chromophore

发色团
  • 文章类型: Journal Article
    高性能电光材料的制备是决定5G通信等光电通信技术应用的关键因素之一,雷达探测,太赫兹,和电光调制器。有机电光材料具有高电光系数(〜1000pm/V)的优点,可以利用光子器件进行电子学和光子学的芯片级集成,与无机电光材料相比。然而,有机非线性光学材料在商用电光调制器等领域的应用也面临着技术瓶颈。获得具有大电光系数(r33值)的有机电光发色团,热稳定性,而长期稳定仍是行业的难点。这篇简要综述总结了最近的重大进展以及获得具有高电光系数和/或强长期稳定性的高性能OEO材料的策略。D-π-A结构的构型,材料的种类,详细总结了分子工程对发色团电光系数和玻璃化转变温度的影响。还讨论了有机电光材料在实际应用中的难点和未来的发展趋势。
    The preparation of high-performance electro-optical materials is one of the key factors determining the application of optoelectronic communication technology such as 5G communication, radar detection, terahertz, and electro-optic modulators. Organic electro-optic materials have the advantage of a high electro-optic coefficient (~1000 pm/V) and could allow the utilization of photonic devices for the chip-scale integration of electronics and photonics, as compared to inorganic electro-optic materials. However, the application of organic nonlinear optical materials to commercial electro-optic modulators and other fields is also facing technical bottlenecks. Obtaining an organic electro-optic chromophore with a large electro-optic coefficient (r33 value), thermal stability, and long-term stability is still a difficulty in the industry. This brief review summarizes recent great progress and the strategies to obtain high-performance OEO materials with a high electro-optic coefficient and/or strong long-term stability. The configuration of D-π-A structure, the types of materials, and the effects of molecular engineering on the electro-optical coefficient and glass transition temperature of chromophores were summarized in detail. The difficulties and future development trends in the practical application of organic electro-optic materials was also discussed.
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  • 文章类型: Journal Article
    α-二羰基与铵或胺的水相反应已被确定为仲棕碳(BrC)的重要来源。然而,在这些反应中大多数发色团的身份和pH的影响仍然很大程度上未知。在这项研究中,化学结构,形成途径,和通过α-二羰基(乙二醛和甲基乙二醛)与铵的水性反应形成的单个BrC发色团的光学性质,氨基酸,通过液相色谱-光电二极管阵列-高分辨率串联质谱对不同pH值的甲胺进行了详细表征。总的来说,鉴定出180个发色团,占不同反应的散装BrC光吸收的29-79%。其中,155个新发现的发色团,包括76个咪唑,57个吡咯,10吡嗪类药物,9吡啶,和3个咪唑吡咯,另外解释9-69%的光吸收,这些发色团主要涉及四个形成途径,包括以前未认识到的氨或甲胺与甲基乙二醛二聚体形成吡咯的反应。这些反应中的pH值对BrC发色团的形成和转化也显示出显着的影响;例如,随着pH从5.0增加到7.0,咪唑在鉴定的发色团中的光吸收贡献从72%降低到65%,吡嗪对甲基乙二醛+铵反应的光吸收贡献从5%增加到13%;同时,更多的小氮杂环转化为低聚物(例如,C9和C12吡咯)通过与甲基乙二醛反应。这些新发现的发色团和提出的形成途径对未来水相BrC的形成和转化的现场研究具有指导意义。
    Aqueous-phase reactions of α-dicarbonyls with ammonium or amines have been identified as important sources of secondary brown carbon (BrC). However, the identities of most chromophores in these reactions and the effects of pH remain largely unknown. In this study, the chemical structures, formation pathways, and optical properties of individual BrC chromophores formed through aqueous reactions of α-dicarbonyls (glyoxal and methylglyoxal) with ammonium, amino acids, or methylamine at different pH\'s were characterized in detail by liquid chromatography-photodiode array-high resolution tandem mass spectrometry. In total, 180 chromophores are identified, accounting for 29-79% of the light absorption of bulk BrC for different reactions. Thereinto, 155 newly identified chromophores, including 76 imidazoles, 57 pyrroles, 10 pyrazines, 9 pyridines, and 3 imidazole-pyrroles, explain additionally 9-69% of the light absorption, and these chromophores mainly involve four formation pathways, including previously unrecognized reactions of ammonia or methylamine with the methylglyoxal dimer for the formation of pyrroles. The pH in these reactions also shows remarkable effects on the formation and transformation of BrC chromophores; e.g., with the increase of pH from 5.0 to 7.0, the light absorption contributions of imidazoles in identified chromophores decrease from 72% to 65%, while the light absorption contributions of pyrazines increase from 5% to 13% for the methylglyoxal + ammonium reaction; meanwhile, more small nitrogen heterocycles transformed into oligomers (e.g., C9 and C12 pyrroles) via reaction with methylglyoxal. These newly identified chromophores and proposed formation pathways are instructive for future field studies of the formation and transformation of aqueous-phase BrC.
