nanothermometer

纳米温度计
  • 文章类型: Journal Article
    需要在生物透明窗口内操作的非接触式光学纳米温度计来研究纳米级的温度敏感生物学现象。据报道,含有Nd3等稀土离子的纳米颗粒是有效的基于发光的比率温度计,然而,通常受到水溶性差和浓度相关的猝灭效应的限制。在这里,我们推出了一种新型的纳米温度计,通过使用低维碳纳米点(CND)作为基质来承载Nd3离子(NdCND)而获得。通过一锅法,小(〜7-12nm),获得水溶性纳米颗粒,具有高(15重量%)Nd3+负载。这种稳定的金属-CND系统在808nm照射时,在第二个生物窗口(BWII)中具有温度依赖性光致发光,从而允许准确和可逆的(加热/冷却)温度测量具有良好的灵敏度和热分辨率。该系统在体外具有显着的生物相容性,并且在组织模型中具有高穿透深度的良好性能。
    Noncontact optical nanothermometers operating within the biological transparency windows are required to study temperature-sensitive biological phenomena at the nanoscale. Nanoparticles containing rare-earth ions such as Nd3+ have been reported to be efficient luminescence-based ratiometric thermometers, however often limited by poor water solubility and concentration-related quenching effects. Herein, we introduce a new type of nanothermometer, obtained by employing low-dimensional carbon nanodots (CNDs) as matrices to host Nd3+ ions (NdCNDs). By means of a one-pot procedure, small (∼7-12 nm), water-soluble nanoparticles were obtained, with high (15 wt %) Nd3+ loading. This stable metal-CND system features temperature-dependent photoluminescence in the second biological window (BW II) upon irradiation at 808 nm, thereby allowing accurate and reversible (heating/cooling) temperature measurements with good sensitivity and thermal resolution. The system possesses remarkable biocompatibility in vitro and promising performance at a high penetration depth in tissue models.
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  • 文章类型: Journal Article
    在纳米和微观尺度上有效测量生命系统中的温度仍然是一个挑战。这里,我们研究了使用2-(蒽-2-基)-1,3-二异丙基胍,1,作为基于荧光寿命测量的纳米温度计及其生物成像应用。在水溶液中,图1以聚集形式示出,并且两种主要聚集体类型(T形和π-π)之间的平衡对温度高度敏感。介质的加热使平衡朝向高度发射的T形聚集体的形成移动。与π-π聚集体和自由单体相比,该物种显示出高荧光发射和长寿命。在水溶液和合成的细胞内缓冲液中,荧光寿命与温度之间均呈线性关系。荧光寿命成像显微镜(FLIM)还显示了寿命与温度之间的线性关系,在MCF7乳腺癌细胞中具有优异的灵敏度,这为其在生物医学领域作为FLIM纳米温度计的潜在用途打开了大门。
    The effective measurement of temperature in living systems at the nano and microscopic scales continues to be a challenge to this day. Here, we study the use of 2-(anthracen-2-yl)-1,3-diisopropylguanidine, 1, as a nanothermometer based on fluorescence lifetime measurements and its bioimaging applications. In aqueous solution, 1 is shown in aggregated form and the equilibrium between the two main aggregate types (T-shaped and π-π) is highly sensitive to the temperature. The heating of the medium shifts the equilibrium toward the formation of highly emissive T-shaped aggregates. This species shows a high fluorescence emission and a long lifetime in comparison with the π-π aggregates and the freé monomer. A linear relationship between the fluorescence lifetime and the temperature both in aqueous solution and in a synthetic intracellular buffer was found. Fluorescence lifetime imaging microscopy (FLIM) also showed a linear relationship between lifetime and temperature with an excellent sensitivity in MCF7 breast cancer cells, which opens the door for its potential use as FLIM nanothermometer in the biomedical field.
