complex interactions between DNA-functionalized single-walled carbon nanotubes (DNA-SWCNTs) and live macrophage cells, enabling in situ phenotype discrimination. Utilizing Raman microscopy, we showcase statistically higher DNA-SWCNT uptake and a significantly lower defect ratio in M1 macrophages compared to M2 and naive phenotypes. NIR fluorescence data also indicate that distinctive intraendosomal environments of these cell types give rise to significant differences in many optical features, such as emission peak intensities, center wavelengths, and peak intensity ratios. Such features serve as distinctive markers for identifying different macrophage phenotypes. We further use a support vector machine (SVM) model trained on SWCNT fluorescence data to identify M1 and M2 macrophages, achieving an impressive accuracy of >95%. Finally, we observe that the stability of DNA-SWCNT complexes, influenced by DNA sequence length, is a crucial consideration for applications, such as cell phenotyping or mapping intraendosomal microenvironments using AI techniques. Our findings suggest that shorter DNA-sequences like GT6 give rise to more improved model accuracy (>87%) due to increased active interactions of SWCNTs with biomolecules in the endosomal microenvironment. Implications of this research extend to the development of nanomaterial-based platforms for cellular identification, holding promise for potential applications in real time monitoring of in vivo cellular differentiation.
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  • 文章类型: Journal Article
    聚合物包裹的单壁碳纳米管(SWNT)是获得高纯度半导体(sc)SWNT溶液的潜在方法。共轭聚合物(CP)可以选择性地分选具有不同手性的sc-SWNT,和聚合物侧链的结构影响这种分选能力。虽然已经进行了广泛的研究来修改物理,光学,通过侧链修饰和CP的电性能,这些修饰对sc-SWNTs分选效率的影响仍未得到充分研究。这项研究调查了将各种共轭侧链引入萘二酰亚胺基CP以创建双轴延伸的共轭模式。具有支链共轭侧链的CP(P3)表现出降低的聚集,提高了包裹能力,并形成了较大的高纯度sc-SWNTs束。掠入射X射线衍射分析证实,sc-SWNT和CPs之间的潜在相互作用是通过π-π堆叠发生的。使用P3/sc-SWNT制造的场效应晶体管器件表现出卓越的性能,具有4.72cm2V-1s-1的显著增强的空穴迁移率和高的耐久性/偏置稳定性。这些发现表明,双轴延伸的侧链修饰是通过使用CP提高sc-SWNT的分选效率和性能的有前途的策略。这一成就可以促进更高效和稳定的电子器件的开发。
    Polymer-wrapped single-walled carbon nanotubes (SWNTs) are a potential method for obtaining high-purity semiconducting (sc) SWNT solutions. Conjugated polymers (CPs) can selectively sort sc-SWNTs with different chiralities, and the structure of the polymer side chains influences this sorting capability. While extensive research has been conducted on modifying the physical, optical, and electrical properties of CPs through side-chain modifications, the impact of these modifications on the sorting efficiency of sc-SWNTs remains underexplored. This study investigates the introduction of various conjugated side chains into naphthalene diimide-based CPs to create a biaxially extended conjugation pattern. The CP with a branched conjugated side chain (P3) exhibits reduced aggregation, resulting in improved wrapping ability and the formation of larger bundles of high-purity sc-SWNTs. Grazing incidence X-ray diffraction analysis confirms that the potential interaction between sc-SWNTs and CPs occurs through π-π stacking. The field-effect transistor device fabricated with P3/sc-SWNTs demonstrates exceptional performance, with a significantly enhanced hole mobility of 4.72 cm2 V-1 s-1 and high endurance/bias stability. These findings suggest that biaxially extended side-chain modification is a promising strategy for improving the sorting efficiency and performance of sc-SWNTs by using CPs. This achievement can facilitate the development of more efficient and stable electronic devices.
