confocal Raman spectroscopy

共聚焦拉曼光谱
  • 文章类型: Journal Article
    皮肤是最大的器官,是人体与其环境之间的多功能界面。它是抵御寒冷的屏障,热,受伤,感染,化学品,辐射或其他外来因素,它也被称为灵魂的镜子。皮肤通过储存脂肪和水参与体温调节。关于活性成分的局部和经皮应用以预防或治疗病理状况,它是令人感兴趣的组织。局部和经皮递送是药物和化妆品施用的新兴途径。它有利于避免副作用和快速代谢。许多制药,技术和化妆品创新最近在该领域被描述和专利。在这次审查中,介绍了皮肤形态和生理学的主要特征,并随后描述了经典和新颖的纳米颗粒真皮和透皮药物制剂。药物和化妆品渗透进入或穿过皮肤屏障的生物物理方面及其在扩散室中的研究,皮肤芯片设备,还显示了高通量测量系统或先进的分析技术。最后简要讨论了当前有关皮肤渗透数学建模的知识和未来的观点,都涉及纳米关节系统。
    Skin is the largest organ and a multifunctional interface between the body and its environment. It acts as a barrier against cold, heat, injuries, infections, chemicals, radiations or other exogeneous factors, and it is also known as the mirror of the soul. The skin is involved in body temperature regulation by the storage of fat and water. It is an interesting tissue in regard to the local and transdermal application of active ingredients for prevention or treatment of pathological conditions. Topical and transdermal delivery is an emerging route of drug and cosmetic administration. It is beneficial for avoiding side effects and rapid metabolism. Many pharmaceutical, technological and cosmetic innovations have been described and patented recently in the field. In this review, the main features of skin morphology and physiology are presented and are being followed by the description of classical and novel nanoparticulate dermal and transdermal drug formulations. The biophysical aspects of the penetration of drugs and cosmetics into or across the dermal barrier and their investigation in diffusion chambers, skin-on-a-chip devices, high-throughput measuring systems or with advanced analytical techniques are also shown. The current knowledge about mathematical modeling of skin penetration and the future perspectives are briefly discussed in the end, all also involving nanoparticulated systems.
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  • 文章类型: Journal Article
    共聚焦拉曼光谱被认为是生物标本分子表征的有力工具。制药和化妆品领域对体外渗透测试(IVPT)的需求不断增长,越来越多地使用重建人类表皮(RHE)皮肤模型进行。在这项研究中,已检查了RHE在10%中性缓冲福尔马林中化学固定24小时,以将RHE样品在4°C下存储长达21天。共聚焦拉曼光谱(CRS)结合主成分分析,揭示了固定的分子水平效应,特别是在角质层和活表皮内的蛋白质和脂质构象中。通过高效液相色谱法进行IVPT,使用咖啡因作为模型化合物,显示福尔马林固定对累积量的影响最小,通量,和12小时后的渗透系数。虽然生化结构发生了变化,该模型作为维持活性分子在皮肤层中的限速扩散的屏障的功能保持完整。这项研究为增强皮肤模型研究的灵活性和实用性开辟了道路,有希望的见解,通过在固定样品中保持性能长达21天,来减轻RHE模型的有限保质期。
    Confocal Raman Spectroscopy is recognised as a potent tool for molecular characterisation of biological specimens. There is a growing demand for In Vitro Permeation Tests (IVPT) in the pharmaceutical and cosmetic areas, increasingly conducted using Reconstructed Human Epidermis (RHE) skin models. In this study, chemical fixation of RHE in 10 % Neutral Buffered Formalin for 24 h has been examined for storing RHE samples at 4 °C for up to 21 days. Confocal Raman Spectroscopy (CRS), combined with Principal Components Analysis, revealed the molecular-level effects of fixation, notably in protein and lipid conformation within the stratum corneum and viable epidermis. IVPT by means of high-performance liquid chromatography, using caffeine as a model compound, showed minimal impact of formalin fixation on the cumulative amount, flux, and permeability coefficient after 12 h. While the biochemical architecture is altered, the function of the model as a barrier to maintain rate-limiting diffusion of active molecules within skin layers remains intact. This study opens avenues for enhanced flexibility and utility in skin model research, promising insights into mitigating the limited shelf life of RHE models by preserving performance in fixed samples for up to 21 days.
