皮肤的光学性质研究

为了确认通过皮肤进行基于卟啉荧光的元创恶性肿瘤诊断的可行性,应用光谱法分析研究了人皮肤的光学特性。通过测量皮肤的反射光谱、透射光谱和荧光光谱分析确定皮肤中的发光物质及其光谱对卟啉荧光的影响。用280nm激发光对皮肤进行激发,测到皮肤在360nm发出的荧光。与牛血清白蛋白的荧光光谱比较,确定发光物质是某类蛋白质。选择350nm激发光对皮肤进行激发,测得了与离体类胡萝卜素荧光452nm相同的荧光,所以皮肤中的发光物质有类胡萝卜素。光谱分析还表明,皮肤的荧光中还有弹性蛋白和还原型烟酰胺腺嘌呤二核苷酸(NADH)的荧光发射,荧光峰分别在400,460nm。黑色素不发荧光,但皮肤中可能还存在氧化的黑色素,它的荧光波长是580nm,这些都与卟啉的荧光波长不同。由此可见皮肤中发光物质不会影响卟啉荧光的探测。由皮肤的透射光谱观察到,卟啉的荧光波长恰好在皮肤的透射窗口内,从而进一步确定了卟啉荧光的无创探测的可能性。     

基于双靶向黑色素纳米粒的肿瘤深穿透光声成像

通过1-(3-二甲基氨基丙基)-3-乙基碳二亚胺和N-羟基丁二酰亚胺反应将透明质酸(hyaluronic acid,HA)和4-羧丁基三苯基溴化膦((4-carboxybutyl) triphenylphosphonium bromide,TPP)分子连接到聚乙二醇-氨基(PEG-NH₂)修饰过的黑色素纳米颗粒(melanin nanoparticles,MNP)表面,设计合成了一种具有双靶向能力的黑色素纳米颗粒(MNP-TPP-HA),赋予了黑色素的双靶向能力。体外三维(3D)多细胞肿瘤球荧光成像和活体肿瘤光声成像实验表明MNP-TPP-HA具有优异的肿瘤靶向穿透能力。     

工程菌产黑色素的抗氧化作用研究

利用黑色素对苯甲酸羟基化产物荧光强度的猝灭作用，研究了重组的苏云金芽孢杆菌(Bacillus thuringiensis)pHTAM菌株产生的黑色素对羟自由基的清除作用，发现其具有与Sigma标准黑色素相当的清除羟基自由基的能力，且优于生物提取的国产商品黑色素；与硫脲等其它常见的抗氧化剂比较，该工程菌产黑色素清除羟自由基的效果明显，尤其是在低剂量时这种优势更为突出。通过动力学研究证实其对羟自由基的清除作用是基于氧化还原反应而非吸附作用。     

Insights on the Inhibitory Power of Flavonoids on Tyrosinase Activity: A Survey from 2016 to 2021

Tyrosinase is a multifunctional copper-containing oxidase enzyme that initiates melanin synthesis in humans. Excessive accumulation of melanin pigments or the overexpression of tyrosinase may result in skin-related disorders such as aging spots, wrinkles, melasma, freckles, lentigo, ephelides, nevus, browning and melanoma. Nature expresses itself through the plants as a source of phytochemicals with diverse biological properties. Among these bioactive compounds, flavonoids represent a huge natural class with different categories such as flavones, flavonols, isoflavones, flavan-3-ols, flavanones and chalcones that display antioxidant and tyrosinase inhibitor activities with a diversity of mechanistic approaches. In this review, we explore the role of novel or known flavonoids isolated from different plant species and their participation as tyrosinase inhibitors reported in the last five years from 2016 to 2021. We also discuss the mechanistic approaches through the different studies carried out on these compounds, including in vitro, in vivo and in silico computational research. Information was obtained from Google Scholar, PubMed, and Science Direct. We hope that the updated comprehensive data presented in this review will help researchers to develop new safe, efficacious, and effective drug or skin care products for the prevention of and/or protection against skin-aging disorders.     

Study of melanin localization in the mature male Calopteryx haemorrhoidalis damselfly wings

Damselflies Calopteryx haemorrhoidalis exhibiting black wings are found in the western Mediterranean, Algeria, France, Italy, Spain and Monaco. Wing pigmentation is caused by the presence of melanin, which is involved in physiological processes including defence reactions, wound healing and sclerotization of the insect. Despite the important physiological roles of melanin, the presence and colour variation among males and females of the C. haemorrhoidalis species and the localization of the pigment within the wing membrane remain poorly understood. In this study, infrared (IR) microspectroscopy, coupled with the highly collimated synchrotron IR beam, was employed in order to identify the distribution of the pigments in the wings at a high spatial resolution. It was found that the melanin is localized in the procuticle of the C. haemorrhoidalis damselfly wings, distributed homogeneously within this layer, and not associated with the lipids of the epicuticle.     