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  • 文章类型: Journal Article
    近红外荧光(NIRF)测温是一种新兴的非接触式测量体内深层温度的方法。基于荧光寿命的方法是有效的,因为它们不受由于激发或检测路径引起的光学损失的影响。此外,深部组织中体温的生理变化及其药理作用尚待充分探索。在这项研究中,我们研究了基于NIRF寿命的方法在使用稀土基颗粒材料测量腹部体内深部组织温度的潜在应用。与Nd3和Yb3共掺杂的β-NaYF4颗粒(激发:808nm,发射:980nm)用作NIRF温度计,它们的荧光衰减曲线是指数的。斜率线性分析(SLA),一种筛选方法,提出用有效数据提取像素。该方法涉及对在切断脉冲激光照射后的三个延迟时间处收集的衰减曲线的半对数图进行线性评估。胃内给药温度计后,采用NIRF时间门控成像装置监测胃温.同时,在麻醉下将加热器连接到小鼠的下腹部。麻醉下胃温度的降低及其通过加热器的恢复表明放置在体内的温度计的荧光寿命的变化。因此,NaYF4:Nd3+/Yb3+用作荧光温度计,其可以基于在808nm激发下在980nm处的荧光寿命的温度依赖性来测量体内温度。这项研究证明了基于稀土的NIRF温度计能够测量活体小鼠的深层组织,使用拟议的SLA方法,可以从使用稀土温度计的NIRF寿命测量温度的分析中排除噪声偏差。
    Near-infrared fluorescence (NIRF) thermometry is an emerging method for the noncontact measurement of in vivo deep temperatures. Fluorescence-lifetime-based methods are effective because they are unaffected by optical loss due to excitation or detection paths. Moreover, the physiological changes in body temperature in deep tissues and their pharmacological effects are yet to be fully explored. In this study, we investigated the potential application of the NIRF lifetime-based method for temperature measurement of in vivo deep tissues in the abdomen using rare-earth-based particle materials. β-NaYF4 particles codoped with Nd3+ and Yb3+ (excitation: 808 nm, emission: 980 nm) were used as NIRF thermometers, and their fluorescence decay curves were exponential. Slope linearity analysis (SLA), a screening method, was proposed to extract pixels with valid data. This method involves performing a linearity evaluation of the semilogarithmic plot of the decay curve collected at three delay times after cutting off the pulsed laser irradiation. After intragastric administration of the thermometer, the stomach temperature was monitored by using an NIRF time-gated imaging setup. Concurrently, a heater was attached to the lower abdomens of the mice under anesthesia. A decrease in the stomach temperature under anesthesia and its recovery via the heater indicated changes in the fluorescence lifetime of the thermometer placed inside the body. Thus, NaYF4:Nd3+/Yb3+ functions as a fluorescence thermometer that can measure in vivo temperature based on the temperature dependence of the fluorescence lifetime at 980 nm under 808 nm excitation. This study demonstrated the ability of a rare-earth-based NIRF thermometer to measure deep tissues in live mice, with the proposed SLA method for excluding the noisy deviations from the analysis for measuring temperature using the NIRF lifetime of a rare-earth-based thermometer.
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  • 文章类型: Journal Article
    用于开发高灵敏度且不含潜在有毒金属的纳米温度计的发光纳米材料的设计已经在多个领域发展起来,比如光电子,传感器,和生物成像。此外,发光纳米温度计具有与非侵入性测量相关的优点,具有广泛的检测范围和纳米/微米尺度的高空间分辨率。我们的研究是第一个,根据我们的知识,以证明基于源自柠檬渣提取物(CD-L)的碳点的荧光膜(薄膜-L)热传感器的详细研究。探索CD-L特性作为抗氧化剂;通过使用来自MTT测定的人非肿瘤皮肤成纤维细胞(HFF-1)细胞系评估其细胞毒性。CD-L用HRTEM表征,DLS,FTIR,UV-VIS,和荧光光谱。这些证实了它们的粒度分布低于10nm,核心和表面有机基团中的石墨结构,和强烈的蓝色发射。CD-L显示出细胞相容性行为和清除生物学重要性的潜在反应性物质:O2•-和HOCl,IC50分别为276.8±4.0和21.6±0.7。薄膜-L发射强度(I425nm)在298至333K范围内是温度依赖性的。薄膜-L发光温度计在333K时显示出2.69%K-1的最大相对热灵敏度。
    The design of luminescent nanomaterials for the development of nanothermometers with high sensitivity and free of potentially toxic metals has developed in several fields, such as optoelectronics, sensors, and bioimaging. In addition, luminescent nanothermometers have advantages related to non-invasive measurement, with their wide detection range and high spatial resolution at the nano/microscale. Our study is the first, to our knowledge, to demonstrate a detailed study of a fluorescent film (Film-L) thermal sensor based on carbon dots derived from lemon bagasse extract (CD-L). The CD-L properties were explored as an antioxidant agent; their cytotoxicity was evaluated by using a human non-tumoral skin fibroblast (HFF-1) cell line from an MTT assay. The CD-L were characterized by HRTEM, DLS, FTIR, UV-VIS, and fluorescence spectroscopy. These confirmed their particle size distribution below 10 nm, graphitic structure in the core and surface organic groups, and strong blue emission. The CD-L showed cytocompatibility behavior and scavenging potential reactive species of biological importance: O2•- and HOCl, with IC50 of 276.8 ± 4.0 and 21.6 ± 0.7, respectively. The Film-L emission intensities (I425 nm) are temperature-dependent in the 298 to 333 K range. The Film-L luminescent thermometer shows a maximum relative thermal sensitivity of 2.69 % K-1 at 333 K.