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  • 文章类型: Journal Article
    采用了一种简便的固态方法来合成NdMgAl11O19的新型磁铅石型氧化物,该氧化物将尖晶石堆叠层(MgAl2O4)与Nd-O6镜面结构集成在一起。所得NdMgAl11O19在锂-硫电池中的硫还原反应(SRR)期间表现出显著的催化活性和转化效率。通过采用原位共焦拉曼光谱和电化学技术的二维投影映射技术,发现Nd-O6的暴露镜面结构可以有效地抑制长链锂多硫化物在硫还原的初始阶段的不期望的歧化反应(S82-→S62-1/4S8),从而促进硫到硫化锂的正过程。这不仅减轻了硫穿梭损失的问题,而且显著改善了转化过程的动力学。利用这些优势,NdMgAl11O19/S阴极的初始容量高达1398mAhg-1,电解质/硫(E/S)比为5.1µLmg-1,硫负载为2.3mgcm-2。即使当硫负载增加到10.02mgcm-2时,阴极在200次循环后仍保持10.01mAhcm-2的可逆面积容量。这种镜像工程策略为提高Li-S电池中阴极的效率提供了有价值和普遍的见解。
    A facile solid-state approach is employed to synthesize a novel magnetoplumbite-type oxide of NdMgAl11O19, which integrates spinel-stacking layers (MgAl2O4) with Nd-O6 mirror plane structures. The resulting NdMgAl11O19 exhibits remarkable catalytic activity and conversion efficiency during the sulfur reduction reaction (SRR) in lithium-sulfur batteries. By employing the 2D projection mapping technique of in situ confocal Raman spectroscopy and electrochemical technique, it is discovered that the exposed mirror plane structure of Nd-O6 can effectively suppress the undesiring disproportionation reaction (S8 2-→S6 2-+1/4 S8) of long-chain lithium polysulfides at the initial stages of sulfur reduction, thereby promoting the positive process of sulfur to lithium sulfide. This not only mitigates the issue of sulfur shuttle loss but also significantly improve the kinetics of the conversion process. Leveraging these advantages, the NdMgAl11O19/S cathode delivered an impressive initial capacity of up to 1398 mAh g-1 at an electrolyte/sulfur (E/S) ratio of 5.1 µL mg-1 and a sulfur loading of 2.3 mg cm-2. Even when the sulfur loading is increased to 10.02 mg cm-2, the cathode retained a reversible areal capacity of 10.01 mAh cm-2 after 200 cycles. This mirror engineering strategy provides valuable and universal insights into enhancing the efficiency of cathodes in Li-S battery.
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  • 文章类型: Journal Article
    由于其独特的物理化学性质,大面积二维(2D)材料在下一代半导体的开发中具有巨大的潜力。共聚焦拉曼光谱(CRM),一种典型的二维材料表征方法,由于系统的聚焦深度受限和衬底的不太理想的水平,具有有限的有效测量区域。我们提出了快速自适应聚焦共聚焦拉曼显微镜(FAFCRM),以实现对大面积2D材料的实时聚焦检测。通过观察电荷耦合器件(CCD)上由于在CCD前面放置一个孔径而引起的光斑变化,该方法在不进行轴向扫描的情况下,每60μm的聚焦分辨率高达100nm。通过所有扫描在聚焦上在25.6mmX25.6mm区域上测量石墨烯。研究结果为二维材料的英寸级无损表征提供了新的视角。
    Large-area two-dimensional (2D) materials possess significant potential in the development of next generation semiconductor due to their unique physicochemical properties. Confocal Raman spectroscopy (CRM), a typical 2D material characterization method, has a limited effective measurement area owing to the restricted focus depth of the system and the less-than-ideal level of the substrate. We propose fast adaptive focusing confocal Raman microscopy (FAFCRM) to realize real-time focusing detection for large-area 2D materials. By observing spot changes on the charge coupled device (CCD) caused by placing an aperture in front of the CCD, the methodology gives a focusing resolution up to 100 nm per 60 μm without axial scanning. A graphene was measured over 25.6 mm × 25.6 mm area on focus through all the scanning. The research results provide new perspectives for non-destructive characterization of 2D materials at the inch level.