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  • 文章类型: Journal Article
    神经生物学家广泛使用绿色基因编码的钙指标(GECIs)来可视化神经元活动。其中,比率GECI允许对活性和非活性神经元群体进行成像。然而,他们不受欢迎,因为它们的性能不如增强GCaMP系列的GECIs。最具特色和发展的比率绿色GECI是FGCaMP7。然而,其大的股票位移绿色(LSS-Green)形式的动态范围和灵敏度明显低于其绿色形式,并且其分子设计不是最佳的。为了解决这些缺点,我们设计了一种比例绿色钙指示剂,叫做FNCaMP,它基于来自A.Niger的明亮mNeonGreen蛋白和钙调蛋白,具有最佳的NTnC样设计。我们比较了FNCaMP和FGCaMP7指标的体外性质,在哺乳动物细胞中,在神经元培养中。最后,我们获得并分析了FNCaMP指示剂的X射线结构。
    Neurobiologists widely use green genetically encoded calcium indicators (GECIs) for visualization of neuronal activity. Among them, ratiometric GECIs allow imaging of both active and non-active neuronal populations. However, they are not popular, since their properties are inferior to intensiometric GCaMP series of GECIs. The most characterized and developed ratiometric green GECI is FGCaMP7. However, the dynamic range and sensitivity of its large Stock\'s shift green (LSS-Green) form is significantly lower than its Green form and its molecular design is not optimal. To address these drawbacks, we engineered a ratiometric green calcium indicator, called FNCaMP, which is based on bright mNeonGreen protein and calmodulin from A. niger and has optimal NTnC-like design. We compared the properties of the FNCaMP and FGCaMP7 indicators in vitro, in mammalian cells, and in neuronal cultures. Finally, we obtained and analyzed X-ray structure of the FNCaMP indicator.
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  • 文章类型: Journal Article
    目的:与无机EO材料相比,有机电光(EO)材料具有优势,因此最近受到了广泛关注。在不同种类的有机EO材料中,有机EO分子玻璃由于其高的发色团负载密度和大的宏观EO活性而具有理想的前景。
    背景:本研究的目的是设计和合成一种新型的有机EO分子玻璃JMG,该玻璃利用Julolidine部分作为电子给体,噻吩部分作为共轭桥,三氟甲基取代的三氰基呋喃衍生物(Ph-CF3-TCF)作为电子受体。
    方法:通过NMR和HRMS表征JMG的结构。光物理性质,玻璃化转变温度,通过紫外可见光谱确定JMG的第一超极化率(β)和偶极矩(μ),DSC测试和DFT计算。
    结果:JMG\的Tg达到79°C,可以形成高质量的光学膜。理论计算表明,JMG的第一超极化率(β)和偶极矩(μ)被计算为730×10-30esu和21.898D。在90℃下以49V/μm的极化电压连接极化10分钟后,极化JMG薄膜的最高EO系数(r33)达到147pm/V。
    结论:成功制备并表征了具有两个叔丁基二苯基甲硅烷基(TBDPS)基团的新型基于菊酯的NLO发色团。引入TBDPS基团作为成膜基团,它也起着隔离小组的作用,可以抑制发色团之间的静电相互作用,提高了极化效率,进一步提高了EO活性。优异的性能赋予JMG在器件制造中的潜在应用。
    OBJECTIVE: Organic electro-optic (EO) materials have recently gained considerable attention owing to their advantages compared to inorganic EO materials. Among different kinds of organic EO materials, organic EO molecular glass exhibits desired prospect because of its high chromophore loading density and large macroscopic EO activity.