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  • 文章类型: Journal Article
    要成功实施,有效的转换,经济实惠的操作和高价值的CO2衍生产品的电化学转化CO2尚未得到解决。受天然CaO-CaCO3循环的启发,在此,我们将CaO引入在可负担的熔融CaCl2-NaCl中的SnO2的电解中,以建立CO2的原位捕获和转化。通过添加的CaO从石墨阳极原位捕获阳极CO2产生CaCO3。SnO2和CaCO3的后续共电解将Sn限制在阴极中的碳纳米管(Sn@CNT)中,并将石墨阳极中O2析出的电流效率提高到71.9%。中间的CaC2被验证为指导CNT自模板生成的核,确保CO2-CNT电流效率和能效分别为85.1%和44.8%,分别。Sn@CNT集成了Sn核心对外部电化学或热刺激的有限响应,具有坚固的CNT护套,导致优异的锂存储性能和作为纳米温度计的有趣应用。基于Ca的熔盐中CO2的熔盐电解用于高级碳材料的无模板生成的多功能性证明了纯CNT的成功生成,Zn@CNT和Fe@CNT。
    To be successfully implemented, an efficient conversion, affordable operation and high values of CO2 -derived products by electrochemical conversion of CO2 are yet to be addressed. Inspired by the natural CaO-CaCO3 cycle, we herein introduce CaO into electrolysis of SnO2 in affordable molten CaCl2 -NaCl to establish an in situ capture and conversion of CO2 . In situ capture of anodic CO2 from graphite anode by the added CaO generates CaCO3 . The consequent co-electrolysis of SnO2 and CaCO3 confines Sn in carbon nanotube (Sn@CNT) in cathode and increases current efficiency of O2 evolution in graphite anode to 71.9 %. The intermediated CaC2 is verified as the nuclei to direct a self-template generation of CNT, ensuring a CO2 -CNT current efficiency and energy efficiency of 85.1 % and 44.8 %, respectively. The Sn@CNT integrates confined responses of Sn cores to external electrochemical or thermal stimuli with robust CNT sheaths, resulting in excellent Li storage performance and intriguing application as nanothermometer. The versatility of the molten salt electrolysis of CO2 in Ca-based molten salts for template-free generation of advanced carbon materials is evidenced by the successful generation of pure CNT, Zn@CNT and Fe@CNT.