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  • 文章类型: Journal Article
    MoS2是具有独特的电子和光学性质的二维层状过渡金属二硫属化物。超薄MoS2的制造至关重要,由于其超薄品种的层间相互作用将变得依赖于厚度,提供厚度控制的可调性和这些属性的不同应用。与许多研究报告了MoS2单层直接带隙发射的详细信息不同,关于厚度引起的间接带隙演化或转变的可靠实验证据仍然很少。这里,标称厚度为30nm的MoO3薄膜的硫化,进行5nm和3nm。所有硫化样品均在室温下用椭圆偏振光谱和光致发光光谱检查,以获得有关其介电函数和边缘发射光谱的信息。这项调查揭示了过渡之间的间接到间接的交叉,与MoS2导带的两个不同的Λ和K谷相关联,通过将其厚度减薄到几层。
    MoS2 is a two-dimensional layered transition metal dichalcogenide with unique electronic and optical properties. The fabrication of ultrathin MoS2 is vitally important, since interlayer interactions in its ultrathin varieties will become thickness-dependent, providing thickness-governed tunability and diverse applications of those properties. Unlike with a number of studies that have reported detailed information on direct bandgap emission from MoS2 monolayers, reliable experimental evidence for thickness-induced evolution or transformation of the indirect bandgap remains scarce. Here, the sulfurization of MoO3 thin films with nominal thicknesses of 30 nm, 5 nm and 3 nm was performed. All sulfurized samples were examined at room temperature with spectroscopic ellipsometry and photoluminescence spectroscopy to obtain information about their dielectric function and edge emission spectra. This investigation unveiled an indirect-to-indirect crossover between the transitions, associated with two different Λ and K valleys of the MoS2 conduction band, by thinning its thickness down to a few layers.
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  • 文章类型: Journal Article
    由于三元无定形固体分散体(ASD)的性能取决于固态特性和聚合物混合,需要全面了解聚合物之间的协同相互作用,以增强溶解性差的药物的溶解和随后的过饱和稳定。通过选择热熔挤出(HME)和真空压缩成型(VCM)作为制备技术,我们操纵了三元法韦仑(EFV)ASD的相位行为,包含羟丙基纤维素(HPC)-SSL或HPC-UL与Eudragit®L100-55(EL100-55)(50:50聚合物比)的组合,导致单相(HME)和异构ASD(VCM)。由于与EL100-55相比,EFV在HPC聚合物中的动力学固态溶解度更高,因此我们通过共聚焦拉曼显微镜观察到更高的药物分布到相分离的三元VCMASD的富含HPC的相中。此外,我们观察到相分离程度的差异取决于所选择的HPC等级。由于HPC-UL表现出明显低于HPC-SSL的熔体粘度,促进了HPC-UL和EL100-55之间部分混溶相的形成。因此,由于需要均匀混合的聚合物相来实现最佳程度的溶解度改善,使用HPC-UL时,溶解性能的制造依赖性差异较小,而不是HPC-SSL,即使用HPC-UL对该方法提供的剪切应力要求较低。
    As performance of ternary amorphous solid dispersions (ASDs) depends on the solid-state characteristics and polymer mixing, a comprehensive understanding of synergistic interactions between the polymers in regard of dissolution enhancement of poorly soluble drugs and subsequent supersaturation stabilization is necessary. By choosing hot-melt extrusion (HME) and vacuum compression molding (VCM) as preparation techniques, we manipulated the phase behavior of ternary efavirenz (EFV) ASDs, comprising of either hydroxypropyl cellulose (HPC)-SSL or HPC-UL in combination with Eudragit® L 100-55 (EL 100-55) (50:50 polymer ratio), leading to single-phased (HME) and heterogeneous ASDs (VCM). Due to higher kinetic solid-state solubility of EFV in HPC polymers compared to EL 100-55, we visualized higher drug distribution into HPC-rich phases of the phase-separated ternary VCM ASDs via confocal Raman microscopy. Additionally, we observed differences in the extent of phase-separation in dependence on the selected HPC grade. As HPC-UL exhibited decisive lower melt viscosity than HPC-SSL, formation of partially miscible phases between HPC-UL and EL 100-55 was facilitated. Consequently, as homogeneously mixed polymer phases were required for optimal extent of solubility improvement, the manufacturing-dependent differences in dissolution performances were smaller using HPC-UL, instead of HPC-SSL, i.e. using HPC-UL was less demanding on shear stress provided by the process.