    BACKGROUND: The objective of this study is to design and synthesize a novel organic EO molecular glass JMG utilizing julolidine moiety as the electron donor, thiophene moiety as the conjugated bridge, trifluoromethyl substituted tricyanofuran derivate (Ph-CF3-TCF) as the electron acceptor.
    METHODS: The JMG\'s structure was characterized through NMR and HRMS. The photophysical property, glass transition temperature, first hyperpolarizability (β) and dipole moment (μ) of JMG were determined through UV-vis spectra, DSC test and DFT calculation.
    RESULTS: JMG\'s Tg reached to 79 °C and it can form high-quality optical film. The theoretical calculation shows that the first hyperpolarizability (β) and dipole moment (μ) of JMG were calculated to 730×10-30 esu and 21.898 D. After connecting poling with the poling voltage of 49 V/μm at 90 ℃for 10 min, the highest EO coefficient (r33) of the poled JMG films reached to 147 pm/V.
    CONCLUSIONS: A novel julolidine-based NLO chromophore with two tert-butyldiphenylsilyl (TBDPS) groups was successfully prepared and characterized. TBDPS group is introduced as the film-forming group, and it also plays the role of isolation group, which can suppress the electrostatic interaction between chromophores, improve the poling efficiency and further enhance the EO activity. The excellent performances endow JMG with potential applications in device fabrication.
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  • 文章类型: Journal Article
    一系列新颖的发色团A,B,C,D,基于Julolidinyl供体和三氰呋喃(TCF)和CF3-三氰呋喃(CF3-Ph-TCF)受体,已经进行了综合和系统研究。3,5-双(三氟甲基)苯衍生物分离基团被引入到发色团C和D的桥中。这些非线性光学发色团显示出良好的热稳定性,它们的分解温度都在220℃以上。使用密度泛函理论(DFT)计算能隙和一阶超极化率(β)。使用简单的反射方法测量宏观电光(EO)活性。含有35重量%掺杂在无定形聚碳酸酯中的发色团D的极化膜的最高EO系数在1310nm下提供54μm/V的值。结果表明,3,5-双(三氟甲基)苯分离基团可以抑制发色团的偶极-偶极相互作用。适度的r33值,良好的热稳定性,发色团的良好产量表明它们在非线性光学领域的潜在用途。
    A series of novel chromophores A, B, C, and D, based on the julolidinyl donor and the tricyanofuran (TCF) and CF3-tricyanofuran (CF3-Ph-TCF) acceptors, have been synthesized and systematically investigated. The 3,5-bis(trifluoromethyl)benzene derivative isolation group was introduced into the bridge in the chromophores C and D. These nonlinear optical chromophores showed good thermal stability, and their decomposition temperatures were all above 220 °C. Density functional theory (DFT) was used to calculate the energy gaps and first-order hyperpolarizability (β). The macroscopic electro-optic (EO) activity was measured using a simple reflection method. The highest EO coefficient of poled films containing 35 wt% of chromophore D doped in amorphous polycarbonate afforded values of 54 pm/V at 1310 nm. The results indicate that the 3,5-bis(trifluoromethyl)benzene isolation group can suppress the dipole-dipole interaction of chromophores. The moderate r33 value, good thermal stability, and good yield of chromophores suggest their potential use in the nonlinear optical area.