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  • 文章类型: Journal Article
    局部温度的准确测定是纳米技术和纳米医学领域最重要的挑战之一。为此,不同的技术和材料进行了广泛的研究,以确定性能最好的材料和技术具有最大的灵敏度。在这项研究中,拉曼技术作为非接触技术用于确定局部温度,并且二氧化钛纳米颗粒(NPs)作为纳米温度计拉曼活性材料进行了测试。根据溶胶-凝胶和溶剂热绿色合成方法的组合合成了生物相容性二氧化钛NP,目的是获得纯锐钛矿样品。特别是,三种不同合成方案的优化允许获得具有明确定义的微晶尺寸和对最终形态和分散性的良好控制的材料。通过X射线衍射(XRD)分析和室温拉曼测量对TiO2粉末进行了表征,为了确认合成的样品是单相锐钛矿二氧化钛,并使用SEM测量,这清楚地显示了NP的纳米尺寸。收集斯托克斯和反斯托克斯拉曼测量值,使用514.5nm的激发激光(CWAr/Kr离子激光),在293-323K的温度范围内,生物应用的兴趣范围。仔细选择激光的功率以避免由于激光照射而可能加热。数据支持评估局部温度的可能性,并表明TiO2NP作为拉曼纳米温度计材料在几度范围内具有高灵敏度和低不确定性。
    The accurate determination of the local temperature is one of the most important challenges in the field of nanotechnology and nanomedicine. For this purpose, different techniques and materials have been extensively studied in order to identify both the best-performing materials and the techniques with greatest sensitivity. In this study, the Raman technique was exploited for the determination of the local temperature as a non-contact technique and titania nanoparticles (NPs) were tested as nanothermometer Raman active material. Biocompatible titania NPs were synthesized following a combination of sol-gel and solvothermal green synthesis approaches, with the aim of obtaining pure anatase samples. In particular, the optimization of three different synthesis protocols allowed materials to be obtained with well-defined crystallite dimensions and good control over the final morphology and dispersibility. TiO2 powders were characterized by X-ray diffraction (XRD) analyses and room-temperature Raman measurements, to confirm that the synthesized samples were single-phase anatase titania, and using SEM measurements, which clearly showed the nanometric dimension of the NPs. Stokes and anti-Stokes Raman measurements were collected, with the excitation laser at 514.5 nm (CW Ar/Kr ion laser), in the temperature range of 293-323 K, a range of interest for biological applications. The power of the laser was carefully chosen in order to avoid possible heating due to the laser irradiation. The data support the possibility of evaluating the local temperature and show that TiO2 NPs possess high sensitivity and low uncertainty in the range of a few degrees as a Raman nanothermometer material.
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  • 文章类型: Journal Article
    传感温度在生物系统中非常重要,因为它对理解各种生理和病理过程具有建设性。然而,用有机荧光纳米温度计实现高灵敏度的温度传感仍然具有挑战性。在这项研究中,我们报道了一种比例荧光纳米凝胶温度计,并研究了其在杀菌温度测定中的应用。纳米凝胶由具有双重发射的极性敏感的聚集诱导的发光剂组成,具有相变功能的热响应性聚合物,和带有净正电荷的离子表面。在温度诱导的相变过程中,纳米凝胶通过响应局部环境中的亲水到疏水变化而在红色发射状态和蓝色发射状态之间表现出可逆和敏感的光谱变化。微妙地建立了两种状态的发射强度比与外部温度之间的相关性,并确定最佳纳米凝胶在水中和模拟生理环境中的最大相对热敏感性为128.42和68.39%°C-1,分别。纳米凝胶进一步用于以视觉和比率方式指示杀菌温度,在快速预测光热抗菌效应和其他与温度相关的生物事件方面具有很大的前景。
    Sensing temperature in biological systems is of great importance, as it is constructive to understanding various physiological and pathological processes. However, the realization of highly sensitive temperature sensing with organic fluorescent nanothermometers remains challenging. In this study, we report a ratiometric fluorescent nanogel thermometer and study its application in the determination of bactericidal temperature. The nanogel is composed of a polarity-sensitive aggregation-induced emission luminogen with dual emissions, a thermoresponsive polymer with a phase transition function, and an ionic surface with net positive charges. During temperature-induced phase transition, the nanogel exhibits a reversible and sensitive spectral change between a red-emissive state and a blue-emissive state by responding to the hydrophilic-to-hydrophobic change in the local environment. The correlation between the emission intensity ratio of the two states and the external temperature is delicately established, and the maximum relative thermal sensitivities of the optimal nanogel are determined to be 128.42 and 68.39% °C-1 in water and a simulated physiological environment, respectively. The nanogel is further applied to indicate the bactericidal temperature in both visual and ratiometric ways, holding great promise in the rapid prediction of photothermal antibacterial effects and other temperature-related biological events.