IR Fourier Spectroscopy in Vivo of Human Skin during Its Ablation on Exposure to YAG:Er Laser Radiation and Polarization of the Light Scattered by the Integument

We consider the possibility of monitoring the process of human skin ablation on exposure to pulsed IR laser radiation with the use of the polarization and IR Fourier spectroscopy of disturbed total internal reflection. The laws of the change in the content of water and proteins in the surface layers of skin as a result of cyclic laser effect have been discovered. The interrelation between the degree of polarization of the backward scattered probe radiation with the wavelength corresponding to the maxima of absorption of an oxygenated form of hemoglobin and the index of erythema occurring due to laser action has been established.     

Probing the Motional Behavior of Eumelanin and Pheomelanin with Solid‐State NMR Spectroscopy: New Insights into the Pigment Properties

Melanin is the most widespread pigment in the animal kingdom. Despite its importance, its detailed structure and overall molecular architecture remain elusive. Both eumelanin (black) and pheomelanin (red) occur in the human body. These two melanin compounds show very different responses to UV‐radiation exposure, which could relate to their microscopic features. Herein, the structural properties and motional behavior of natural eu‐ and pheomelanin extracted from black and red human hair are investigated by means of solid‐state NMR spectroscopy. Several 1D and 2D NMR spectroscopic techniques were combined to highlight the differences between the two forms of the pigment. The quantitative analysis of the ¹H NMR wide‐line spectra extracted from 2D ¹H–¹³C LG‐WISE experiments revealed the presence of two dynamically distinguishable components in both forms. Remarkably, the more mobile fraction of the pigment showed a higher mobility with respect to the proteinaceous components that coexist in the melanosome, which is particularly evident for the red pigment. An explanation of the observed effects takes into account the different architecture of the proteinaceous matrix that constitutes the physical substrate onto which melanin polymerizes within the eu‐ and pheomelanosomes. Further insight into the molecular structure of the more mobile fraction of pheomelanin was also obtained by means of the analysis of 2D ¹H–¹³C INEPT experiments. Our view is that not only structural features inherent in the pure pigment, but also the role of the matrix structure in defining the overall melanin supramolecular arrangement and the resulting dynamic behavior of the two melanin compounds should be taken into account to explain their functions. The reported results could pave a new way toward the explanation of the molecular origin of the differences in the photoprotection activity displayed by black and red melanin pigments.     

Absorption spectra and light penetration depth of normal and pathologically altered human skin

A three-layered skin model (stratum corneum, epidermis, and dermis) and engineering formulas for radiative transfer theory are used to study absorption spectra and light penetration depths of normal and pathologically altered skin. The formulas include small-angle and asymptotic approximations and a layer-addition method. These characteristics are calculated for wavelengths used for low-intensity laser therapy. We examined several pathologies such as vitiligo, edema, erythematosus lupus, and subcutaneous wound, for which the bulk concentrations of melanin and blood vessels or tissue structure (for subcutaneous wound) change compared with normal skin. The penetration depth spectrum is very similar to the inverted blood absorption spectrum. In other words, the depth is minimal at blood absorption maxima. The calculated absorption spectra enable the power and irradiation wavelength providing the required light effect to be selected. Relationships between the penetration depth and the diffuse reflectance coefficient of skin (unambiguously expressed through the absorption coefficient) are analyzed at different wavelengths. This makes it possible to find relationships between the light fields inside and outside the tissue. __________ Translated from Zhurnal Prikladnoi Spektroskopii Vol. 74, No. 3, pp. 387–394, May–June, 2007.     

Colorimetric metal ion binding of catechol-based coatings inspired by melanin and molecular imprinting

Catechol-containing biomolecules and related synthetic materials are of interest for a broad range of applications. Our group has been interested in the potential of eumelanin, a catechol-containing biomaterial and the black-to-brown pigment in humans, and synthetic eumelanin analogues for water purification applications. In an attempt to apply the strategy of molecular imprinting towards lead-binding synthetic eumelanin coatings, we developed a PbO₂-mediated synthesis that was subsequently tested with a number of catechols in addition to the eumelanin and polydopamine monomers l-dopa and dopamine. Although this strategy did not provide significant improvements in affinity or selectivity, we found that the PbO₂-mediated oxidative polymerisation of 1,2-dihydroxybenzene generates a coating that darkens visibly upon binding Pb²⁺ and other metal ions. Oxidative polymerisation of catechol with sodium periodate also yields a coating with this colorimetric response. Of eight metal ions tested, the coatings are most responsive to Pb²⁺ and Cu²⁺, as analysed by quantitative colorimetry. With further optimisation, these coatings could prove useful for the colorimetric sensing of metal ions.     

绿色安全染发剂的研究进展及展望

染发已成为人们的日常需要与时尚选择。目前广泛使用的化学染发剂主要成分为对苯二胺类物质,其引起的致敏性、致癌性与致突变性等问题日益凸显。生物质染发剂及仿生染发剂与化学合成染发剂相比具有安全低毒、资源可再生、环境友好等优点。本文以近年来国内外对绿色安全染发剂的研究为基础,从头发的组成结构和显色机理出发,从生物质染发剂以及仿生染发剂两个方面总结了绿色安全染发剂的研究现状与发展瓶颈,并对其应用前景进行了展望,旨在为安全无毒、绿色健康染发剂的研发提供参考。