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  • 文章类型: Journal Article
    褐碳(BrC)因其对气候的显著影响而受到越来越多的关注。然而,对其化学成分和来源的有限知识限制了气候模型估计的气溶胶辐射强迫的精度。在这项研究中,研究了青岛夏季和冬季大气颗粒物中PM2.5的化学成分和水溶性BrC(WS-BrC)的光学性质,中国。总的来说,虽然有轻微的昼夜变化,季节性差异较为明显。由于排放源和气象条件的影响,含碳气溶胶的污染较重发生在冬季。相比之下,WS-BrC在365nm处的吸收AAE和质量吸收效率(MAE365)表明,冬季WS-BrC具有更强的波长依赖性和光吸收能力,这可能与生物质燃烧源的贡献有关。365nm处的光吸收系数(Abs365)与非海盐K之间的强相关性进一步证实了这一点,生物质燃烧排放的指标。采用激发-发射矩阵荧光光谱法结合平行因子分析法对水溶性有机碳(WSOC)中4种不饱和度较高的荧光组分(C1~C4)进行了鉴定,这表明青岛的WSOC主要与腐殖质样发色团有关。值得注意的是,C1与模拟海洋气溶胶的水溶性发色团相似,这证明了海洋排放对沿海地区大气颗粒物确实有一定的影响。此外,来源分析结果表明,WS-BRC起源于不同季节的不同陆源。目前的结果可能有助于提高对沿海城市WS-BrC光学特性的认识,优化全球气候模式,制定空气管理政策。
    Brown carbon (BrC) has been attracting more and more attention owing to its significant effects on climate. However, the limited knowledge on its chemical composition and sources limits the precision of aerosol radiative forcing estimated by climate models. In this study, the chemical components of PM2.5 and optical properties of water-soluble BrC (WS-BrC) were investigated from atmospheric particles collected in summer and winter in Qingdao, China. On the whole, though there were slight diurnal variations, seasonal differences were more obvious. Due to the influence of emission sources and meteorological conditions, the heavier pollution of carbonaceous aerosols occurred in winter. By comparison, the absorption Ångström exponent (AAE) and mass absorption efficiency of WS-BrC at 365 nm (MAE365) showed that WS-BrC in winter had stronger wavelength dependence and light absorption capacity, which might be associated with biomass burning source contributions. This was further confirmed by a strong correlation between the light absorption coefficient at 365 nm (Abs365) and non-sea salt K+, an indicator for biomass burning emissions. Four fluorescent components (C1∼C4) with high unsaturation in water-soluble organic carbon (WSOC) were identified by excitation-emission matrix fluorescence spectroscopy combined with parallel factor analysis method, which showed that WSOC in Qingdao was mainly related to humic-like chromophores. It is worth noting that C1 was similar to the water-soluble chromophore of simulated marine aerosols, which proved that marine emissions do have a certain impact on atmospheric particulate matter in coastal areas. In addition, the results of source analysis showed that WS-BrC originated from different terrestrial sources in different seasons. The current results may help to improve the knowledge of optical properties of WS-BrC in coastal cities, optimize the global climate model and formulate air management policies.
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  • 文章类型: Journal Article
    在大自然中,许多能够变形伪装的神秘生物,颜色伪装,和自我修复激发了科学家开发各种仿生软机器人。然而,将所有上述功能系统集成到单个软致动器系统中仍然是一个挑战。在这里,我们通过简单的硫醇-烯光加成方法将多刺激响应的四芳基丁二腈(TASN)发色团化学引入液晶弹性体(LCE)网络。所获得的TASN-LCE软致动器不仅表现出响应于热和机械压缩的可逆形状变形和可逆颜色变化行为,而且还表现出优秀的自我修复能力,重新编程和回收特性。我们希望这样的TASN-LCE执行器系统具有动态失真,热-和机械-变色伪装,和自我修复功能将为进一步开发多功能仿生软机器人设备铺平道路。
    In nature, many mysterious creatures capable of deformation camouflage, color camouflage, and self-healing have inspired scientists to develop various biomimetic soft robots. However, the systematic integration of all the above functionalities into a single soft actuator system still remains a challenge. Here we chemically introduce a multi-stimuli-responsive tetraarylsuccinonitrile (TASN) chromophore into a liquid crystal elastomer (LCE) network through a facile thiol-ene photoaddition method. The obtained TASN-LCE soft actuators not only exhibit reversible shape-morphing and reversible color-changing behavior in response to heat and mechanical compression, but also show excellent self-healing, reprogramming and recycling characteristics. We hope that such a TASN-LCE actuator system endowed with dynamic distortion, thermo- and mechano-chromic camouflage, and self-healing functionalities would pave the way for further development of multifunctional biomimetic soft robotic devices.