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  • 文章类型: Journal Article
    纳米级酶的热行为对生命现象具有重要意义。通过现有方法无法准确检测纳米级酶的这种非平衡状态实时热行为。在这里,开发了一种新的方法来检测这种热行为。酶-量子点(QD)缀合物可以通过将温度敏感的氨基-AgInS2QD化学接枝到酶上获得,其中QD充当灵敏度为-2.82%°C-1的纳米温度计。检测酶-QD缀合物的光致发光强度变化,可以获得酶的实时热行为。在催化过程中,酶-QD缀合物在纳米微区显示出比环境温度高6°C的温度差,具有良好的可重复性(最大误差为4%),而溶液温度几乎不变。该方法的温度分辨率约为0.5°C,检测限为0.02mgmL-1的酶,并在空间上确保氨基-AgInS2QDs与酶定量结合;因此,它可以准确地检测酶的放热行为,并可以扩展到其他生物体的检测。该方法灵敏度高,稳定性好,和可靠性,表明其在纳米尺度和相关生命现象中研究生物的热行为方面具有巨大的潜在应用价值。
    The thermal behavior of enzymes in nanoscale is of great significance to life phenomena. This nonequilibrium state real-time thermal behavior of enzymes at nanoscale cannot be accurately detected by existing methods. Herein, a novel method is developed for the detection of this thermal behavior. The enzyme-quantum dot (QD) conjugates can be obtained by chemically grafting temperature-sensitive amino-AgInS2 QDs to the enzyme, where the QDs act as nanothermometers with a sensitivity of -2.82% °C-1 . Detecting the photoluminescence intensity changes of the enzyme-QD conjugates, the real-time thermal behavior of enzymes can be obtained. The enzyme-QD conjugates show a temperature difference as high as 6 °C above ambient temperature in nano-microregions with good reproducibility (maximum error of 4%) during catalysis, while solution temperature hardly changed. This method has a temperature resolution of ≈0.5 °C with a detection limit of 0.02 mg mL-1 of enzyme, and spatially ensured that the amino-AgInS2 QDs are quantitatively bound to the enzyme; thus, it can accurately detect the exothermic behavior of the enzyme and can be extended to other organisms\' detection. This method has high sensitivity, good stability, and reliability, indicating its great potential application in investigating the thermal behavior of organisms in nanoscale and related life phenomena.
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  • 文章类型: Journal Article
    鉴于金纳米簇(AuNC)的许多有前途的应用,纳米测温是生物学和医学研究的一个重要领域。这里,通过使用稳态和时间分辨光致发光光谱,我们证明了高度发光的绿色发射6-氮杂-2-硫代胺/l-精氨酸稳定的Au纳米簇(ATT/ArgAuNC)的温度依赖性光物理性质。重要的是,这些高度光稳定和生物相容性AuNC的热响应特性是可逆的,这使该探针在进一步的生物分析应用中具有广阔的前景。此外,已经在体外和体内阐明了蛋白质-NC相互作用机制,该机制决定了NC与活生物体的复杂行为。如从共聚焦激光扫描显微镜(CLSM)所证明的,这些超小的AuNC通过易位穿过膜而在细胞质中积累。通过使用荧光寿命成像显微镜(FLIM)技术对人骨肉瘤细胞系(MG-63细胞)进行的体内温度传感检查揭示了这些基于寿命的纳米传感器在生物医学和生物技术中的乐观应用。
    In view of many promising applications of gold nanoclusters (AuNCs), nanothermometry is an important field of research in biology and medicine. Here, we demonstrate the temperature dependent photophysical properties of highly luminescent green emitting 6-aza-2-thiothymine/l-arginine-stabilized Au nanosclusters (ATT/Arg Au NCs) by using steady state and time-resolved photoluminescence spectroscopy. Significantly, thermoresponsive properties of these highly photostable and biocompatible Au NCs are reversible, which endow the probe for further bioanalytical applications with great prospects. Additionally, protein-NC interaction mechanism has been elucidated in vitro and in vivo that dictates the complex behavior of the NCs with living organisms. These ultrasmall Au NCs are observed to accumulate in the cellular cytoplasm by translocating through the membrane as evidenced from the confocal laser scanning microscopy (CLSM). In vivo temperature sensing examined with human osteosarcoma cell line (MG-63 cell) by employing fluorescence lifetime imaging microscopy (FLIM) technique reveals the optimistic application of these lifetime-based nanosensors in biomedicine and biotechnology.