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  • 文章类型: Journal Article
    具有发光氧缺陷的单壁碳纳米管(SWNT)的共价官能化增加了它们的亮度,并使它们能够用作光学生物传感器或荧光探针,用于在第二生物学窗口(NIR-II)中的体内成像。然而,由于反应条件的受限窗口或需要用紫外光进行受控照射,获得具有高亮度的发光缺陷对于当前的功能化方法是具有挑战性的。这里,我们报告了一种通过类似Fenton反应引入发光氧缺陷的方法,该方法使用良性且廉价的化学物质,无需光照。(6,5)用这种方法官能化的水分散体中的SWNT显示明亮的E11*发射(1105nm),其具有比原始E11发射高3.2倍的峰强度和3%的可再现的光致发光量子产率。官能化可以在很宽的反应参数范围内进行,甚至在高浓度(100mgL-1)下使用未分类的纳米管原料,获得大量明亮发光的SWNT。我们进一步发现,引入的氧缺陷在光照下重排,这提供了对氧缺陷的结构和动力学的额外见解。最后,具有氧缺陷的超短SWNT的功能化也能够实现高光致发光量子产率。在与生物相容性聚乙二醇化磷脂或单链DNA进行表面活性剂交换后,它们的优异发射特性得以保留,使其适用于体内NIR-II成像和多巴胺传感。
    The covalent functionalization of single-walled carbon nanotubes (SWNTs) with luminescent oxygen defects increases their brightness and enables their application as optical biosensors or fluorescent probes for in vivo imaging in the second-biological window (NIR-II). However, obtaining luminescent defects with high brightness is challenging with the current functionalization methods due to a restricted window of reaction conditions or the necessity for controlled irradiation with ultraviolet light. Here, we report a method for introducing luminescent oxygen defects via a Fenton-like reaction that uses benign and inexpensive chemicals without light irradiation. (6,5) SWNTs in aqueous dispersion functionalized with this method show bright E11* emission (1105 nm) with 3.2 times higher peak intensities than the pristine E11 emission and a reproducible photoluminescence quantum yield of 3%. The functionalization can be performed within a wide range of reaction parameters and even with unsorted nanotube raw material at high concentrations (100 mg L-1), giving access to large amounts of brightly luminescent SWNTs. We further find that the introduced oxygen defects rearrange under light irradiation, which gives additional insights into the structure and dynamics of oxygen defects. Finally, the functionalization of ultrashort SWNTs with oxygen defects also enables high photoluminescence quantum yields. Their excellent emission properties are retained after surfactant exchange with biocompatible pegylated phospholipids or single-stranded DNA to make them suitable for in vivo NIR-II imaging and dopamine sensing.
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  • 文章类型: Journal Article
    单壁碳纳米管(SWNT)具有强且稳定的近红外(nIR)荧光,可用于选择性检测目标分析物,即使在单分子水平上,通过改变它们的荧光强度或发射峰值波长。SWNT已被用作用于检测多种分析物的NIR光学传感器。然而,高成本,长制造时间,和较差的分布限制了将SWNT传感器固定在固体基材上的当前方法。最近,我们小组报告了一种高荧光产量的SWNT固定方案,长寿,荧光分布,和传感器响应,不幸的是,这个过程需要5天才能完成。在这里,我们报告了一种改进的方法来固定SWNT传感器,只需要2天,并导致更高的荧光强度,同时保持高水平的SWNT分布。我们对原始和新的合成方法进行了表面形态和化学成分测试,并比较了传感器的响应速率。这种将SWNT传感器连接到平台的新方法的开发允许在短短2天内创建传感系统,而不会牺牲原始传感器的有利特性。5天平台
    Single-walled carbon nanotubes (SWNT) have a strong and stable near-infrared (nIR) fluorescence that can be used to selectively detect target analytes, even at the single molecule level, through changes in either their fluorescence intensity or emission peak wavelength. SWNTs have been employed as NIR optical sensors for detecting a variety of analytes. However, high costs, long fabrication times, and poor distributions limit the current methods for immobilizing SWNT sensors on solid substrates. Recently, our group reported a protocol for SWNT immobilization with high fluorescence yield, longevity, fluorescence distribution, and sensor response, unfortunately this process takes 5 days to complete. Herein we report an improved method to immobilize SWNT sensors that only takes 2 days and results in higher fluorescence intensity while maintaining a high level of SWNT distribution. We performed surface morphology and chemical composition tests on the original and new synthesis methods and compared the sensor response rates. The development of this new method of attaching SWNT sensors to a platform allows for creation of a sensing system in just 2 days without sacrificing the advantageous characteristics of the original, 5-day platforms.