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  • DOI:
    文章类型: Journal Article
    酒渣鼻是一种难以控制的慢性炎症性皮肤病,据报道对患者有负面的社会心理影响。寻求新的方法来针对病症的许多体征和症状,同时还改善患者的生活质量。
    我们评估了Kleresca®生物光子平台的功效(KLOXTechnologiesInc.,拉瓦尔,加拿大),产生荧光能量(FLE),诱导一种新形式的光生物调节来治疗酒渣鼻。我们还评估了患者对其面部外观的满意度以及对治疗前后对他人的看法的担忧。
    9名患者每周接受一次FLE治疗,共4周。患者和治疗临床医生在整个治疗过程中和治疗后完成问卷调查,以对酒渣鼻的体征和症状进行分级,并捕获患者对治疗及其病情的看法。
    FLE可显着减少面部的炎性红斑反应,改善与酒渣鼻相关的潮红和红斑,并对患者的自我认知和情绪健康产生积极影响。
    我们的结果支持FLE作为一种有效的,酒渣鼻的无创治疗方式。
    UNASSIGNED: Rosacea is a difficult-to-manage chronic inflammatory skin condition reported to have a negative psychosocial impact on patients. Novel approaches are sought to target the many signs and symptoms of the condition while also improving the quality of life of patients.
    UNASSIGNED: We assessed the efficacy of the Kleresca® biophotonic platform (KLOX Technologies Inc., Laval, Canada), which creates fluorescent light energy (FLE), to induce a novel form of photobiomodulation for treating rosacea. We also assessed patient satisfaction with their facial appearance and concerns about perceptions of others before and after treatment.
    UNASSIGNED: Nine patients were treated once a week for four weeks with FLE. Patients and the treating clinician completed questionnaires throughout and after the treatment to grade the rosacea signs and symptoms and capture patients\' perceptions of the treatment and their condition.
    UNASSIGNED: FLE significantly reduced the inflammatory erythematous reaction of the face, improved flushing and erythema associated with rosacea, and had a positive impact on patients\' self-perception and emotional wellbeing.
    UNASSIGNED: Our results support FLE as an effective, noninvasive treatment modality for rosacea.
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  • 文章类型: Journal Article
    在视网膜色素上皮(RPE)中高表达,RPE特异性65-kDa(RPE65)酶对于产生11-顺式视网膜(11cRAL)是必不可少的,视紫红质和视锥光色素的发色团。RPE65缺乏可导致Leber先天性黑蒙2型(LCA2),其中光漂白的全反式视网膜异构化为光敏11cRAL被阻断,最终导致严重的视网膜功能障碍和变性。相关的老鼠模型,它们是通过基因敲除或由自发突变引起的,形态学上存在早发性和快速视网膜视锥细胞变性,包括短波长敏感的视锥蛋白(S-视蛋白)的丢失和中波长敏感的视锥蛋白(M-视蛋白)的错位。研究表明,常规Rpe65基因替代疗法,由腺相关病毒(AAV)载体介导,可以恢复RPE65蛋白。然而,AAV转染和Rpe65转基因表达至少需要一到两周,并且该治疗不能完全阻断早发性视锥细胞变性。确定基因治疗前延迟视锥细胞变性的可行性,我们研究了11cRAL治疗对早期LCA2视网膜变性12(rd12)小鼠模型的影响.类似于人类患者,小鼠模型携带Rpe65基因的自发突变,导致内源性11cRAL再生中断。我们发现RPE65缺乏对啮齿动物视网膜血管没有明显影响。在红光照射下,从出生后(P)14天至P21天对rd12小鼠腹腔注射外源性11cRAL。最后一次注射三天后,使用暗视和明视视网膜电图观察到视网膜功能的显着恢复。使用光学相干断层扫描和对缺陷视网膜的组织学分析,我们发现了感光体外段(OS)厚度的变化;这种变化可以通过早期11cRAL治疗来挽救。此外,治疗特别保留了M-和S-视蛋白,两者都在视锥细胞内保持适当的定位,如野生型小鼠所示。相比之下,年龄匹配的未经治疗的rd12小鼠的特征是视网膜S-视蛋白丢失和M-视蛋白从感光细胞OS到内节的错误定位,外核层,或外丛状层。值得注意的是,11cRAL治疗不能长时间维持视网膜功能。最后一次注射后十天,视杆和M锥视网膜电图显著下降,S锥反应几乎熄灭。我们的研究结果表明,早期11cRAL治疗对于恢复rd12小鼠模型的视网膜功能和挽救形态学是有用的,早发性和快速的视锥变性可以在基因治疗之前延迟。
    Highly expressed in the retinal pigment epithelium (RPE), the RPE-specific 65-kDa (RPE65) enzyme is indispensable to generate 11-cis-retinal (11cRAL), a chromophore for rhodopsin and cone photopigments. RPE65 deficiency can lead to Leber congenital amaurosis type 2 (LCA2), in which the isomerization of photobleached all-trans-retinal into photosensitive 11cRAL is blocked, ultimately causing severe retinal dysfunction and degeneration. The related mouse models, which are constructed through gene knockout or caused by spontaneous mutations, morphologically present with early-onset and rapid retinal cone cells degeneration, including loss of short-wavelength-sensitive cone opsins (S-opsins) and mislocalization of medium-wavelength-sensitive