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  • 文章类型: Journal Article
    尽管对二苯甲酮-3(BP3)的大量实验表明它可以渗透到皮肤中,体内渗透情况和尿代谢趋势尚未研究。在这项研究中,选择含有5.72%BP3的防晒霜用于人体皮肤暴露。共聚焦拉曼被成功地用于研究BP3在防晒剂中的体内皮肤渗透。在皮肤暴露2小时内,使用防晒霜15、30、60和120分钟后,半定量平均值分别为5.50、13.48、15.79和15.00μg/cm2,分别,表明BP3在60-120分钟内穿透角质层。在人类四肢暴露一次后,BP3迅速代谢并通过尿液排出,并在第6小时达到峰值浓度,而其代谢物2,4-二羟基二苯甲酮(BP1)在第9小时达到峰值浓度。同时,6%BP3和1%BP1在48h内通过尿液排泄,但2,2'-二羟基-4-甲氧基二苯甲酮(BP8)的浓度较低,尽管它在暴露后48小时内变化很大。在连续曝光期间,发现BP3浓度与暴露时间之间存在显着相关性(p<0.05),表明BP3浓度在更长的暴露时间增加。因此,拉曼光谱与人体样品分析相结合,为评估个人护理添加剂在人体内的吸收和代谢提供了新的途径。
    Although numerous experiments on benzophenone-3 (BP3) have shown that it can permeate into the skin, the in vivo penetration situation and urinary metabolic trend have not yet been investigated. In this study, sunscreen containing 5.72% BP3 was selected for human-skin exposure. Confocal Raman was successfully used to investigate in vivo skin penetration of BP3 in sunscreen. During 2 h of skin exposure, the semi-quantitative mean values were 5.50, 13.48, 15.79, and 15.00 μg/cm2 after application of sunscreen for 15, 30, 60, and 120 min, respectively, indicating that BP3 penetrated the stratum corneum during 60-120 min. After a single exposure of human limbs, BP3 was quickly metabolized and excreted through urine and reached its peak concentration in the 6th hour, whereas its metabolite 2,4-dihydroxybenzophenone (BP1) reached its peak concentration in the 9th hour. Meanwhile, 6% BP3 and 1% BP1 were excreted through the urine within 48 h, but the concentration of 2,2\'-dihydroxy-4-methoxybenzophenone (BP8) was low, although it varied greatly within 48 h after exposure. During consecutive exposures, a significant correlation (p < 0.05) between BP3 concentration and exposure time was found, indicating that BP3 concentration increased at longer exposure times. Therefore, combining Raman spectroscopy and human sample analysis provided a new way to assess absorption and metabolism of personal care additives in the human body.
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  • 文章类型: Journal Article
    蓝莓花青素(BA)是增强食品生物活性的功能性成分,BA的稳定性引起了人们的极大兴趣。使用共聚焦拉曼光谱原位分析了储存在聚丙烯和玻璃瓶中的水溶液中的BA稳定性,并且优化了可接受的聚焦深度。用多变量剖析解释了BA降解的拉曼特征。在65℃以上加热2h或紫外线照射(10W)96h时,BA的降解速率显著加快。一级动力学反应速率随pH值和温度的增加以及紫外线照射时间的延长而加快。多因素的协同作用促进了BA的降解。这项研究提供了一个原位,花色苷稳定性的无损分析方法,这在食品工业中非常有用,可以优化加工,storage,和运输措施,以减少BA的降解。
    Blueberry anthocyanin (BA) is a functional ingredient to enhance the biological activity of food, and the stability of BA is of great interest. BA stability in aqueous solutions stored in polypropylene and glass bottles was analyzed in-situ using confocal Raman spectroscopy, and the acceptable depth of focus was optimized. The Raman characteristics of BA degradation were explained by multivariate analysis. The degradation rate of BA was significantly accelerated by heating above 65 °C for 2 h or ultraviolet irradiation (10 W) for 96 h. The first order kinetic reaction rate was accelerated with the increase of pH value and temperature and the prolongation of ultraviolet irradiation time. The synergistic effect of multiple factors promoted BA degradation. This study provides an in-situ, nondestructive method for the analysis of anthocyanin stability, which has great utility in the food industry to optimize processing, storage, and transportation measures to reduce the degradation of BA.