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  • 文章类型: Journal Article
    掺杂有不同量的Nd3+的TiO2纳米颗粒(0.5、1和3wt。%)通过溶胶-凝胶法合成,并使用Nd3的热敏辐射跃迁之间的荧光强度比评估为潜在的温度纳米探针。XRD表征确定了所有掺杂样品中的锐钛矿相。用SEM观察纳米粒子的形貌,TEM和HRTEM显微镜。通过EDXS获得TiO2中Nd3+的相对量,并通过XPS和NEXAFS研究了钛和钕的氧化态,分别。Nd3+存在于所有样品中,与钛不同,除了Ti4+,观察到显著量的Ti3+;Ti3+的相对浓度随着TiO2纳米颗粒中Nd3+的量增加而增加。研究了合成纳米粒子的光致发光,350,514和600nm的激发波长。当Nd3浓度增加时,与TiO2中缺陷的存在有关的宽带的发射强度增加。使用600nm激发,Nd3+离子的4F7/2→4I9/2、4F5/2→4I9/2和4F3/2→4I9/2跃迁,以760nm为中心,821nm,和880纳米,分别,被观察到。最后,研究了温度对合成纳米粒子光致发光强度的影响,具有600nm的激发波长。在288-348K范围内收集光谱。为了提高温度,4F7/2→4I9/2和4F5/2→4I9/2跃迁的发射强度显著增加,与4F3/2→4I9/2过渡相反,其中强度发射下降。跃迁I821I880=F5/24I49/2F43/2I49/2和I760I880=F47/2I49/2F43/2I49/2之间的荧光强度比用于计算传感器的相对灵敏度。I760I880的相对灵敏度接近3%K-1,I821I880的相对灵敏度接近1%K-1。
    TiO2 nanoparticles doped with different amounts of Nd3+ (0.5, 1, and 3 wt.%) were synthetized by the sol-gel method, and evaluated as potential temperature nanoprobes using the fluorescence intensity ratio between thermal-sensitive radiative transitions of the Nd3+. XRD characterization identified the anatase phase in all the doped samples. The morphology of the nanoparticles was observed with SEM, TEM and HRTEM microscopies. The relative amount of Nd3+ in TiO2 was obtained by EDXS, and the oxidation state of titanium and neodymium was investigated via XPS and NEXAFS, respectively. Nd3+ was present in all the samples, unlike titanium, where besides Ti4+, a significantly amount of Ti3+ was observed; the relative concentration of Ti3+ increased as the amount of Nd3+ in the TiO2 nanoparticles increased. The photoluminescence of the synthetized nanoparticles was investigated, with excitation wavelengths of 350, 514 and 600 nm. The emission intensity of the broad band that was associated with the presence of defects in the TiO2, increased when the concentration of Nd3+ was increased. Using 600 nm for excitation, the 4F7/2→4I9/2, 4F5/2→4I9/2 and 4F3/2→4I9/2 transitions of Nd3+ ions, centered at 760 nm, 821 nm, and 880 nm, respectively, were observed. Finally, the effect of temperature in the photoluminescence intensity of the synthetized nanoparticles was investigated, with an excitation wavelength of 600 nm. The spectra were collected in the 288-348 K range. For increasing temperatures, the emission intensity of the 4F7/2→4I9/2 and 4F5/2→4I9/2 transitions increased significantly, in contrast to the 4F3/2→4I9/2 transition, in which the intensity emission decreased. The fluorescence intensity ratio between the transitions I821I880=F5/24I49/2F43/2I49/2 and I760I880=F47/2I49/2F43/2I49/2 were used to calculate the relative sensitivity of the sensors. The relative sensitivity was near 3% K-1 for I760I880 and near 1% K-1 for I821I880.
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