cone opsins (M-opsins). Studies have shown that routine Rpe65 gene replacement therapy, mediated by an adeno-associated virus (AAV) vector, can restore RPE65 protein. However, AAV transfection and Rpe65 transgene expression require at least one to two weeks, and the treatment cannot fully block the early-onset cone degeneration. To determine the feasibility of delaying cone degeneration before gene therapy, we investigated the impact of 11cRAL treatment in an early-age LCA2 retinal degeneration 12 (rd12) mouse model. Similar to human patients, the mouse model carries a spontaneous mutation in the Rpe65 gene, which results in disrupted endogenous 11cRAL regeneration. We found that RPE65 deficiency did not notably affect rodent retinal vessels. Under red light illumination, the rd12 mice were intraperitoneally injected with exogenous 11cRAL from postnatal day (P) 14 to P21. Three days after the last injection, a notable recovery of retinal function was observed using scotopic and photopic electroretinograms. Using optical coherence tomography and histological analyses of the deficient retinas, we found changes in the thickness of the photoreceptor outer segment (OS); this change could be rescued by early 11cRAL treatment. In addition, the treatment notably preserved M- and S-opsins, both of which maintained appropriate localization inside cone cells, as shown by the wild-type mice. In contrast, the age-matched untreated rd12 mice were characterized by retinal S-opsin loss and M-opsin mislocalization from the photoreceptor OS to the inner segment, outer nuclear layer, or outer plexiform layer. Notably, 11cRAL treatment could not maintain retinal function for a long time. Ten days after the last injection, the rod and M-cone electroretinograms significantly decreased, and S-cone responses almost extinguished. Our findings suggest that early 11cRAL treatment is useful for restoring retinal function and rescuing morphology in the rd12 mouse model, and the early-onset and rapid cone degeneration can be delayed before gene therapy.
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  • 文章类型: Journal Article
    Mitochondria are essential organelles because of their function in energy conservation. Here, we show an involvement of mitochondria in phytochrome-dependent light sensing in fungi. Phytochrome photoreceptors are found in plants, bacteria, and fungi and contain a linear, heme-derived tetrapyrrole as chromophore. Linearization of heme requires heme oxygenases (HOs) which reside inside chloroplasts in planta. Despite the poor degree of conservation of HOs, we identified two candidates in the fungus Alternaria alternata. Deletion of either one phenocopied phytochrome deletion. The two enzymes had a cooperative effect and physically interacted with phytochrome, suggesting metabolon formation. The metabolon was attached to the surface of mitochondria with a C-terminal anchor (CTA) sequence in HoxA. The CTA was necessary and sufficient for mitochondrial targeting. The affinity of phytochrome apoprotein to HoxA was 57,000-fold higher than the affinity of the holoprotein, suggesting a \"kiss-and-go\" mechanism for chromophore loading and a function of mitochondria as assembly platforms for functional phytochrome. Hence, two alternative approaches for chromophore biosynthesis and insertion into phytochrome evolved in plants and fungi.
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