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  • 文章类型: Journal Article
    如今,可穿戴设备产生的不断增加的电磁波正在成为人类健康的新兴问题,因此,对可拉伸的电磁干扰(EMI)屏蔽材料的要求很高。大象树干能够抓住脆弱的植被和撕裂树木,这不仅归功于它们的肌肉,也归功于它们折叠的皮肤。灵感来自大象树干的皱纹皮肤,在这里,我们提出了一种基于单壁碳纳米管(SWCNT)的闪烁导电膜,用于多功能EMI应用。导电膜具有夹层结构,通过在拉伸的弹性乳胶圆柱形基材的两侧涂覆SWCNTs来制备。收缩引起的扭曲导电网络可以承受高达200%的拉伸应变。通常,当拉伸方向平行于电场的极化方向时,在200%的拉伸应变下,总的EMI屏蔽效率可以令人惊讶地从38.4增加到52.7dB。这主要是由SWCNT的连接增加造成的。此外,该薄膜在多个电压下也具有良好的焦耳加热性能,能够释放受伤关节的疼痛。这种独特的特性使得应变可调的多功能EMI屏蔽和可穿戴的热疗应用成为可能。
    Nowadays, the increasing electromagnetic waves generated by wearable devices are becoming an emerging issue for human health, so stretchable electromagnetic interference (EMI) shielding materials are highly demanded. Elephant trunks are capable of grabbing fragile vegetation and tearing trees thanks not only to their muscles but also to their folded skins. Inspired by the wrinkled skin of the elephant trunks, herein, we propose a winkled conductive film based on single-walled carbon nanotubes (SWCNTs) for multifunctional EMI applications. The conductive film has a sandwich structure, which was prepared by coating SWCNTs on both sides of the stretched elastic latex cylindrical substrate. The shrinking-induced winkled conductive network could withstand up to 200% tensile strain. Typically, when the stretching direction is parallel to the polarization direction of the electric field, the total EMI shielding effectiveness could surprisingly increase from 38.4 to 52.7 dB at 200% tensile strain. It is mainly contributed by the increased connection of the SWCNTs. In addition, the film also has good Joule heating performance at several voltages, capable of releasing pains in injured joints. This unique property makes it possible for strain-adjustable multifunctional EMI shielding and wearable thermotherapy applications.
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  • 文章类型: Journal Article
    近年来,有机小分子(OSM)和单壁碳纳米管(SWCNT)的复合材料作为柔性热电(TE)材料引起了人们的广泛关注。这里,我们合成了噻吩并[2',3\':4,5]噻吩并[3,2-b]噻吩并[2,3-d]噻吩(TTA)和2,6-二溴噻吩并[2\',3\':4,5]噻吩并[3,2-b]噻吩并[2,3-d]噻吩(TTA-2Br)并将其与SWCNT复合,获得热电TTA/SWCNT和TTA-2Br/SWCNT复合材料。发现吸电子Br基团的引入降低了TTA-2Br的最高分子轨道能级和带隙(Eg)。因此,OSM/SWCNT复合薄膜的塞贝克系数(S)和功率因数(PF)显著进步。此外,TTA-2Br和SWCNT之间合适的能量势垒有利于能量过滤效果,这进一步提高了40wt%TTA-2Br/SWCNT复合膜的热电性能,具有最佳的热电性能(室温下PF=242.59±9.42μWm-1K-2),良好的热稳定性,机械灵活性。此外,使用40重量%TTA-2Br/SWCNT复合膜和n型SWCNT膜制备的热电发电器(TEG)在20°C的温差下可产生102.8±7.4nW的输出功率。这项工作为制备具有显着增强的热电性能的OSM/SWCNT复合材料提供了新的见解。
    Composites of organic small molecules (OSMs) and single-walled carbon nanotubes (SWCNTs) have drawn great attention as flexible thermoelectric (TE) materials in recent years. Here, we synthesized thieno[2\',3\':4,5]thieno[3,2-b]thieno[2,3-d]thiophene (TTA) and 2,6-dibromothieno[2\',3\':4,5]thieno[3,2-b]thieno[2,3-d]thiophene (TTA-2Br) and compounded them with SWCNTs, obtaining thermoelectric TTA/SWCNT and TTA-2Br/SWCNT composites. The introduction of the electron-withdrawing Br group was found to decrease the highest molecular orbital energy level and bandgap (Eg) of TTA-2Br. As a result, the Seebeck coefficient (S) and power factor (PF) of the OSM/SWCNT composite films were significantly improved. Moreover, suitable energy barrier between TTA-2Br and SWCNTs facilitates the energy filtering effect, which further enhances thermoelectric properties of the 40 wt % TTA-2Br/SWCNT composite film with optimum thermoelectric properties (PF = 242.59 ± 9.42 μW m-1 K-2 at room temperature), good thermal stability, and mechanical flexibility. In addition, the thermoelectric generator (TEG) prepared using 40 wt % TTA-2Br/SWCNT composite films and n-type SWCNT films can generate an output power of 102.8 ± 7.4 nW at a temperature difference of 20 °C. This work provides new insights into the preparation of OSM/SWCNT composites with significantly enhanced thermoelectric properties.