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  • 文章类型: Journal Article
    已知Si在电池的电化学循环期间由于与Li插入和提取相关的大体积变化而开裂和分层。然而,已经通过实验发现,200nm厚和小于7μm宽的图案化Si岛电极可以以纯弹性方式变形。受此启发,我们使用电化学电池与浸没物镜耦合并设计用于短工作距离的模型多晶Si岛电极的原位拉曼应力表征。5μm宽的Si岛电极在锂化过程中显示出抛物线的应力分布,而对于15μmSi岛电极,观察到电极中心的应力平台。建立了具有耦合的电化学机械(ECM)物理的连续模型,以了解应力测量。在建模和实验数据之间达成了定性协议,临界尺寸效应可以通过Li浓度和静水压力梯度之间的竞争所控制的Li扩散通量来解释。低于临界尺寸,应力梯度将Li推向边缘,电极体积可以自由膨胀,在超过临界尺寸时,应力平台抑制Li扩散到边缘,并通过开裂迫使破坏性应力消除。这项工作代表了一种有前途的方法,用于原位表征电池电极中的ECM耦合,并提出了进一步改进的建议。
    Si is known for cracking and delamination during electrochemical cycling of a battery due to the large volume change associated with Li insertion and extraction. However, it has been found experimentally that patterned Si island electrodes that are 200 nm thick and less than 7 μm wide can deform in a purely elastic manner. Inspired by this, we performed in situ Raman stress characterization of model poly-crystalline Si island electrodes using an electrochemical cell coupled with an immersion objective lens and designed for a short working distance. A 5 μm wide Si island electrode showed a parabolic stress profile during lithiation, while for a 15 μm Si island electrode, a stress plateau in the center of the electrode was observed. A continuum model with coupled electro-chemo-mechanical (ECM) physics was established to understand the stress measurement. A qualitative agreement was reached between modeling and experimental data, and the critical size effect could be explained by the Li diffusive flux as governed by competition between the Li concentration and hydrostatic stress gradients. Below the critical size, the stress gradient drives Li toward the edges, where the electrode volume is free to expand, while above the critical size, the stress plateau inhibits Li diffusion to the edge and forces destructive stress relief by cracking. This work represents a promising methodology for in situ characterization of ECM coupling in battery electrodes, with suggestions provided for further improvement.
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  • 文章类型: Journal Article
    使用手持式非侵入性共聚焦拉曼系统(CRS)评估特应性皮炎(AD)和牛皮癣之间的皮肤生化差异,这是炎症性皮肤病。使用具有在671nm和785nm下操作的激发激光器的便携式内部CRS系统来获取指纹和高波数区域中的拉曼光谱测量。据推断,水的相对量在以下皮肤序列中减少:健康,牛皮癣和AD。此外,观察到神经酰胺亚类的差异趋势,使神经酰胺3在病灶AD和牛皮癣皮肤中低于健康,与健康皮肤相比,神经酰胺2显示出病灶性AD减少和病灶性银屑病增加的对比趋势。与病灶AD和健康皮肤相比,病灶性银屑病中的胆固醇含量明显更高。这些差异可以有助于皮肤状况的客观分类和新的疾病特异性局部治疗的制定。本文受版权保护。保留所有权利。
    A handheld non-invasive confocal Raman system (CRS) was used to evaluate the differences in skin biochemicals between atopic dermatitis (AD) and psoriasis, which are inflammatory skin conditions. Raman spectral measurements in the fingerprint and high wavenumber region were acquired using a portable in-house CRS system with excitation lasers operating at 671 and 785 nm. It was deduced that relative amount of water decreases in the following sequence of skin: healthy, psoriasis and AD. Moreover, differential trends were observed for the subclasses of ceramides such that ceramide 3 is lower in the lesional AD and psoriasis skin as compared to healthy, while ceramide 2 showed a contrasting trend of decrease in lesional AD and increase in lesional psoriasis as opposed to healthy skin. Amount of cholesterol was significantly higher in lesional psoriasis as compared to lesional AD and healthy skin. These differences can aid in an objective classification of the skin conditions and in the formulation of new disease-specific topical treatments.
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