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  • 文章类型: Journal Article
    程序性细胞死亡-配体1阳性(PD-L1)外泌体在癌症诊断和治疗领域中起着至关重要的作用。然而,由于生物标本的复杂性,再加上异质性,低折射率(RI),外泌体的表面覆盖密度不足,传统的表面等离子体共振(SPR)传感器仍不能满足临床检测要求。本研究利用单壁碳纳米管(SWCNT)的特殊电学和光学属性作为SPR传感的基底,从而显著增强灵敏度。此外,sp2杂交的SWCNT具有加载特定识别元件的能力。此外,通过Ti与磷酸盐基团的配位相互作用和Fe3O4的铁磁性,可以借助外部磁场实现复杂样品中有效的外泌体分离和富集。由于Fe3O4@TiO2的高质量和高RI,响应信号经历放大,从而进一步提高了SPR生物传感器的性能。用该方法构建的SPR生物传感器的线性范围为1.0×103至1.0×107颗粒/mL,检测限(LOD)为31.9颗粒/mL。在临床血清样本分析中,可以将癌症患者与曲线下面积(AUC)为0.9835的健康个体区分开。本研究不仅为外泌体直接检测建立了新的平台,而且为其他生物标志物的灵敏检测提供了新的视角。
    Programmed cell death-ligand 1 positive (PD-L1+) exosomes play a crucial role in the realm of cancer diagnosis and treatment. Nevertheless, due to the intricate nature of biological specimens, coupled with the heterogeneity, low refractive index (RI), and scant surface coverage density of exosomes, traditional surface plasmon resonance (SPR) sensors still do not meet clinical detection requirements. This study utilizes the exceptional electrical and optical attributes of single-walled carbon nanotubes (SWCNTs) as the substrate for SPR sensing, thereby markedly enhancing sensitivity. Furthermore, sp2 hybridized SWCNTs have the ability to load specific recognition elements. Additionally, through the coordination interaction of Ti with phosphate groups and the ferromagnetism of Fe3O4, efficient exosomes isolation and enrichment in complex samples are achievable with the aid of an external magnetic field. Owing to the high-quality and high-RI of Fe3O4@TiO2, the response signal experiences amplification, thus further improving the performance of the SPR biosensor. The linear range of the SPR biosensor constructed by this method is 1.0 × 103 to 1.0 × 107 particles/mL, with a limit of detection (LOD) of 31.9 particles/mL. In the analysis of clinical serum samples, cancer patients can be differentiated from healthy individuals with an Area Under Curve (AUC) of 0.9835. This study not only establishes a novel platform for exosomes direct detection but also offers new perspectives for the sensitive detection of other biomarkers.
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  • 文章类型: Journal Article
    单壁碳纳米管(SWCNT)具有可穿戴和柔性设备所需的优异的电子和机械性能。SWCNT膜的制备是制造各种器件的第一步。这项工作开发了一种可扩展且可行的方法,基于表面张力梯度诱导的Marangoni流,在水表面上组装SWCNT薄膜。薄膜具有40厘米×30厘米(可延伸)的大面积,可调厚度为15~150nm,高达96%的高透明度,和一个体面的导电性。它们准备直接转移到各种基材上,包括灵活的。柔性应变传感器是用柔性衬底上的膜制造的。这些传感器具有高灵敏度和可重复性。通过实现多功能人体运动传感,包括回应声音,监测动脉搏动,检测关节和肌肉动作,组装的SWCNT薄膜显示了在智能设备中应用的潜力。
    Single-walled carbon nanotubes (SWCNTs) present excellent electronic and mechanical properties desired in wearable and flexible devices. The preparation of SWCNT films is the first step for fabricating various devices. This work developed a scalable and feasible method to assemble SWCNT thin films on water surfaces based on Marangoni flow induced by surface tension gradient. The films possess a large area of 40 cm × 30 cm (extensible), a tunable thickness of 15∼150 nm, a high transparency of up to 96%, and a decent conductivity. They are ready to be directly transferred to various substrates, including flexible ones. Flexible strain sensors were fabricated with the films on flexible substrates. These sensors worked with high sensitivity and repeatability. By realizing multi-functional human motion sensing, including responding to voices, monitoring artery pulses, and detecting knuckle and muscle actions, the assembled SWCNT films demonstrated the potential for application in smart devices.
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  • 文章类型: Journal Article
    我们一直在通过主客体化学进行碳纳米管分离。在这里,一种新的大环主体分子,铜系留方形纳米球拍,是设计的,合成并应用于单壁碳纳米管(SWNT),用于基于直径的分离。铜离子和纳米球团的二吡喃部分之间的络合产生了Cu束缚的方形纳米球团,这被吸收所证实,拉曼和MALDI-TOF质谱。用纳米球拍和铜(II)提取SWNT后,发现原位形成的正方形Cu纳米颗粒将SWNT互锁以将其分散在2-丙醇中。在彻底洗涤提取的SWNT之后,通过拉曼光谱确认互锁。通过将互锁的SWNT与纳米球拍一起脱金属来回收原始SWNT。提取的SWNT的拉曼光谱和吸收光谱表明,在其直径范围为0.76至1.20nm的≈20种SWNT中,只有几种直径范围为0.94至1.10nm的SWNT的直径富集。GFN2-xTB方法的理论计算支持了直径选择性,这表明正方形Cu纳米片的最优选SWNT直径为1.04nm。
    We have been working with carbon nanotube separation through host-guest chemistry. Herein, a new macrocyclic host molecule, Cu-tethered square nanobrackets, is designed, synthesized and applied to single-walled carbon nanotubes (SWNTs) for their diameter-based separation. The complexation between copper ions and dipyrrin moieties of the nanobracket gives Cu-tethered square nanobrackets, which is confirmed by absorption, Raman and MALDI-TOF mass spectra. Upon extraction of SWNTs with the nanobracket and copper(II), in situ-formed square Cu-nanobrackets are found to interlock SWNTs to disperse them in 2-propanol. The interlocking is confirmed by Raman spectroscopy after thorough washing of the extracted SWNTs. Pristine SWNTs were recovered through demetalation of the interlocked ones along with the nanobracket. Raman and absorption spectroscopies of the extracted SWNTs reveals the diameter enrichment of only several kinds of SWNTs in the diameter range from 0.94 to 1.10 nm among ≈20 kinds of SWNTs from 0.76 to 1.20 nm in their diameter range. The diameter selectivity is supported by the theoretical calculations with the GFN2-xTB method, indicating that the most preferred SWNT diameter for the square Cu-nanobrackets is 1.04 nm.
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  • 文章类型: Journal Article
    由芴基甲氧羰基(Fmoc)结合的氨基酸和肽衍生的水凝胶在生物医学应用中显示出巨大的潜力。包括药物输送,组织再生,和组织工程。这些水凝胶可以是可注射的,提供水凝胶植入的微创方法。鉴于其长期应用的潜力,有必要对其性能进行长期的无损评估。因此,我们介绍了采用单壁碳纳米管(SWCNT)作为近红外(NIR)荧光探针的水凝胶表征平台。我们的方法涉及从芳族Fmoc-氨基酸产生超分子自组装水凝胶。将SWCNT整合到水凝胶中保持其结构和机械性能,建立SWCNT作为水凝胶的光学探针。我们证明了在凝胶化过程中SWCNTNIR荧光变化与水凝胶内的流变变化相关。此外,掺入水凝胶中的SWCNT的单颗粒追踪提供了对水凝胶形态差异的见解。此外,水凝胶的分解过程可以通过SWCNT荧光调制来监测。SWCNT作为非光漂白荧光传感器的独特属性,在生物透明的窗口发射,为长期研究水凝胶动力学提供了一种非破坏性方法。该平台可应用于广泛的自组装水凝胶,以促进我们对超分子组装技术的理解和应用。
    Hydrogels derived from fluorenylmethoxycarbonyl (Fmoc)-conjugated amino acids and peptides demonstrate remarkable potential in biomedical applications, including drug delivery, tissue regeneration, and tissue engineering. These hydrogels can be injectable, offering a minimally invasive approach to hydrogel implantation. Given their potential for prolonged application, there is a need for non-destructive evaluation of their properties over extended periods. Thus, we introduce a hydrogel characterization platform employing single-walled carbon nanotubes (SWCNTs) as near-infrared (NIR) fluorescent probes. Our approach involves generating supramolecular self-assembling hydrogels from aromatic Fmoc-amino acids. Integrating SWCNTs into the hydrogels maintains their structural and mechanical properties, establishing SWCNTs as optical probes for hydrogels. We demonstrate that the SWCNT NIR-fluorescence changes during the gelation process correlate to rheological changes within the hydrogels. Additionally, single particle tracking of SWCNTs incorporated in the hydrogels provides insights into differences in hydrogel morphologies. Furthermore, the disassembly process of the hydrogels can be monitored through the SWCNT fluorescence modulation. The unique attribute of SWCNTs as non-photobleaching fluorescent sensors, emitting at the biologically transparent window, offers a non-destructive method for studying hydrogel dynamics over extended periods. This platform could be applied to a wide range of self-assembling hydrogels to advance our understanding and applications of supramolecular assembly technologies.
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